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Details:
The industrial production methods of oxalic acid mainly include sodium formate method, oxidation method, oxo synthesis method, ethylene glycol oxidation method, propylene oxidation method and carbon monoxide coupling method.
Reaction formula
Reaction formula
1. The sodium formate method purifies carbon monoxide and reacts with sodium hydroxide under pressure to form sodium formate, and then dehydrogenates at high temperature to form sodium oxalate, which is then subjected to lead (or calcification), acidification, crystallization and dehydration. The finished oxalic acid is obtained. The synthesis pressure of carbon monoxide and sodium hydroxide is generally 1.8-2.0 MPa. The dehydrogenation temperature was 400 °C.
2. The oxidation method uses starch or glucose mother liquor as a raw material to oxidize with nitric acid-sulfuric acid in the presence of a rhodium catalyst to obtain oxalic acid. The nitrogen oxides in the exhaust gas are sent to the absorption tower for recovery to form dilute nitric acid.
3. Carbonylation method Carbon monoxide is purified to more than 90%, carbonylation reaction with butanol in the presence of palladium catalyst to form dibutyl oxalate, and then oxalic acid is obtained by hydrolysis. The method is divided into liquid phase method and gas phase method. The gas phase reaction condition is low, and the reaction pressure is 300-400 kPa. The liquid phase reaction pressure is 13.0-15.0 MPa.
4. Ethylene glycol oxidation method is obtained by using ethylene glycol as a raw material and oxidizing with air in the presence of nitric acid and sulfuric acid.
5. Propylene oxidation process The oxidation process is carried out in two steps. The first step is oxidized with nitric acid to convert propylene to alpha-nitrolactic acid; and then further catalytically oxidized to obtain oxalic acid. The second step can also use a mixed acid as an oxidant. The propylene oxidation process produces industrial grade oxalic acid dihydrate with a total yield of greater than 90% based on propylene.
Raw material consumption quota: coke (84%) 510kg / t, sulfuric acid (100%) 950kg / t, caustic soda (100%) 920kg / t.
Oxalic acid is naturally present in the form of salts in many plant cell membranes. In the past, industrially, wood chips and strong bases were co-melted at 240 to 250 ° C. First, oxalate was prepared, and then acidified to obtain oxalic acid. Later, oxalic acid was produced by sodium formate dehydrogenation. Industrially, carbon monoxide (such as yellow phosphorus production tail gas) is absorbed by caustic soda, and sodium formate is obtained. The latter is dehydrogenated at 380 ° C to obtain sodium oxalate, and then treated with lime and sulfuric acid to prepare oxalic acid.