TABLE OF CONTENTS

1.1

OVERVIEW OF FORMIC ACID...................................................................................2

1.2

PHYSICAL AND CHEMICAL PROPERTIES...............................................................3

1.3

USES AND APPLICATION..........................................................................................4

1.4

PRODUCTION OF FORMIC ACID..............................................................................7

1.4.1

SODIUM FORMATE..............................................................................................7

1.4.2

HYDROLYSIS OF FORMAMIDE...........................................................................7

1.4.3

BUTANE LIQUID-PHASE OXIDATION..................................................................7

1.4.4

METHYL FORMATE HYDROLYSIS......................................................................8

1.5

PATENTED PRODUCTION OF FORMIC ACID...........................................................8

1.5.1

PRODUCING FORMIC ACID FROM A CARBOHYDRATE-CONTAINING

MATERIAL........................................................................................................... 8

1.5.2

MANUFACTURING FORMIC ACID BY METHYL FORMATE HYDROLYSIS.....11

1.5.3

MANUFACTURING FORMIC ACID BY METHYL FORMATE HYDROLYSIS.....13

1.6

PROCESS SELECTION...........................................................................................16

1.6.1
1.7

SCORING METHOD..........................................................................................17

CATALYST................................................................................................................ 19

1.7.1

CATALYST SELECTION....................................................................................19

1.7.2

CATALYST PHASE............................................................................................20

1.8

MODIFIED FORMIC ACID PROCESS......................................................................21

1.9

PROCESS FLOW DIAGRAM (PFD).........................................................................22

1.10

PROCESS DETAILS.................................................................................................23

1.10.1

CARBONYLATION OF CARBON MONOXIDE AND METHANOL...................23

1.10.2

SEPARATION OF REACTANT........................................................................24

1.10.3

HYDROLYSIS REACTION OF METHYL FORMATE.......................................24

1.10.4

SEPARATION OF METHANOL.......................................................................25

REFERENCES.................................................................................................................... 26

CHAPTER 1

PROCESS BACKGROUND

1.1

OVERVIEW OF FORMIC ACID

John Ray an English naturalist was claimed to be the first person that discovered formic acid
back in 1671. It is found as active ingredient in dead ants. So, its name came from Latin
word for ant which is formica. A French chemist, Joseph Gay-Lussac was the first person to
synthesize formic acid from hydrocyanic acid. Followed by another French chemist,
Marcellin Bathelot had synthesized formic acid from carbon monoxide back in 1855 but the
idea still being applied until nowadays (Laffitte, 2005).
In petrochemical processing, formic acid is a by-product of acetic acid production, by
oxidation of n-butane. After the end of the World War 2, the production of formic acid has
been introduced through the process. In United States, this process is the main method to
produce formic acid. Inversely in Europe at that time, the production of formic acid is far
more advanced with many types of methods. The methods are including the acetic acid byproduct in petrochemical processing, the acidolysis of formamide by sulfuric acid, the
acidolysis of alkali metal formate, and sodium formate decomposition. The most prevailing
method even until today is the carbonylation of methanol to methyl formate with the
presence of catalyst, followed by the hydrolysis of methyl formate to formic acid
(Gunardson, 1998). The reactions are shown below as Equation 1 and 2.

C H 3 OH +CO HCOOC H 3
Methanol
2

Methyl formate

[1]

HCOOC H 3 + H 2 O C H 3 OH + HCOOH
Methyl formate

[2]

Formic acid

Based on equations 1 and 2, it can be simplified that formic acid is produced by reaction of
carbon monoxide with water as depicted in Equation 3.

CO+ H 2 O HCOOH

[3]
(Source: Gunardson, 1998)

1.2

PHYSICAL AND CHEMICAL PROPERTIES

Formic acid is also known as methanoic acid, formylic acid, or hydrogen carboxylic acid,
which is the simplest carboxylic acid (PubChem, 2015). It consists of one carbon atom, two
oxygen atoms and two hydrogen atoms with the molecular formula of

CH 2 O2 . Formic

acid is a clear, colorless liquid with pungent and irritating odor. As it is the simplest carboxylic
acid, it is miscible in water with release of heat and fumes in air. Carboxylic acid is stable
and it must be prevented from strong bases, strong oxidizing agents and powdered metals.
It is also a hygroscopic which is the ability to adsorb water from its surrounding. Table 1.1
shows the physical and chemical properties of formic acid.
Table 1.1: Physical and chemical properties of formic acid.
Physical properties
Formula

