TO STUDY MANUFACTURING OF FORMIC

ACID

Prepared By:
1.Amar Ghatge
2.Shreyas Ghodinde
3.Sagar Patil
 Aim of the Project

• Main aim of our project is to Study The Manufacturing Process

Of Formic Acid At Industrial Level And To Design The
Equipments And Plant Design.
 Objectives of the Project
• Studying the manufacturing methods for Formic acid At RCF.

• Perform a literature survey for the various available methods based on

experimental level and Industrial level.

• Studying the existing plant design and various critical Equipments.

• Studying the Economical Aspects such as demand-supply position,

Import-Export in India and world.
INTRODUCTION:
• Formic acid (HCOOH) is the first, or single carbon atom, homolog of the fatty acid
series.
• 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.
• Joseph Gay-Lussac first synthesized formic acid from hydrocyanic acid by the French
chemist.
• It is an industrial chemical of moderate importance, with world consumption in 1980
estimated at 200 million lb/yr and an anticipated growth rate of 4%/yr.
 CHEMICAL STRUCTURE OF FORMIC ACID

• Formic acid is a colorless liquid having a pungent, penetrating odor at room temperature. It is miscible
with water and most polar organic solvents, and is somewhat soluble in hydrocarbons.

• In hydrocarbons and in the vapor phase,

it consists of hydrogen-bonded dimers

rather than individual molecules.

• Owing to its tendency to hydrogen-bond,

gaseous formic acid does not obey the ideal gas law.
 PROPERTIES

•Molecular formula : CH2O2

•Molecular weight : 46.03 gm/mole
•Appearance : Colourless liquid
•Odour : Highly pungent and penetrating odour
•Boiling point : 100 - 1010C
•Melting point : 8.2 - 8.40C
•Density : 1.22gm/cm3
•Flashpoint : 48.00C
•Auto ignition temperature : 601.00C
•Solubility : Miscible with water
 END USERS OF FORMIC ACID
1. Antioxidants (Natural Rubber and plasticizers) 9. Formate production (Sodium-potassium-
calcium formate)

2. Glass silage (Preservation of green grass fodder) 8. Leather treatment (Picking, tanning &
dyeing)

3. Lysine formate (Production of for feed additives) 10. Neutralization reactions (De-acidifying)

4. Bleaching (Wood & cotton, pulp & paper) 11.Chemigraphing (Electronic systems)

5. Coagulation (Natural rubber) 12. Coolant agent (Potassium formate in cold

storage)

6. Deicing (Formates for airport runways) 13. Degreasing (Industrial plants and waste
water treatment)

7. Desulfurization (Gas washing) 14. Dyeing (Textile & Leather)

8. Feed additives (Formates for animal nutrition) 15. Fish silage (Salmonella control)
 Various Production Routes
There are many routes that were used and are still used to produce Formic Acid:

• From Sodium Formate

• From Synthesis Gas

• From Formamide

• From By-products

Among these methods the very common and easy route is from Synthesis Gas which includes Methanol
carbonylation, followed by hydrolysis of the ester and rectification of the products to produce formic acid.
 From Sodium Formate
Raw material used are:
• Sodium Hydroxide
• Carbon monoxide
• Sulfuric acid

REACTIONS Involved:
1. NaOH + CO HCOONa
2. 2HCOONa + H2S04 HCOOH + Na2S04
• Sodium hydroxide (97 to 98 %) is charged into a reactor equipped with agitator a
packed tower. Carbon monoxide, free from carbon dioxide which is obtained is
reacted with the caustic soda at 150 – 200 C temperature under a pressure of 100
– 150 psi. 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 is 90 – 95 %.
• The another, sodium formate route to formic acid depends on the salt being
available as either the by-product of pentaerythritol manufacture or as a
product of the reaction between sodium hydroxide and carbon monoxide under
pressure.

