Synthesis of acetic acid via methanol

hydrocarboxylation with CO2 and H2

By Q. Qian, J. Zhang, M. Cui & B. Han

By Ahmad Aljaber, Suviti Chari and Nerissa Schuit

Table of Contents
Background and history(timeline) of Acetic acid Processes (Commercial processes and uses & comparative cat cycles)
Aims and Objectives of paper and novel aspects of this process
Why use CO2? & challenges
Methodology/Process
- reaction eq. In entirety ( what do you mean ness!)
-overall mechanism (w/ limitations)
- step by step 1-5
- role or Rh/Ru & Ru Red Elim and Rh Ox Add etc.
- effect of each factor w/ evidence (any limitations pointed out)
- ligand
- promotor
- solvent
- Catalyst ratio & precursors
- CO2/H2 ratio
- mechanistic pathway discussion (CO/CO2)
- his evidence for CO2 pathway

- Analysis of the limitations and breadth of the scope of the technology (HI + Acetic acid engineering issue &
separation)
- Usefulness (activation of CO2)
Background
- 1960 BASF - Co & I2 - 600 atm, 230oC 90% selectivity
- 1970/1986 Monsanto - Rh - 30-50 bar 150oC-200oC >90% selectivity
- 1980 Celanese (Monsanto modification) - LiI promotor to reduce H2O content
- 1996 Cativa - Ir + promotor - 150-200oC P=30-50 bar (~85% yield)
- Acetica -
- Acetaldehyde Oxidation - Co or Cr 150oC 55 bar 95% yield
- Showa Denko Partial Ox of Ethylene - Pd cat 300oC 12-15 bar 86%
selectivity
- 2005: Sabic - Ethane oxidation 150-450 oC 15-750psi

Cost: $500-600
Methods of Acetic Acid Production
History of Acetic Acid

BASF Celanese Cativa (BP)

Cobalt iodide Modified version of Monsanto Iridium + promoter

P=10000 psi 90% selectivity P=500 psi >90% selectivity P= 500 psi 99% selectivity

1970 1986 2013

1960 1980 1996

Monsanto BP SaaBre

Rhodium Monsanto technology was Production of acetic acid directly

acquired by BP company from syngas.
P=500 psi 90% selectivity
Reducing cost by 50 $ /tonne
PET
Environmental Issues
Acetic acid production from methanol and synthesis gas has high selectivity and
conversion

Cheap and renewable resource ( price? Vs CO )

Carbon fixation into value added chemicals
Benefits and Limitations of using CO2 for AA
synthesis
- Cheap and renewable resource ( price? Vs CO )
- Carbon fixation into value added chemicals

- Low selectivity, low activity

- High reaction temperatures
- Toxic/expensive reactants
Objectives
Utilisation of CO2
Increasing yield and selectivity
Mechanistic understanding
 Methanol Carbonylation using CO2

Yield (MeOH based) = 70.3% Yield (Monsanto) = 99% ΔH°298K = -137.6 kJ/mol ΔH°298K = -137.98 kJ/mol

TOF = 30.8 /hr Yield (Cativa) = >99% ΔG°298K = -66.4 kJ/mol ΔG°298K = -88.88 kJ/mol
Yield (MeOH based) = 70.3% Yield (Monsanto) = 99%

TOF = 30.8 /hr Yield (Cativa) = >99%

ΔH°298K = -137.6 kJ/mol ΔH°298K (Monsanto) = -138.0 kJ/mol

ΔG°298K = -66.4 kJ/mol ΔG°298K (Monsanto) = -88.9 kJ/mol

Proposed Mechanism
Reaction factors investigated
● Ligand : Imadizole
Vs. pyridine, PPh3,
2,2’- bipyridine, PPN-Cl
● Solvent : DMI
Vs. NMP, THF, cyclohexane,
water
● Catalyst system :
Ru3(CO)12/Rh2(OAc)4
60/60
● Catalyst promoter : LiI
Vs. NaI, KI, LiCl, KBr, SnCl4
Cata
Proposed Mechanistic Pathways
1. CO Pathway 2. CO2 Pathway
Methanol Carbonylation Methanol hydrocarboxylation

[insert general outline] [reinsertion of

Limitations of their method

Issues with CO2

- Low selectivity, low activity

- High reaction temperatures
- Toxic/expensive reactants (DMI as a solvent,
- Scaling up may need changes to plant?
-
Benefits
● CO2 activation
○ CO2 economy
The U.K.
Appendix and Supporting Information
Acetic Acid Consumption ‘17
Factors:
Promoter:
- Found LiI - best promoter
- Li+ has strongest lewis acidity & small ion size to reach coordination site
- I- has the strongest nucleophilicity, aids in C-C bonding during the formation of
acetic acid

Solvent:
- Stabilisation of catalyst required
- Organic solvent necessary for solubilising power. However strong organic
solvents DMSO, DMF , toluene etc decompose catalyst (black ppt. observed)
- Fine tuning with solvent sphere for the complex required. DMI found as best
Catalyst system
Rh(OAc) found as major catalyst

Ru(OAc) as co-catalsyt

Ratios: 60/60, 40/40