Formic acid

References

CH 2 O2

Perry and Green, 1999

Structure
PubChem, 2015

46.03

Molecular weight

Perry and Green, 1999

Perry and Green, 1999

Form and color

Colorless liquid

Specific gravity

1.22020/4

Melting point, C

8.6

Boiling point, C

100.8

Physical state

Liquid

Avogadro Chem, 1999

Pungent odor

Avogadro Chem, 1999

Auto-ignition point, C

434

Avogadro Chem, 1999

Flash point, C

69

Avogadro Chem, 1999

Strong acid

Avogadro Chem, 1999

Miscible in ether, acetone,

ONeil, 2006

Odor

pH
Miscibility

Perry and Green, 1999

Perry and Green, 1999
Perry and Green, 1999

ethyl acetate, methanol,

ethanol.
Miscible partially in benzene,
toluene, and xylenes.
Water solubility

1.3

100000 mg/L at 25 C

Riddick et al., 1985

USES AND APPLICATION

The major use of formic acid (methanoic acid, HCOOH) in Europe is as a preservative and
antibacterial agent in livestock feed. It can stop or delay certain decay processes of fresh
hay or other silage. In the same time, it can kill salmonella bacteria in the livestock feed. To
do so, formic acid can be sprayed on them (Laffitte, 2005). When it is used in silage, it
serves a dual function. Besides acts as antibacterial, formic acid also allows the sprayed
silage to begin its fermentation process at a certain temperature. This will greatly reducing
the overall time to produce the livestock feed while in the same time increasing the
nutritional value of the finished product. Therefore, it allows the silage to be preserved
longer and this is very beneficial where it can be kept for winter supply where silage cannot
be produced in that season (Acidpedia, 2015).
4

To kill mites that attack the honey bees, formic acid has been used by some
beekeepers. In textile industries formic acid is used for dyeing, finishing, and leather
tanning. Formic acid has proven itself to be perfect for use in textile because of it acidic
nature. Some metal salts can be produced from formic acid like nickel, cadmium, and
potassium formates. In perfume industries, it is used as solvent for perfumes. In addition, it
is used in manufacturing lacquers, glass, vinyl resin plasticizers. In food industries, it is used
as flavor, fragrance, and synthesis of an artificial sweetener which is aspartame (Laffitte,
2005).
Formic acid has been recently developed to help fight slippery road conditions.
Austria and Switzerland are example of countries that have applied this application. In winter
season at these countries, roads condition is very dangerous. The roads are very slippery
where formate, salts that are derived from formic acid is used to increase the gripping ability
of the roads. Furthermore, formate salt is said to be more environmentally friendly compare
to other alternative salts (Acidpedia, 2015). Table 1.2 shows the summary usages and
applications of formic acid in industries.
Table 1.2: Applications of formic acid in industries (BASF, 2014).
Industries
Cleaning and caring

Application
Detergents
Floor Cleaner
General use cleaner
Industrial Cleaners

Food and Beverage

Sanitary Cleaners
Alcoholic drinks, Beer
Food processing

Livestock breeding, Pets

Disinfectant (food processing)

Pigs
Fattening pig
Piglet
Sow
Poultry
Breeder
Ruminants
Calf
5

Cattle
Manufacturing

Dairy cow
Chemical Manufacturing
Manufacturing of cleaners
Manufacturing of pesticide, fertilizer
Manufacturing of pharmaceuticals
Fluid and gas treatment
Gas purification
Water preparation
Rubber Processing
Tires
Water treatment, Drinking water
Industrial
Municipal

Mining, Oil & Gas

Sugar processing
Oil and gas extraction

Textiles and Leather

Boring
Finishing of textiles
Bleaching (textiles)
Mercerization (textile finishing)
Pretreating (textile finishing)
Leather manufacture
Tanning, Retanning

1.4

PRODUCTION OF FORMIC ACID

Based on Reutemann & Kieczka, (2005), there are four methods to produce formic acid
which are:
1. Sodium formate
6

2. Hydrolysis of formamide
3. Butane liquid-phase oxidation
4. Methyl formate hydrolysis

1.4.1

SODIUM FORMATE

Production of formic acid from sodium formate is a traditional ways. Even though, the
technology is the oldest technology used to produce formic acid but it have some
disadvantages such as poor working conditions and serious pollution. Long time, many
industries apply this technology to produce formic acid but nowadays they prefer to choose
another technology (Reutemann & Kieczka, 2005).

