Melamine - Synthesis

Synthesis

Melamine was first synthesized by the German chemist Justus von Liebig in 1834. In early production, first calcium cyanamide is converted into dicyandiamide, then heated above its melting temperature to produce melamine. However, today most industrial manufacturers use urea in the following reaction to produce melamine:

6 (NH₂)₂CO → C₃H₆N₆ + 6 NH₃ + 3 CO₂

It can be understood as two steps.

First, urea decomposes into cyanic acid and ammonia in an endothermic reaction:

(NH₂)₂CO → HCNO + NH₃

Then, cyanic acid polymerizes to form melamine and carbon dioxide:

6 HCNO → C₃H₆N₆ + 3 CO₂

The second reaction is exothermic but the overall process is endothermic.

The above reaction can be carried out by either of two methods: catalyzed gas-phase production or high pressure liquid-phase production. In one method, molten urea is introduced onto a fluidized bed with catalyst for reaction. Hot ammonia gas is also present to fluidize the bed and inhibit deammonization. The effluent then is cooled. Ammonia and carbon dioxide in the off-gas are separated from the melamine-containing slurry. The slurry is further concentrated and crystallized to yield melamine. Major manufacturers and licensors such as Orascom Construction Industries, BASF, and Eurotecnica have developed some proprietary methods.

The off-gas contains large amounts of ammonia. Therefore, melamine production is often integrated into urea production, which uses ammonia as feedstock.

Crystallization and washing of melamine generates a considerable amount of waste water, which is a pollutant if discharged directly into the environment. The waste water may be concentrated into a solid (1.5–5% of the weight) for easier disposal. The solid may contain approximately 70% melamine, 23% oxytriazines (ammeline, ammelide, and cyanuric acid), 0.7% polycondensates (melem, melam, and melon). In the Eurotecnica process, however, there is no solid waste and the contaminants are decomposed to ammonia and carbon dioxide and sent as off gas to the upstream urea plant; accordingly, the waste water can be recycled to the melamine plant itself or used as clean cooling water make-up.