Production of formaldehyde from methanol

Formaldehyde is a chemical compound that is produced from methanol or methane at elevated temperate by catalytic, vapor-phase oxidation. It has many applications as it is a common building block for the synthesis of more complex compounds and materials. It is used to produce urea formaldehyde resin, melamine resin, phenol formaldehyde resin, polyoxymethylene plastics, 1,4-butanediol, and methylene diphenyl diisocyanate. The major consumption for this material is in construction, automotive and furniture markets. It is commercially sold as a 37% to 50% aqueous solution, with 37% being the most widely used grade which may also contain 0-15% methanol and a polymerisation inhibitor. The world production of formaldehyde has reached 32.5 million metric tons by 2012 with average price of US $380-437/Ton FOB. The process of production of formaldehyde can be summarized by reaction of methanol and oxygen in a vapor-phase catalytic reactor according to the following reactions:
CH3OH 1 O2 HCHO H 2O 2
CH 3OH HCHO H 2

(1) (2)

The first reaction is exothermic in nature while the second one is endothermic. Reaction (1) is desired and the reactor is generally run so that the overall reaction is slightly exothermic with selectivity of 9 with outlet temperature of 200C. In this project it is required to design a plant that produces 60,000 tons/yr formalin having 37 wt% of formaldehyde in water according to the following process description: Fresh methanol at 25C and 1 atm mixes with recycled methanol at 68.3C and 1.2 atm, pumped at 3 atm and then vaporized at 150C. Fresh air available at 25C and 1 atm is compressed and mixed with methanol stream before entering the reactor. In reactor section, the conversion of methanol is 87.4%. The exit reactor temperature is 343C. Fresh water is sent through the absorber at 30C and 138 kPa where is set to absorb 99% of the formaldehyde that enters. The exit liquid stream is then heated to 102C before entering the formalin distillation column. It is worth notice that most of the methanol is recovered in the distillate of distillation column where it is recycled back to the inlet of fresh methanol at 68.3C and 110 kPa. The bottoms from distillation column are pumped for storage. Deionized water at 30C is added to achieve the 37 wt% solution of formaldehyde in water.

The following are specification for the catalyst: The catalyst bulk density is 1500 kg catalyst/m3 of reactor volume with void fraction of 0.5. The catalyst particles are spherical, with a 1 mm diameter. The following kinetic information for the methanol oxidation reaction:
1 CH3 OH 2 O2 HCHO H2 O

The rate expression is:

k1 pm 1 k 2 pm Where p is a partial pressure in atm, and m refers to methanol. The rate expression in Eq. (A-2) is only valid when oxygen is present in excess. The constants are defined as: ln k1 12.50 8774 T ln k 2 17.29 7439 T where T is in Kelvin. The rate data as follows for the side reaction: rm1 [mole / g catalyst / hr ]
CH 3OH HCHO H 2

The rate expression is:

rm2 [mole / g catalyst / hr ]
' 0 k1 p m.5 ' 0 1 k 2 p m.5

The constants are defined as:

' ln k1 16 .9 12500 T ' ln k 2 25.0 15724 T Standard enthalpies of reaction (298 K, 1 atm) for the two reactions are given as:
o H1 = - 156 kJ/mol methanol

o H 2 = + 85 kJ/mol methanol

flow rate of stream 10 (mol/h) Temp C 200 Methanol 13605.99967 O2 0 H2 9437.812468 Formald 94378.12468 N2 159768.6825 water 84940.31221 Temperature of stream 11 is 30 c, 99% of formaldehyde is recovered in the bottom of the absorber and almost all methanol as well, the rest of the gases are in the off-gas. We need the flow rate of the water in stream 11. (mass of formaldehyde)/(mass of formaldehyde and water) should be greater than 0.37 or 37% after the absorber.