1.4.2

HYDROLYSIS OF FORMAMIDE

This method to produce formic acid was developed by German BASF Company. The
process to produce formic acid has three stages. The first stage involves a carbonylation of
methanol to produce methyl formate. The second stage is to produce formamide through
ammonolysis of ethyl formate. And the third stage is by using sulfuric acid to hydrolyze
formamide to formic acid and ammonium sulfate. But after years employ this method, the
technology claims having higher cost of production (Reutemann & Kieczka, 2005).

1.4.3

BUTANE LIQUID-PHASE OXIDATION

Formic acid is produced as a by-product by applying the liquid phase oxidation of n-butane.
In this method, butane becomes a hydrocarbon. In the first separation process from
oxidation product, butane which do not react yet with volatile neutral constituents and water
are separated first. Formic acid is produced in the next column. The possibility of getting the
percentage of formic acid is about 90wt% and can also obtain at 98wt% in further separation
(Reutemann & Kieczka, 2005).

1.4.4

METHYL FORMATE HYDROLYSIS

Methyl formate hydrolysis is the latest method used by most of the industries in the world to
produce formic acid. The method usually modified by different of technologies depends on
requirement of the company. This technology has been used by Kemira-Leonard, BASF and
USSR. This method is basically has two stages. The first stage is known as carbonylation
process and second stage are known as hydrolysis process. For the carbonylation process,
methanol is carbonylated with carbon monoxide. Some of researcher found out
homogenous catalyst used during this process can speed up the reaction. Then, the main
product from the carbonylation process which is methyl formate is hydrolyzed to formic acid.
The hydrolysis process is newly found out to be economically feasible after years of
reasearch. This method is found to be less heat consumption, most reasonable process,
and less cost compare to another method. But in order to achieve high purity of formic acid,
the azeotrope may form between water and formic acid where good separation technique is
needed (Reutemann & Kieczka, 2005).

1.5

PATENTED PRODUCTION OF FORMIC ACID

In this sub-topic, three different patented productions of formic acid will be discussed. In
order to understand the formic acid production in industries scale, studying industries patent
is the best way to do so where the process is more realistic, practical, and in details.

1.5.1

PRODUCING FORMIC ACID FROM A CARBOHYDRATE-CONTAINING

MATERIAL (Fitzpatrick et. al., 2012).

By using acid treatment, carbohydrate molecules like glucose polymer, galactose, or similar
hexone sugars can be hydrolyzed to become hexone monomers. Further hydrolysis will
result to the formation of formic acid and levulinic acid. Example of carbohydrate-containing
materials that can be used as raw material of the process are paper pulp, wood, food waste,
switch-grass, waste paper and straw. The raw material must containing cellulose for the
hydrolysis process to produce sugar. The process is consisting of multiple reactions or steps
as shown in Table 1.3.
8

Table 1.3: Process steps of formic acid production from a carbohydrate-containing material.
STEP
1st

PROCESS
Sugar (intermediate hydrolysate) is produced by acid hydrolysis of the raw

2nd

material that containing cellulose

Further hydrolysis of the intermediate hydrolysate to become end product

3rd

containing formic acid.

Separation process of formic acid from the hydrolysate product.

The yield of formic acid can be greater than 55% and theoretically can be greater
than 70%. To initiate the process, an acid like sulphuric acid, nitric acid, phosphoric acid,
hydrochloric acid, hydrofluoric acid, or hydrobromic acid is added to the raw material and the
mixed becoming aqueous slurry. Temperature and pressure of the process conditions is
adjusted for allowing the hydrolysis process. Table 1.4 below shows the summary of the
process while Figure 1.1 shows the process flow diagram (PFD) of the process.
Table 1.4: Process summary of formic acid produced from carbohydrate-containing material.

PARAMETER
Year of process patent
Raw material

PROCESS CHARACTERISTIC
2012
1. Carbohydrate-containing
material
(Example, paper pulp, wood, food waste,
switch-grass, waste paper and straw)
2. Sulphuric acid, nitric acid, phosphoric acid,
hydrochloric acid, hydrofluoric acid, or

By product
Highest possible process temperature
Highest possible process pressure
Yield percentage
Catalyst
Operating equipment

hydrobromic acid
1. Levulinic acid
2. Carbon monoxide gas
3. Water
235 C
Not mentioned
55%
Not used.
1. Grinder
2. Mixer
3. Pump
4. Plug flow reactor (PFR)
5. Continuous stirred tank reactor (CSTR)
6. Flash tank
9

Figure 1.1: PFD of formic acid production from a carbohydrate-containing material

(Fitzpatrick et. al., 2012).

