Formaldehyde from Methanol Process

Formaldehyde is the main constituent for manufacturing valuable chemicals like melamine, urea and phenolic resins. It is available in 37% aqueous solution. It is identified by some of its properties like molecular weight about 30.3, boiling point -118 oC, melting point at -19 oC and density of 0.815 at -20 oC.

Formaldehyde Manufacturing Technologies:

Out of two important methods of manufacture formaldehyde in large scale, methanol process route is optimized and established for industrial production.

  1. Non-catalytic oxidation of methane/ butane or propane.
  2. Dehydrogenation of methanol by catalytic oxidation.
    1. Silver catalyst process
    2. Metal oxide catalyst process

The catalytic oxidation process is an optimized production method. Let us discuss the technology in this process. It is a simple process as per the stoichiometric reaction steps are shown below.

1. Oxidation of methanol with oxygen present in the air

  • CH3OH + ½ O2 → HCHO + H20     ∆H = -37 Kcal

2. Pyrolysis endothermic reaction

  • CH3OH → HCHO + H2                ∆H = +20 Kcal

3. Side reaction – complete combustion producing heat energy

  • CH3OH + 3/2 O2 → 2H2O +CO2     ∆H = -162 Kcal

Brief process description of methanol dehydration for formaldehyde production:


Silver Catalyst Method:  Initially Air compressed to pressure 0.2 atm by an air compressor and fed to the bottom of methanol vaporizer. The ratio of methanol and air maintained about 35-45%. This mixture heated to the reaction temperature 550-600 oC by series of preheater before entering into the silver catalyst reactor. The catalytic reactor is fixed bed type filled with silver catalyst used for converting methanol to formaldehyde. The fraction of conversion depends on the catalyst type and the temperature of the reactor at fixed operating pressure. Advance reactor controls both reactions, exothermic combustion reaction and endothermic dehydration reaction simultaneously in a single step.

The product stream sent to purification and recovery section. Unreacted methanol fed back to the process of methanol vaporizer. Recycle stream contains 15% unreacted methanol of feed to the vaporizer. Formaldehyde obtained as the heavy end of alcohol stripper column. It is in the form of aqueous containing 63% water. The overall process has yield ranging from 85-90% on the weight basis.

Technology challenges on formaldehyde catalytic oxidation are the selection of catalyst and air to methanol ratio. When metal oxides are mixed, and then there are chances of obtaining greater than 90% overall yield of desired product. Reducing the concentrations of CO + CO2 in the streams is one of the demanding tasks for a process engineer.


Process flow diagram of Formaldehyde manufacturing by silver catalyst methanol process

Process flow-diagram of silver catalyst process

Methanol stripper: In above flow diagram the unreacted methanol is stripped out from formaldehyde solution and recycled to the process. The downstream from methanol stripper requires further purification column to remove water and increase the purity of formaldehyde or adjust it concentration as per customer order. However, by using a single vacuum distillation column the separation can be achieved eliminating the two stripping columns.

Metal oxide catalyst process: Iron–molybdenum oxide catalyst replaced the costly silver improving the methanol conversion to 99% it surfaces is very much suitable for formation of H2CO.  The reactions in the shell and tube reactor are completely exothermic. 250-345oC temperature is maintained in the reactor by removing the excess energy from reactor tube using dowtherm oil.
Iron-molybdenum oxide catalyst process to produce formaldehyde from methanol

Process flow diagram to produce formaldehyde by
metal oxide catalyst process