Formaldehyde is a clear, reactive gas under ambient conditions.

It is usually marketed
as a liquid solution, typically at 37 weight percent formaldehyde solution, combined with
water and up to 15 percent methanol. Therefore, all production comparisons shown in
this report are made on a 37 weight percent basis. However, higher concentrations are
sold and are required for the production of some derivative products such as polyacetal
resins. The market trend is to sell solutions at higher concentrations to reduce shipping
costs. Stabilizers are usually required when shipping higher concentrations of
formaldehyde solutions.

The only production technologies for formaldehyde of commercial significance are

based on the
1. partial oxidation and dehydrogenation of methanol using a silver catalyst, or
2. partial oxidation of methanol using a metal (molybden/iron) oxide-based catalyst
(“Formox” process).

In the silver catalyst route, vaporized methanol with air and steam is passed over a thin
bed of silver-crystal catalyst at about 600 to 700 °C. 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. The silver catalyst process uses an excess of methanol. The
main formaldehyde forming reactions for this process are shown below
(dehydrogenation of methanol to formaldehyde and partial oxidation of methanol):

1. Oxidation of methanol with oxygen present in air

CH3OH + ½ O2 → HCHO + H2O ∆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

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
reactions, exothermic combustion reaction and endothermic dehydration reaction
simultaneously in single step.
The hot gases from the reaction are very quickly cooled to ca. 150 °C and washed in a
counter flow 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%

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

Technology challenges on formaldehyde catalytic oxidation are 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.
The Formox Process
The Formox formaldehyde process is widely used all over the world. There are many
reasons for this, where the most important ones are probably
 The high yield that this process gives,
 The high formaldehyde concentration and
 The low content of methanol in the product.
 The high steam production,
 High level of safety,
 The simplicity and reliability of the process, in addition to low operating cost.
 This process is also environmental friendly

Catalysts
In the Formox process a metal oxide is used as a catalyst. The metal oxide is a mixture
of iron and molybdenum and the atomic ratio of Mo:Fe is 1.5-2.0. Small amounts of
V2O5, CuO, Cr2O3, CoO, and P2O5 are also present. The catalyst is dispersed on an
inert support.
The catalyst has two active sites: the metal-site, where absorptions occur directly on the
molybdenum atom, and the oxygen-site. In the process a two-step oxidation reaction
occurs. When converting methanol to formaldehyde the catalyst is reduced. The oxygen
content in the feedstock will then oxidize the catalyst and prepare it for a new methanol
molecule. A catalyst of this type usually has an effective lifetime of between 12 – 18
months. The overall methanol conversion in the Formox process ranges from 95 – 99%
and is dependent on the catalyst selectivity, activity and temperature

When producing formaldehyde, methanol is mixed with excess air, which reacts over a
modified iron-molybdenum oxide catalyst. In the feed, the ratio between methanol and
air cannot exceed 1:13 in order to avoid explosions. The gas mixture is non-explosive
when the methanol content in the inlet is below 6.5%. However, to obtain the desired
product replacing some of the fresh air with process gas from the absorption allows for
methanol content above 6.5% without making the mixture explosive.

Reactions
In the Formox process vaporized methanol is mixed with air in the reactor and
formaldehyde is formed. The reaction is described

𝐶𝐻3O𝐻+1/2𝑂2⇌𝐻𝐶𝐻𝑂+𝐻2𝑂 −215 𝑘𝐽/𝑚𝑜𝑙. (1)

The methanol is absorbed on the active site on the catalyst, which in this case is on the
surface of the Mo-atom. The reaction on the catalyst surface involves two sites. The
methoxy-group (-OCH3) will absorb on the metal-site and the hydrogen will absorb on
the oxygen-site.

There are four side reactions in the formaldehyde process

 1
HCHO +2 O2 ⇌ CO+H2O (2)

2CH3OH ⇌ CH3-O-CH3+H2O (3)

1
HCHO +2 O2 ⇌ CHOOH (4)

HCHO+O2 ⇌ CO2+H2O (5)

Carbon monoxide is formed in reaction (2), and in reaction (3) the formation of dimethyl
ether occurs. The formation of these by-products occurs when formaldehyde desorbs
from the catalyst at a slower rate. Dimethyl ether and carbon monoxide are formed in a
greater extent than the by-products formed from reaction (4) and (5). In reaction (4)
formic acid is generated and carbon dioxide is formed in reaction (5). These two
reactions occur outside the reactor after formalin is produced. All the by-products
formed in reaction (2) – (5) are undesired.

At atmospheric pressure and between temperature ranges of 270 – 400 °C the

conversion of methanol to formaldehyde is almost complete. In other words, the
undesired side reactions (2)-(5) will be reduced.

Process and Equipment

The main components in the Formox formaldehyde process are

1. Recirculation blowers
2. Prevaporizer A prevaporizer is a spiral heat exchanger that heats the methanol to
gas
3. Vaporizer Process gas with methanol from the prevaporizer flows inside the tube
and hot process gas from the reactor works as the heating medium. Methanol is
then sprayed on the tube plate and heated to gas
4. Reactor The process gas with methanol is fed to reactor where it enters 14600
vertical tubes filled with FeMo catalyst. The tubes are 1400 mm long and have a
loading profile that consists of inert (300 mm), mix of inert and pure catalyst (400
mm), pure catalyst (600 mm) and inert (100 mm) from top to bottom. When the
gas passes the catalyst, the methanol is oxidized to formaldehyde. This is a very
exothermic reaction and consequently a cooling medium is required. The process
uses excess air and the temperature in the reactor is isothermally controlled to a
temperature of about 340 °C. When heat is evolved due to the reaction inside the
tubes the cooling medium will boil on the outside and vaporize. When the gas
leaves the reactor it is cooled in the vaporizer. After the gas is cooled it is fed to
the bottom of the absorption column.
5. Condenser The vaporized coolingmedium from the reactor will flow to the
condenser, which has vertical tubes, where it will condense with the use of water.
As the medium cools down, the water will evaporate and produce steam, which is
transported to the steam storage room. The condensed cooling medium will then
flow back to the reactor
6. Absorber The process water fed to the top of the column controls the
formaldehyde concentration in the product