1.5.2

MANUFACTURING FORMIC ACID BY METHYL FORMATE HYDROLYSIS

(Hohenschutz et al., 1980).

This process is introduced to improve the formic acid production by using acidolysis of
formamide with sulfuric acid which has been claim to produce too much of ammonium
sulfate as the by product, which is not favorable. This patent is also claimed to have better
process properties compare to German Patent No. 2,407,157, which is the production of
formic acid by methyl formate hydrolysis. The process is said to be unacceptable due to the
usage of special distillation process to repressed high rate of re-esterification resulting from
the usage of a catalyst. The special distillation process uses a large amount of steam which
is seem uneconomical because the formic acid produced only 75% purity by weight which is
contrast from higher purity demand. Hohenschutz et al., (1980), has introduced the better
process of formic acid production by improving the method by using methyl formate
10

hydrolysis. The process uses raw material of methyl formate with purity of 97% by mole
percent with the remaining component of methanol, water, and a bases which is 1-(1-npentyl)-imidazole. The process is consisting of multiple reactions or steps as shown in Table
1.5:
Table 1.5: Process steps of formic acid production by methyl formate hydrolysis.

STEP
1st

PROCESS
Methyl formate, water, and 1-(1-n-pentyl)-imidazole are introduced into a
tubular reactor. Hydrolysis of methyl formate occurs in the reactor and

2nd

producing formic acid.

The outlet stream of the reactor is send to the 1st packed column to

3rd

separate the unreacted methyl formate and recycled it back to the reactor.
The stream containing formic acid, water, and the base is send to the 2 nd
packed column to separate water which is also being recycled back to the

th

reactor.
The remaining stream is send to the 3rd packed column to separate the
base from the product, formic acid. The base is recycled back to the

th

reactor.
The formic acid is further treated in the 4th packed column to produced

higher purity of formic acid.

This whole process is achieving 99% of formic acid yield while the conversion of methyl
formate is 64%. For every ton of formic acid produced, 2.2 ton of steam utility is used for the
entire process. This process is claimed to be more economical compared to the other
methods that has been mention before. The main key that contributed to its advantageous
process is the usage of the base in the methyl formate hydrolysis. This is because the base
can form a saltlike bond with formic acid which is sufficiently strong to withdraw the product
from the hydrolysis equilibrium. The other advantages of the process are no by-product
produced and low energy consumption. The summary of the process characteristics is
shown in Table 1.6 below.

Table 1.6: Process summary of formic acid production by methyl formate hydrolysis

PARAMETER
Year of process patent

PROCESS CHARACTERISTIC
1980
11

Raw material
By product
Highest

possible

process

temperature
Highest possible process pressure
Yield percentage
Purity
Catalyst
Operating equipment

1.5.3

1. Methyl formate
2. 1-(1-n-pentyl)-imidazole
3. Water
No by product
130 C

1.
2.
3.
4.
5.

10 atm
99%
Not mentioned
No catalyst
Tubular flow reactor (PFR)
1st packed column
2nd packed column
3rd packed column
4th packed column

MANUFACTURING FORMIC ACID BY METHYL FORMATE HYDROLYSIS

(Huang et. al., 2012)

In this patent, formic acid is produces by reacting carbon monoxide and methanol by
carbonylation reaction with a present of heterogeneous catalyst to produce methyl formate.
In further reaction of methyl formate with water by hydrolysis process is producing formic
acid. The process consists of 6 main steps. Table 1.7 shows the main steps of the formic
acid production.
Table 1.7: Process step of formic acid production by methyl formate hydrolysis.

STEP
1st

PROCESS
Carbonylation reaction of methanol with carbon dioxide in a CSTR with the
present of a heterogeneous catalyst. The reaction is producing methyl

2
3rd

formate.
The mixture of the reactor is sent to a first separator which is a flash column.
The mixture from the first separator containing methyl formate is sent to a

4th

second separator which is a distillation column.