4HCHO + CH3CHO + NaOH C(CH20H)4 + HCOONa

• Companies having access to by-product salt may continue to use this process,
but in the absence of an inexpensive source of sodium formate, this process is
not competitive beacuse it requires the consumption of CO, caustic and
sulfuric acid, with the need to dispose of byproduct sodium sulfate.
• Also The addition of concentrated sulfuric acid to dry sodium formate results
in quite extensive decomposition with formation of carbon monoxide.
• The disadvantages are of a chemical nature in so far as decomposition
phenomena which can not completely be avoided during the reaction of solid
formates with concentrated sulphuric acid and necessarily lead to losses of
formic acid.
 From Formamide
Raw Material used:
• Ammonia
• Carbon Monoxide
• Sulfuric Acid

Reactions:
• NH3 + CO HCONH2
• 2 HCONH2 + H2S04 + 2H20 2 HCOOH + (NH4)2S04
Process
• In the production of formic acid via formamide, the formamide
may be produced by the reaction of ammonia and carbon
monoxide at high pressure in an alcoholic medium utilizing an
alkaline catalyst.
• The formamide intermediate then reacts with dilute sulfuric
acid to yield formic acid and aunnonium sulfate.
 FACTS
• This process has been practiced on an industrial scale in Europe, where
formamide is also used to manufacture HCN.
• The future of this route in Europe will, therefore, be affected by the hydrogen
cyanide demand and a significant factor will be the demand for HCN in the
production of acrylonitrile.
• Generally, the high price of formamide as obtained from the small scale plants
currently available and the need of an outlet for byproduct sulfate, makes this
route anything but attractive. Also, the recently reported teratogenicity of
formamide calls for stringent environmental and safety precautions
 Produced As By-Product
• In the manufacture of acetic acid by the catalytic oxidation of
paraffin hydrocarbons formic acid is obtained as a by-product.
• The bulk of the formic acid production in earlier years had been via
by-product from the liquid phase oxidation of butane to acetic acid.
• With the advent of other routes to acetic acid that are based on
cheaper raw materials and hence more economic than hydrocarbon
oxidation, it is not likely that expansion will occur in acetic acid,
and hence formic acid, capacity by this route.
From Producer/ Synthesis Gas)

Raw materials:

• Methanol
• CO
• Catalyst : potassium methylate
• H2O
• REACTION INVOLVED

METHYL FORMATE SECTION:

CO + CH3OH HCOOCH3

Carbon Monoxide + Methanol Methyl Formate

FORMIC ACID SECTION:

HCOOCH3 + H2O HCOOH + CH3OH

Methyl Formate + Water Formic Acid + Methanol

OVER ALL REACTION :

CO + H2O HCOOH
Carbon Monoxide Water Formic Acid
 METHYL FORMATE SECTION
• Measured quantity of Methanol, Carbon Monoxide and catalyst Potassium
Methylate are fed to Methyl Formate(MF) reactor.
• Liquid consist of Methyl formate, methanol, catalyst and dissolved salt is
taken from the bottom of the MF reactor in to vaporiser where most of the
MF is evaporates and fed to MF column. From the bottom of vaporiser
catalyst rich methanol solution is fed to the MF reactor top.
• Methyl formate is removed from the top of the MF column and taken to MF
storage tank. Methanol is removed from the bottom of MF column and fed to
Wet methanol tank for reuse.
 FORMIC ACID SECTION
• Measured quantity of MF and water are fed to Formic Acid Reactor. Hydrolysis of methyl formate
gives diluted Formic acid.

• From FA reactor the liquid consist of Formic acid, Methanol, M.F. and water is taken to 1st distillation
column.

• M.F. and methanol is removed from top and sent to MF column.

• 36 % Formic Acid is taken from bottom to 2nd distillation column.

• Water is taken out from the top of 2ndcolumn and feed back to FA Reactor. From the bottom of 2nd
column 82% Formic Acid is taken to the 3rdcolumn.

• 98% Formic Acid is taken out from the top of the 3rd column and mixed with bottom liquid of
2ndcolumn in a mixer to make 85% Formic Acid and transferred to batch tank. The bottom liquid of
3rd column is recycled back to 2nd column
Formic Acid Methanol Water
Advantages of the new formic acid production technology:
• Process flow simplicity with minimum number of technological steps
• Low capital investment
• Low cost of the final product
• Environmental safety of production:
1. All emissions from the process are purified at special gas cleaning
system;
2. The technological process allows avoiding contamination of sewage;
3. Full environmental safety can significantly reduce the sanitary protection
zone.
• High quality of the product produced
• Automatic dosing of methanol and air
Formic acid reduction capacity at the end of 2014

Process Capacity, t/a Percentage of total

capacity, %
Hydrolysis of methyl formate 770 000 81
Acidolysis of alkali formates 180 000 19
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