Methanol acetic acid from

Catalysts. Iodine and its compounds ate very active catalysts for many reactions (133). The principal use is in the production of synthetic mbber via Ziegler-Natta catalysts systems. Also, iodine and certain iodides, eg, titanium tetraiodide [7720-83-4], are employed for producing stereospecific polymers, such as polybutadiene mbber (134) about 75% of the iodine consumed in catalysts is assumed to be used for polybutadiene and polyisoprene polymeri2a tion (66) (see RUBBER CHEMICALS). Hydrogen iodide is used as a catalyst in the manufacture of acetic acid from methanol (66). A 99% yield as acetic acid has been reported. In the heat stabiH2ation of nylon suitable for tire cordage, iodine is used in a system involving copper acetate or borate, and potassium iodide (66) (see Tire cords). 

Acetic acid from methanol by the Monsanto process, CH3OH -1-CO CH3COOH, rhodium iodide catalyst, 3 atm (44 psi), 150°C (302°F), 99 percent selectivity of methanol. 

Formation of acetic acid from methanol and carbonylation of alcohols still are important industrial problems, but milder conditions are needed. Other metals, such as rhodium, have proved to be more suitable. 

In homogeneous catalytic systems we witnessed a new process for the production of acetic acid from methanol and carbon monoxide using a transition metal complex, thus displacing the earlier process employing ethylene as the starting material. The use of immobilized enzymes makes possible the commercial conversion of glucose into fructose. 

The insertion of ligated CO into metal-carbon -bonds (or rather the migration of an alkyl group to a coordinated CO) is a key step in a variety of synthetic and catalytic important processes, e.g., in hydroformylation (145), the Fischer-Tropsch reaction (146) and the synthesis of acetic acid from methanol (147). 

Whatever the source of synthesis gas, it is the starting point for many industrial chemicals. Some examples to be discussed are the hydroformylation process for converting alkenes to aldehydes and alcohols, the Monsanto process for the production of acetic acid from methanol, the synthesis of methanol from methane, and the preparation of gasoline by the Mobil and Fischer-Tropsch methods. 

Catalysts used to convert ethylene to vinyl acetate are closely related to those used to produce acetaldehyde from ethylene. Acetaldehyde was first produced industrially by the hydration of acetylene, but novel catalytic systems developed cooperatively by Farbwerke Hoechst and Wacker-Chemie have been used successfully to oxidize ethylene to acetaldehyde, and this process is now well established (7). However, since the largest use for acetaldehyde is as an intermediate in the production of acetic acid, the recent announcement of new processes for producing acetic acid from methanol and carbon monoxide leads one to speculate as to whether ethylene will continue to be the preferred raw material for acetaldehyde (and acetic acid). 

The acetyl iodide formed reacts with water or methanol to give acetic acid or methyl acetate. The latter is subsequently hydrolyzed to acetic acid. Methyl iodide is regenerated according to equation (78). The synthesis of acetic acid from methanol catalyzed by complexes of cobalt, rhodium and iridium has been reviewed.469... 

The recent dramatic increase in the price of petroleum feedstocks has made the search for high selectivities more urgent. Several new processes based on carbon monoxide sources are currently competing with older oxidation processes.103,104 The more straightforward synthesis of acetic acid from methanol carbonylation (Monsanto process) has made the Wacker process obsolete for the manufacture of acetaldehyde, which used to be one of the main acetic acid precursors. Several new methods for the synthesis of ethylene glycol have also recently emerged and will compete with the epoxidation of ethylene, which is not sufficiently selective. The direct synthesis of ethylene... 

The novel synthesis required fewer process steps, and this resulted in lower costs and investment. In 1969, another advance was announced—the synthesis of acetic acid from methanol and carbon monoxide with essentially no by-products or co-products.15 16... 

A cobalt/iodide catalyzed process to make acetic acid from methanol, introduced by BASF around 1960, grew out of the carbonylation studies by... 

The main large-scale metal catalyzed reactions involving addition of CO (rather than CO + H2) to an organic substrate are the manufacture of acetic acid from methanol and the related production of acetic anhydride from methyl acetate. The syntheses of some other carboxylic acids and the conversion of a substituted benzyl alcohol to ibuprofen involve similar reactions. 

Rhodium compounds and complexes are also commercially important catalysts. The hydroformylation of propene to butanal (a precursor of hfr(2-ethyUiexyl) phthalate, the PVC plasticizer) is catalyzed by hydridocarbonylrhodium(I) complexes. Iodo(carbonyl)rhodium(I) species catalyze the production of acetic acid from methanol. In the flne chemical industry, rhodium complexes with chiral ligands catalyze the production of L-DOPA, used in the treatment of Parkinson s disease. Rhodium(II) carboxylates are increasingly important as catalysts in the synthesis of cyclopropyl compounds from diazo compounds. Many of the products are used as synthetic, pyrethroid insecticides. Hexacyanorhodate(III) salts are used to dope silver halides in photographic emulsions to reduce grain size and improve gradation. 

The synthesis of acetic acid from methanol and CO is a process that has been used with great commercial success by Monsanto since 1971. The mechanism of this process is complex a proposed outline is shown in Figure 14-16. As in the hydroformylation process, the individual steps of this mechanism are the characteristic types of... 

An Rh(I) complex containing CO is used industrially to synthesize acetic acid from methanol (CH3OH -I- CO CH3COOH). see also Platinum. 

Encouraged by the interesting results obtained in the high-pressure synthesis of acetic acid from methanol and carbon monoxide using nickel, cobalt, and iron halides as catalysts (5-7), the synthesis of glycolic acid from formaldehyde, carbon monoxide and water has been studied using various nickel, cobalt, and iron catalysts. 

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