The mixture from the second separator containing methyl formate is sent to

nd

a reactive distillation column (RDC). In the RDC, water is introduced and

5th

reacts with the methyl formate to produce formic acid by hydrolysis reaction.
The mixture from the DC is conveyed to a third separator which is a
12

th

distillation column.
The mixture from the third separator containing formic acid is sent to a forth
separator (distillation column) to produce high impurity of formic acid.

The process consists of many separation processes because formic acid and water
is forming azeotrope mixture. Although the process consists of many separation processes,
the purity of the produced formic acid is very high which is 99% by weight percent. The
summary of the process characteristics is shown in Table 1.8 while Figure 1.2 shows the
process flow diagram (PFD) of the process.

Table 1.8: Process summary of formic acid production by methyl formate hydrolysis.

PARAMETER
Year of process patent
Raw material
By product
Highest

possible

process

temperature
Highest possible process pressure
Yield percentage
Purity
Catalyst
Operating equipment

PROCESS CHARACTERISTIC
2012
1. Carbon monoxide
2. Methanol
3. Water
No by product
107 C
40 atm
Not mentioned
99% (by weight percent)
Sodium methoxide or ion-exchange resin
1. Plug flow reactor (PFR) or Continuous
2.
3.
4.
5.
6.

13

stirred tank reactor (CSTR)

First separator (Flash tank)
Second separator (distillation column)
Reactive distillation column
Third separator (distillation column)
Fourth separator (distillation column)

Figure 1.2: PFD of formic acid production by methyl formate hydrolysis (Huang et. al., 2012).
.

14

1.6

PROCESS SELECTION

To select the best process to be applied in the formic acid production, some characteristics
of the process are being compared. Parameters that need to be considered in the process
selection are year of the process patented, cost of raw materials, safety, product purity, use
of catalyst, and environmental effect. Table 1.9 shows the reasons of why each parameter
should be considered in process selection.
Table 1.9: Comparison parameters and its significant in process selection.

COMPARISON

DESCRIPTION

PARAMETER
Year of process patented

Year of the process patented represent which process is the

latest technology used in the formic acid production. The
newest technology is favorable due to the improvement that

Cost of raw materials

has been made compared to the older one.

Cheap cost of raw material is advantageous so that the product
can be sold at low price compared to the same product with

Safety

expensive raw material.

Safety is important to make sure the production is not halted
due to accident happen in the workplace. One of the causes
that can initiate accident is the operating conditions of the
process.

High

temperature

and

pressure

of

operating

conditions has higher probability to cause an accident due to

the

dangerous

conditions.

Therefore,

low

operating

temperature and pressure is favorable for safer working

Product purity

condition.
Product purity is also representing the quality of the product.
Product with low purity will make the customer need to execute
additional purification process. If there is the same product with
higher purity, the customer will choose the product with high

Use of catalyst

purity due to its higher quality.

Usage of catalyst also representing the operating cost.
Regenerating or replacing the catalyst will increase the
operating cost and in the same time difficult to dispose the
15

used up catalyst, where additional cost will be spent.

Environmental effect of a process can be identified based on

Environmental effect

the emission of gas produced, waste water, or by products.

Process that produce gas, liquid, or solid pollutants to the
environment is not favorable. Besides, additional process is
required to treat the pollutants before being released to the
environment. This will cost a huge amount of money.

1.6.1

SCORING METHOD

One of the methods that can be used to choose the best process is by using concept
scoring method. This is a quantitative method where the criteria of each process are being
scored based on its favorability. The process criteria will be scored from range 1 to 5 based
on the process properties either it is:
1= Bad

2= Quite bad

3= Good

4= Very good

5= Outstanding

For any process that has no information on its criteria will be scored as bad or 1 due to the
information limitation which is assume as unfavorable in process selection. Each criterion is
also being weighted based on the importance of the parameter to be considered in the
process

selection.

Total

Score Weightage fraction

score

of

each

process

will

be

calculated

by

. Table 1.10 shows the concept scoring method. To make

the cost of raw material can be compared, the cost of each material is identified based on its
recent market value. The costs of the materials are being referred from Malaysia External
Trade Development Corporation (MATRADE), except cost of water which is referred from
the India water tariff for industrial usage. Based on the result of the concept scoring method,
manufacturing formic acid by methyl formate hydrolysis invented by Huang et al., (2012), will
be selected as it has the highest score of 2.72.

16

Table 1.10: Concept scoring method for process selection.

