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1.1.1. INTRODUCTION
Acetic acid – important raw material used for the production of vinyl acetate, acetic anhydride,
polymer-grade terephthalic acid (PTA), etc.
Production of PTA – the most important and leading reason for the increase of demand of acetic acid;
growth rate in per capita consumption of acetic acid in Asia is typically 7 to 8 percent per annum
Methanol carbonylation process – world's leading acetic acid production process, synthesis from
methanol and carbon monoxide
Other methods:
Oxidation of acetaldehyde
Direct oxidation of ethylene, etc.
Chiyoda ACETICA® - developed and owned by Chiyoda, to produce acetic acid by the carbonylation
of methanol and carbon monoxide.
The ACETICA process for producing acetic acid is based on the presence of a proprietary
heterogeneous rhodium catalyst in the active rhodium complex that is chemically immobilized on a
polyvinylpyridine resin. To minimize attrition of the solid catalyst material, a bubble column reactor
is employed.
This immobilized catalyst system has the following advantages over the conventional liquid rhodium
catalyst:
Handling of the catalyst is easy because it need not be recovered by separating the rhodium
from the reaction liquid.
A high level of reactor productivity can be obtained because the concentration of rhodium
can be increased without the limitations imposed by solubility.
The formation of by-products can be suppressed because operation is conducted under a
low water concentration.
The corrosive environment is moderated because the concentration of hydrogen iodide is
decreased.
Esterification:
Etherification:
Etherification:
Hydrogen iodide is formed in the reaction solution by hydrolysis of the metal iodide:
Certain amounts of methanol and acetic acid may react with the methyl iodide as shown below:
The detailed pathway of the Rh complex catalyst supported on solid resin can be depicted as two
interacting cycles, as shown in Fig. 1.1.1.
Promoter (CH3I): The ACETICA process uses methyl iodide as the promoter for the carbonylation
reaction, as described earlier. The method of producing CH3I in a methyl iodide generator is
The active rhodium complex, [Rh(CO)2I2], is immobilized by the ion exchange on the
quaternizedpolyvinylpyridine resin.
Because the ion-exchange equilibrium favors the solid
phase, almost all Rh in the reaction mixture is immobilized
on the resin support.
Liquid By-Products. Very small amounts of liquid by-products are produced at the initial stage of plant
operation, and their concentrations come to equilibrium,except for some heavy by-products such as
propionic acid. These heavy by-products are eliminated with small purges from the purification unit.
1.1.2.4. Iodide-Removal ReactionTo minimize iodide loss, most of the iodide compounds in the crude
product are recovered and returned to the synthesis section from the distillation section. Small amounts
of iodide compounds remain in the distilled product, and these are removed by a proprietary adsorbent.