The commercial production of formaldehyde was first started in Germany in the 1880s but the

development of a methanol synthesis route in the 1920s gave the spur to the development of large-
scale manufacture. Today there are two main routes: oxidation-dehydrogenation using a silver
catalyst involving either the complete or incomplete conversion of methanol

In the silver catalyst route, vapourised methanol with air and steam is passed over a thin bed of
silver-crystal catalyst at about 650oC. Formaldehyde is formed by the dehydrogenation of methanol.
The heat required for the endothermic reaction is obtained by burning hydrogen contained in the off-
gas produced from the dehydrogenation reaction.

 Manufacture of Formaldehyde from Methanol

 (HCHO) can be manufactured from methanol via two different reaction routes:
1. Deation or oxidative dehydrogenation in the presence of Ag or Cu catalysts.
2. Oxidation in the presence of Fe-containing MoO, catalysts.
The oxidative dehydrogenation process with Ag or Cu metal is operated above the explosion limit
with a small quantity of air.
 
In the oxidation process, a small amount of methanol is reacted below the explosion limit with a
large excess of air. The thermal energy balance of the reaction is essential for process design in
this manufacturing method.

To 1:
Ag catalysts are preferred for the dehydrogenation and oxidative dehydrogenation of methanol.
In the BASF, Bayer, Borden, Celanese, Degussa, Du Pont, ICl, Mitsubishi Gas, Mitsui Toatsu, and
Monsanto processes the catalyst (silver crystals or gauze) is arranged as a few centimeter thick
layer in the reactor. In the CdF Chimie process, silver is supported on carborundum. In the initial
step methanol is dehydrogenated:

Hydrogen can be combusted exothermically on addition of air, resulting in the following formal
equation for the oxidative dehydrogenation:

A less-than-stoichiometric amount of air is employed in the industrial process. The air is fed so
that the reaction temperature remains constant (± 5 °C) in the range 600-720 °C. At
temperatures of about 600-650°C, conversion of methanol is incomplete, and a methanol recycle
is necessary. At higher temperatures of 680-720 °C and with the addition of H 2O, there is almost
complete conversion of the methanol in a single pass. The water has another favorable effect on
the life of the Ag catalyst in that the steam delays the deactivation caused by sintering of the thin
layer of red-hot silver crystals. The catalyst has a lifetime of 2-4 months and the spent catalyst
can be easily regenerated electrolytically without loss of Ag. The catalyst is sensitive to traces of
other metals as well as halogens and sulfur.
The hot gases from the reaction are very quickly cooled to ca. 150 °C and washed in a
counterflow with H2O in several absorption stages. The solution is stabilized towards
polymerization with a residual amount of methanol (1-2 wt%). A distillation can follow to produce
concentrated formaldehyde solutions (37 to 42 wt%). The yield of formaldehyde exceeds 92%
with a selectivity of over 98%.
The byproducts are CO and CO2. There is virtually no formic acid present.