CRITERION

WEIGHT

Year of
patented
Cost of raw
materials

10%
14%

Formic acid production from a

carbohydrate-containing material
(Fitzpatrick et. al.)
CHARACTERISTIC
2012
Carbohydratecontainining material
(USD 0.5/kg of paper)

SCORE
4

Product purity
Use of catalyst
Environmental
effect

Total score
Rank

15 %

20%
5%
18%

Highest operating
temperature is 235C
while the pressure is not
mentioned.
50%
No
Producing carbon
monoxide gas, a
greenhouse effect gas.

CHARACTERISTIC
2012

SCORE
4

Carbon monoxide (USD

0.0223/kg)
5

Sulfuric acid (USD

0.29/kg)
Safety

Formic acid production by

methyl formate hydrolysis
(Huang et al.)

1
5

Formic acid production by methyl

formate hydrolysis (Hohenschutz
et al.)
CHARACTERISTIC
1980
Methyl formate (USD
1.2/kg)

Methanol (USD 0.28/kg)

Water (USD 0.1/m3)

Water (USD 0.1/m3)

1-(1-n-pentyl)-imidazole

Highest operating
temperature and
pressure are 107C and
40 atm, respectively.
99%
Yes
Released a small
amount of methanol,
methyl formate, and
carbon monoxide
through purge stream.

2.03
2

5
2

2.72
1

17

SCORE
1

(USD 2/kg)
Highest operating
temperature and pressure
are 130C and 10 atm,
respectively.
>75%
No
Released a small amount
of methanol, methyl
formate, and formic acid
through purge stream.

3
5

2.04
3

1.7

CATALYST

Based on the process selection, formic acid production invented by Huang et al., (2012) is
selected. This patent has proposed using sodium methoxide or ion exchange resin catalyst
for the carbonylation process of methanol and carbon monoxide. Therefore, a selection of
catalyst must be made in order to identify which catalyst is the best for the process. The
selection will be made based on safety because this is the most concern criteria for catalyst
usage.

1.7.1

CATALYST SELECTION

Based on Kwok et al., (2013) on their study on fire and explosion safety of sodium
methoxide as catalyst in industries, the study revealed that this substance is very
hazardous. This catalyst is very reactive with water, air, and carbon dioxide where all of
these elements present in the surrounding air. So, the catalyst must be stored in an air tight
container where is must not be exposed to the surrounding. The study has revealed that
self-heating is possible at temperature slightly higher than the room temperature and the
dust explosion test is resulting that its dust is explosive. But what make it more surprising is
that, the present of methanol along with the catalyst is not favorable where it will increase its
flammability. The mixture of sodium methoxide solution in methanol can become flammable.
This study also reported that this catalyst also can cause hot-spot formation, so this hot-spot
can cause the mixture of methanol and sodium methoxide to catch in fire. In the formic acid
production process, methanol is used for carbonylation process. Therefore, the probability of
explosion and fire is very high if sodium methoxide is used. Although this catalyst has been
used in some industries, more safety precaution is needed in order to handle this catalyst.
Rather than risking workers life, it is more appropriate to use a safer catalyst.
As proposed by Huang et al., (2012), ion exchange resin can be used as the catalyst
for carbonylation of methanol with carbon monoxide. Based on material safety data sheet
(MSDS) of ion exchange resin developed by Thermo Fisher Scientific (2015), the hazardous
identification of this catalyst is only hazardous to eye where wearing personnel protective
equipment is adequate. Its autoignition point is greater than 500C while there is no data on
18

flammability, explosive, and toxicology level where in other means, this catalyst does not
exhibits those types of hazards. Therefore, it is concluded that ion exchange resin is
selected to be used as catalyst in formic acid production process due to its safer usage
compare to sodium methoxide.

1.7.2

CATALYST PHASE

The other concern that needs to be considered is the phase of catalyst. This is because
there are two types of ion exchange resin catalyst phases sold in market which are solid and
liquid. A study was done by Lin et al., (2014) on the properties of solid and liquid sulphuric
acid catalyst on sugar hydrolysis. The study revealed that liquid catalyst result 60% yield in 2
hours while solid catalyst results 30% yield in 12 hours. This shows that, liquid catalyst is
more efficient compared to solid type where it can produce higher conversion and faster
reaction. Therefore, liquid ion exchange resin catalyst is selected for the carbonylation
reaction process in formic acid production. Inversely for hydrolysis process of methyl
formate to formic acid, solid ion exchange resin catalyst will be used because reactive
distillation column is used. This equipment is capable of handling solid catalyst only
(Klemola, 1998). So, liquid catalyst is not possible for this equipment. Table 1.11 concluded
the selected type of catalyst for reactions present in the formic acid production process.
Table 1.11: Types of catalyst for formic acid production process.
Reaction
Carbonylation of methanol with carbon monoxide

Catalyst
Liquid ion exchange resin

to produce methyl formate.

