The Monsanto Acetic Acid Process

Presented By

1. Ahmed Elsayed khabaza 1528016

2. Roaa Imam Abdelhady 1527102

3. Sara Salah El-dein Hussien 1527110

4. Sara Hossam El-dein Rabiaa 1528295

5. Aya Gamal Abdelnasser 1528178

 Dedicate
we sincerely would like to thank
Dr. Ahmed A. El – sherief
for his great efforts which have
been useful also for his enless
support
 The Monsanto Acetic Acid Process
Practical kinetic example: The Monsanto Acetic Acid Process
The synthesis of acetic acid from methanol is probably the most important
industrial process in homogenous catalysis
worldwide requirements are about 5.5 106 t/a

Monsanto process invented 1966, before

oxidation of ethanol

oxidation of acetaldehyde

naphta oxidation

Carbonylation of methanol (Co-catalyst)

Carbonylation of methanol (Rh-catalyst)

[cat]
H3COH + CO H3CCOOH
04.04.2018 CHE323-FS18-3
 The Monsanto Acetic Acid Process
Practical kinetic example: The Monsanto Acetic Acid Process
Comparison of the processes
selectivity T/°C p/atm
Naphta oxidation BP 65-70 185 48

MeOH / CO (Co cat) 90 230 600

MeOH / CO (Rh cat) 99 150-200 30-60

MeOH / MeOAc carbonylation (Rh cat) high 150-200 30-50

- CH3COI + CH3-I

catalytic cycle: H2O

COMe
I I
Rh
+ CO I CO
3a
6 (!) reactions are interlinked to form one closed working catalytic system
The Monsanto Acetic Acid Process
Practical kinetic example: The Monsanto Acetic Acid Process

Many studies focused on the rds of the cycle, namely

[RhI2(CO)2]- + H3C-I {RhI3(CH3)(CO)2}-

1a 2a
polar solvents and addition of I- accelerate the reaction

{RhI3(CH3)(CO)2}- (2a) difficult to detect spectroscopically

The next step, CO insertion, is fast

{RhI3(CH3)(CO)2}- [RhI3(CO-CH3)]-
2a 3a

very careful analysis of the i.r. spectra

2a and 3a become „visible“

 : increases and decreases with 1a

1H and 13C NMR in deep cold solution of CH3-I confirm the finding from i.r.
i.r. pattern discloses a fac,cis-dicarbonyl structure

The detection of 2a allows for determination of the individual steps

 Practical kinetic example: The Monsanto Acetic Acid Process

k1 k2
[Rh(CO)2I2]- + MeI [MeRh(CO)2I3] [(MeCO)Rh(CO)I3
k-1 k-2
1a 2a 3a

k1k2[MeI]
rate constant:
k1+ k2

k1[MeI]
ratio of concentrations: [2a] = k2 = k obs [1a]
[1a] k1+ k2 [2a]

[1a]
can be estimated from i.r. intensities which allows for the determination of k 2
[2a]
COMe COMe heating in the presence of exc. H3C-I
I I I I
Rh can be isolated Rh allows for the determination of k -2
I CO I CO
3a 3a label exchanges between COCH3 and CO
Practical kinetic example: The Monsanto Acetic Acid Process

from these experiments, a complete set of data could be deduced

Practical kinetic example: The Monsanto Acetic Acid Process
what about the remaining processes leading to acetic acid ?

COMe COMe
I I + CO OC I red. elim.
Rh Rh
I CO I CO
- H3C-COI
3a 4a I
3a is immediatly trapped by CO

4a eliminates H3C-COI rather slowly (t1/2 = 12h at r.t.

difficulty to measure accurate kinetics (due to traces of water)

[Rh(CO)2I2]- + 2HI [Rh(CO)2I4]- + H2

O
COMe direct attack +
C
OC I Me NR1R2
Rh
I CO
I O
4a red. elim. + C amine attack
Me I
 Practical kinetic example: The Monsanto Acetic Acid Process
further reactions: conversion of other alkyl-iodides to acids

acid acid

CO H CO
I I I CO I I CO I I
Rh Rh Rh Rh Rh
I CO I CO I CO I CO I CO
I I I

H CO
I CO HI / C2H4 I I CO I I
Rh Rh Rh Rh acid
I CO I CO I CO I CO
1a I I

other alkenes can be used by substituting ethene

isomerization of alkenes or conversion to acids

Evidence of SN2 mechanism

Square-planar complexes are those in which the metal ion dsp2 hybridized its outer d8electrons

orbitals. These include Pt(II), Pd(II), Au(III), Ni(II), Rh(I) and Ir(I). These complexes are (spin

paired).

1) Square-planar complexes are coordinatively unsaturated with a sixteen-electron valence shell.

2) these metal centers would follow an associatively activated mechanism since this would

generate an eighteen-electron valence shell, five-coordinate transition state. Square-planar

complexes are also not sterically hindered thus the incoming ligand can attack the complex

from above or below the plane.

 summary
Acetic acid is a major organic chemical that is manufactured in enormous quantities. It is used
in numerous processes that include production of monomers as precursors for
polymerization, as a solvent,

The rate-determining step in the process is believed to be oxidative addition of CH3I to the
rhodium complex, producing an octahedral rhodium +3 complex.

The second step entails an insertion reaction or could also involve migration of the CH3 to a
neighboring CO to give a Rh–C(O)CH3 linkage or movement of the CO.
After the addition of a molecule of CO, reductive elimination of CH3COI generates the initial
rhodium complex ion.

 The acetyl iodide that is released in the last step of the process reacts with water to produce
acetic acid,

CH3COI + H2O CH3COOH + HI

 In an alternate procedure, the acetyl iodide is converted to methyl acetate if methanol is the
solvent for the process.

CH3COI + CH3OH CH3COOCH3 + HI

 Methyl iodide is regenerated by the reaction

CH3OH + HI CH3I + H2O

MCQs
1. The rate determining step of reaction found to be ;
a. CH3I elimination b. .CH3I insertion c. carbonyl insertion
.
2. The reaction proceeds via ;
a. Associative mechanism b. Dissociative mechanism c. Non

3. Finally methyl iodide is regenerated by reaction of acetyl iodide with ;

a. Methanol b. water c. acetic acid

4. The intermediate formed has ……..coordination number than/as starting compound

a. Higher b. same c. lower

5. After addition of a molecule of CO, ………of CH3COI generates the initial complex ion
a. Oxidative addition b. reductive elimination c. Non

6. The oxidation state of initial complex is ……., while that of the intermediate is…..
a. i / ii b. i / iii c. iii / ii

7. The coordination numbers of initial , intermediate and final complexes are respectively ;
a. 16,18,16 b. 18,16,18 c. 16,18,18

8. Type of hybridization of metal incorporated in initial complex

a. dsp2 b. d2sp c. sp3
 ]

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