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    Advanced Catalysis

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    Suviti Chari
    This document summarizes a study on the synthesis of acetic acid via methanol hydrocarboxylation using CO2 and H2. The researchers investigated various factors to improve the yield and selectivity of the process, including ligands, promoters, solvents, and catalyst ratios. A Ru3(CO)12/Rh2(OAc)4 catalyst system with a 60/60 ratio achieved a 70.3% yield. The study proposes that LiI is the best promoter and N,N'-dimethylimidazole is the optimal solvent. The work provides a potential route for activating and utilizing CO2 in chemical synthesis.

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    Advanced Catalysis

    Uploaded by

    Suviti Chari
    115 views24 pages
    This document summarizes a study on the synthesis of acetic acid via methanol hydrocarboxylation using CO2 and H2. The researchers investigated various factors to improve the yield and selectivity of the process, including ligands, promoters, solvents, and catalyst ratios. A Ru3(CO)12/Rh2(OAc)4 catalyst system with a 60/60 ratio achieved a 70.3% yield. The study proposes that LiI is the best promoter and N,N'-dimethylimidazole is the optimal solvent. The work provides a potential route for activating and utilizing CO2 in chemical synthesis.

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    Acetic acid via methanol hydrocarboxylation with CO2 and H2

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    Advanced catalysis

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    This document summarizes a study on the synthesis of acetic acid via methanol hydrocarboxylation using CO2 and H2. The researchers investigated various factors to improve the yield and selectivity of the process, including ligands, promoters, solvents, and catalyst ratios. A Ru3(CO)12/Rh2(OAc)4 catalyst system with a 60/60 ratio achieved a 70.3% yield. The study proposes that LiI is the best promoter and N,N'-dimethylimidazole is the optimal solvent. The work provides a potential route for activating and utilizing CO2 in chemical synthesis.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    115 views24 pages

    Advanced Catalysis

    Uploaded by

    Suviti Chari
    This document summarizes a study on the synthesis of acetic acid via methanol hydrocarboxylation using CO2 and H2. The researchers investigated various factors to improve the yield and selectivity of the process, including ligands, promoters, solvents, and catalyst ratios. A Ru3(CO)12/Rh2(OAc)4 catalyst system with a 60/60 ratio achieved a 70.3% yield. The study proposes that LiI is the best promoter and N,N'-dimethylimidazole is the optimal solvent. The work provides a potential route for activating and utilizing CO2 in chemical synthesis.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 24

    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 ● Catalyst system :
    Ru3(CO)12/Rh2(OAc)4
    Vs. pyridine, PPh3, 60/60
    2,2’- bipyridine, PPN-Cl

    ● Solvent : DMI ● Catalyst promoter : LiI


    Vs. NMP, THF, cyclohexane, Vs. NaI, KI, LiCl, KBr, SnCl4
    water
    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

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