Hydrolysis of methyl formate with water to

Solid ion exchange resin

produce formic acid and methanol.

19

1.8

MODIFIED FORMIC ACID PROCESS

Based on the process selection, the process patented by Huang et al., (2012) is selected.
This process will be applied in this formic acid production design process with some
modifications. There are two major modifications that have been done which are the removal
of the first separation device (flash drum) and the fourth separation device (distillation
column).
The reason of eliminating flash drum usage will be discussed in simulation chapter
(Chapter 7) under ASPEN PLUS process design sub-topic. The justification is discussed
under that topic because it requires some simulation data in order to explain the reason.
Therefore, it will be more appropriate and understandable to explain the reason with the aid
of stream summary result of the simulation.
The elimination of the fourth separation device is because of different target product
purity. Formic acid and water mixture exhibits azeotropic mixture where more separation
devices are required to separate the water from formic acid. To do so Huang et al., (2012) is
using two distillation columns to achieve the required product purity. The third separation
device is able to produce 85% purity of formic acid and further separation process with the
fourth separation device can produce 99% purity of formic acid. In this formic acid process
design, the required product purity is only 85%. Thus, the fourth separation device is not
required for this formic acid process design. The reason of producing 85% product purity will
be discussed in simulation chapter (Chapter 7) under separation process efficiency subtopic.
The finalized and modified process flow diagram of the formic acid process is
depicted as in Figure 1.3 and the process details are discussed in the next sub topic.

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1.9

PROCESS FLOW DIAGRAM (PFD)

C-101
Compressor

E-101
Heat exchanger

R-101
CSTR

T-102
Dist. Column 1

T-102
Reactive dist. column

P-101
Pump

M-101
Mixer

C-102
Compressor

E-105
Heat exchanger

T-103
Dist. Column 2

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1.10

PROCESS DETAILS

The main equipment used in the formic acid plant includes a reactor, first separation device,
a reactive distillation device, and second separation device. The reactant for formic acid,
methyl formate is produced in the reactor by performing a carbonylation reaction process of
carbon monoxide and methanol with the present of ion exchange resin catalyst. The process
to produce formic acid is done by hydrolyzing the produced methyl formate in excess water
at the reactive distillation device.
The overview of the overall process can be seen below:
1. Carbonylation reaction of carbon monoxide and methanol to produce methyl formate
in reactor.
2. Separation of unreacted methanol from the mixture in the first separation device.
3. Hydrolysis reaction of methyl formate and external water to produce formic acid and
methanol in the reactive distillation column.
4. Separation of methanol from the mixture in the second separation device to produce
high purity of formic acid.

1.10.1

CARBONYLATION OF CARBON MONOXIDE AND METHANOL

The reactor is used as the site for carbonylation process. The reactor used is a

continuous stirred tank device (CSTR). The reactor is set at a pressure of 20 50atm and a
temperature of 60 - 1000C. The reactant, carbon monoxide (CO) and methanol (CH 3OH) are
supplied into the reactor from their own loading chamber. The formula for the carbonylation
reaction is:

C H 3 OH +CO HCOOC H 3

H R =29 kJ /mol

The reaction is done in the presence of a heterogeneous catalyst. In this plant, the catalyst
used is ion-exchange resin. Based on Gunardson (1998), the concentration of the catalyst
must be maintained at 2wt % of the total mass in the reactor. The output of the reactor
includes the reaction product, methyl formate, HCOOCH 3 as well as some of the unreacted
reactants, carbon monoxide and methanol.
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1.10.2

