CHME 405 Chemical Process Industry
Summary Sheet
Process: Formic Acid
Introduction
Formic acid, HCOOH or HCO2H is the simplest carboxylic acid and also called as methanoic acid. It is a
colorless liquid having a highly pungent, penetrating odour at room temperature. It is miscible with water and
most polar organic solvents, and is somewhat soluble in hydrocarbons.
In the 15th century it was aware that venom of bee, ant stings and ant hills gives off an acidic vapour. John Ray
described the isolation of formic acid by the distillation of large numbers of ants in 1671. Ants secrete the
formic acid for attack and defense purposes. The name formic acid comes from the Latin word for ant, formica,
referring to its early isolation by the distillation of ant bodies. Joseph Gay-Lussac first synthesized formic acid
from hydrocyanic acid by the French chemist. Marcellin Berthelot, developed a synthesis from carbon
monoxide in 1855, the method with some modifications still in used.
Until the late 1960s, formic acid became available as a byproduct of acetic acid production it was only of minor
interest in the chemical industry. Now finds use as antibacterial in livestock feed and
preservative.
Formic acid consists of hydrogen-bonded dimers rather than individual molecules in
hydrocarbons and in the vapour phase. Due to its tendency to hydrogen-bond, gaseous
formic acid does not obey the ideal gas law. Solid formic acid consists of an
effectively endless network of hydrogen-bonded formic acid molecules. It also forms a
low-boiling azeotrope with water (22.4%) and liquid formic acid also tends to
supercool. Esters, salts, and the anion derived from formic acid are referred to as
formates.
Process
Formic Acid
Raw Materials
Basis 1000kg Formic acid (90%)
Sodium Hydroxide 880kg
Carbon monoxide 655kg
Sulfuric acid 1035kg
Reaction
Sodium formate
CHME 405 Chemical Process Industries (CPI)
Fall 2022 © Dr. Fadwa Eljack
Manufacturing process (block diagram) and Description
Sodium hydroxide (97 to 98 %) was charged into a reactor equipped with agitator a packed tower. Carbon
monoxide, freed from carbon dioxide which is obtained by the incomplete combustion of coke is reacted with
the caustic soda at 150 – 200oC temperature under a pressure of 100 – 150psi. The resulting reaction product is
crude sodium formate.
Crude sodium formate was acidified with dilute sulfuric acid, resulting formic acid distilled off. Due to the
proximity of the formic acid and water boiling points, only dilute formic acid (below 75%) can be obtained by
distillation. 85 – 90% formic acid is obtained by separating it from Na2SO4 by distillation. The yield based on
sodium hydroxide charged is 90 – 95 %. The yield based on sodium hydroxide charged is 90 – 95 %.
From producer gas
As an alternate procedure, producer gas (carbon monoxide and hydrogen) and a dilute sodium hydroxide solution
(25 – 30%NaOH) may be reacted under essentially the same conditions. The effluent liquor may be dried to yield
sodium formate.
From methyl formate
The acid hydrolysis of methyl formate also results into formic acid. Methanol and carbon monoxide are reacted at
about 2000C under the pressure of 20 – 25atm to give methyl formate. By the action of water and catalytic amounts
of sulfuric acid methyl formate is converted to dilute formic acid and methanol. Essentially anhydrous or
concentrated formic acid may be obtained by subjecting methyl formate to reaction with glutaric or oxalic acid with
an admixed esterification catalyst such as sulfuric acid. Formic acid is liberated, while methyl esters of the dibasic
acid are hydrolyzed with water to liberate methanol. The regenerated dibasic acid is recovered.
Engineering Aspects
Effect of acid concentration
The addition of concentrated sulfuric acid to dry sodium formate results in quite extensive
decomposition with formation of carbon monoxide.
CHME 405 Chemical Process Industries (CPI)
Fall 2022 © Dr. Fadwa Eljack
The decomposition is minimized by adding concentrated sulfuric acid to slurry of powdered sodium
formate
Amount of Catalyst
Formic acid from carbonylation of methanol in liquid phase is carried out with aid of basic catalyst such as
sodium methoxide. The amount of water and CO 2 in starting material must be minimized because they cause
deactivation of catalyst.
Thermodynamics and kinetics
Typical reaction conditions appear to be 80oC, 44atm pressure and 2.5%w/w of catalyst. The
hydrolysis of methyl formate is technologically demanding for a number of reasons. The equilibrium
of hydrolysis is relatively unfavorable. It depends on the concentration of water, and favors the use
of high stoichiometric excesses of water. Due to presence of highly volatile methyl formate, formic
acid is a sufficiently strong acid to catalyze the re-esterification reaction
Properties
Molecular formula : CH2O2
Molecular weight : 46.03 g/mole
Appearance : Colorless liquid
Odor : Highly pungent and penetrating odor
Boiling point : 100 – 101oC
Melting point : 8.2 - 8.4oC
Density : 1.22gm/cm3
Flashpoint : 48.0oC
Auto ignition temperature : 601.00C
Solubility : Miscible with water
Uses
Formic acid is used as preservative and antibacterial agent in livestock feed. It also added to feed to kill
E. coli bacteria in the poultry industry
In the production of leather including tanning, dyeing and finishing of textile because of its acidic nature
As a coagulant in the production of rubber
In place of mineral acids for various cleaning products such as lime scale remover and toilet bowl
cleaner
As a miticide against the tracheal mite
For formylation of methyl aniline to N-methylformanilide in toluene
As a volatile pH modifier in HPLC and capillary electrophoresis
Treatment of formic acid with sulfuric acid is a convenient source of carbon monoxide, as it
decomposed by sulfuric acid
CHME 405 Chemical Process Industries (CPI)
Fall 2022 © Dr. Fadwa Eljack
CHME 405 Chemical Process Industries (CPI)
Fall 2022 © Dr. Fadwa Eljack