SEPARATION OF REACTANT

The output of the reactor is then fed to the first separator unit. The main function of
employing this unit is to separate the unreacted methanol from the mixture to be recycled to
the reactor. This will facilitate the carbonylation reaction process thus increasing the
production rate. The pressure for this separation unit is set at 3 5atm. It includes a
distillation column, a reboiler device, a condenser device and a reflux device.
The bottom product from the distillation column is fed to the reboiler device. The
output of the reboiler device is a mixture with high content of methanol that has higher
boiling point than the feed stream for the distillation column. This mixture is divided into two
streams with one re-entering the distillation column while the other is recycled to the reactor
unit.
The top product from the distillation column is fed to the condenser device and then
to the reflux device. For safety reasons, the condenser device is designed to vaporize any
remaining carbon monoxide in the stream. The output of the reflux device is a mixture of
methanol and methyl formate. It is divided into two streams with one stream refluxed back to
the distillation column while the other stream is fed to the reactive distillation column.

1.10.3

HYDROLYSIS REACTION OF METHYL FORMATE

The reactive distillation unit is used as the process unit for hydrolysis process. The pressure
for this unit is set at 3 5atm. This unit includes a reactive distillation column, a reboiler
device, a condenser device, and a reflux device. The reactive distillation column includes
several reactive trays and stripping trays. The reactive trays are filled with ion-exchange
resin, a heterogeneous catalyst to prepare for the reaction process. The stripping trays are
situated below the reactive trays and are used to separate the mixtures. The column is
divided into two zones which are reactive zone, where reactive trays reside and stripping
zone, region which has stripping trays.
In this unit, the reaction occurs at the reactive zone. The reactants, methyl formate
and water react in a hydrolysis reaction to produce formic acid and methanol. The reaction
formula is:
23

HCOOC H 3 + H 2 O C H 3 OH + HCOOH

H g =+16.3 kJ /mol

Water for the reaction is provided from a loading chamber into the reactive trays. Position of
the water inlet is higher than the feed inlet on the reactive distillation column due to water
having a higher boiling point than the feed. The most preferred position for the water inlet is
at the highest reactive tray. Water moves down the column while methyl formate vaporizes
upwards during the hydrolysis reaction.
The top product from the reactive distillation column is fed to the condenser device
and then into a reflux device. This stream mainly consists of unreacted methyl formate and
needs to be refluxed back into the column. Heterogeneous catalyst can also be filled in the
reflux device to maximize the conversion rate.
The bottom product from the reactive distillation column is fed to the reboiler device.
The output of the reboiler device consists mainly of unreacted water as well as formic acid
and methanol. It is divided into two streams where one of them is sent back to the reactive
distillation column. The other stream is fed to the second separator unit. This stream must
be controlled to minimize the amount of methyl formate found inside.

1.10.4

SEPARATION OF METHANOL

The output of the reboiler device is fed to the second separation unit. This unit is used to
recycle methanol back to the reactor to facilitate the carbonylation reaction process and in
the same time to produce high purity of formic acid. The pressure set for this separation unit
is 3 5atm. This unit includes a distillation column, a reboiler device, a condenser device
and a reflux device.
The top product from the distillation column is fed to the condenser device and then
to the reflux device. The mixture on the outlet of the reflux device mainly consists of
methanol. One part of this mixture is refluxed back into the distillation column while the other
part is recycled to the reactor to be used in carbonylation reaction process. A pump is
employed in the recycle stream due to the pressure in the reactor being higher than the
pressure in the second separation unit.

24

The bottom product from the distillation column is fed to the reboiler device. The
output of the reboiler device consists mainly of formic acid and excess water. It is divided
into two streams where one of them is sent back to the distillation column while the other is
taken as the desired product. The product stream has higher boiling point when compared to
the feed for the third separation unit. The concentration of the formic acid in the product
mixture is expected to be about 85wt%.
In the overall process, the net reaction is between water and carbon monoxide to
produce formic acid. This is found through deduction of the two processes involved;
carbonylation and hydrolysis to produce a net chemical formula of:

C H 3 OH +CO HCOOC H 3
HCOOC H 3 + H 2 O C H 3 OH + HCOOH
CO+ H 2 O HCOOH

From the overall reaction, it is found that in order to produce formic acid with high purity, the
mole ratio between carbon monoxide and water used in the production should be 1:1 during
a constant time period. This helps prevent unreacted reactants from blending with the
production of formic acid (Huang et al., 2012).
All of the justifications of equipment sequence, choice of equipment, separation
process efficiency, and operating pressure are discussed in simulation chapter (Chapter 7).
In the same chapter, raw materials purity, inlet and outlet pressure/temperature are also
discussed.

25

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