CHAPTER I

INTRODUCTION TO OXALIC ACID

1.1

INTRODUCTION

Oxalic acid or the IUPAC name is ethanedioic acid is an organic compound with the
molecular formula H2C2O4. Oxalic acid can be classified as the simplest dicarboxylic
acid and one of the type of reducing sugar. It is a colourless crystalline solid that
forms a colourless solution in water. It is soluble in water and have a good acid
strength because in term of acid strength, it is stronger than acetic acid. Oxalate (
2
C2 O4 ) acts as conjugate base is a chelating agent for metal cations. Typically,
oxalic acid occurs as the dihydrated with the molecular formula H 2C2O4.2H2O. Figure
1.1 shows the skeletal formula of oxalic acid while figure 1.2 shows that the structural
formula of oxalic acid.
Carbon
Hydrogen

Oxygen
Figure 1.1: Skeletal Formula of Oxalic Acid (Wikipedia, 2015)

Figure 1.2: Structural Formula of Oxalic Acid (Wikipedia, 2015)

1.1.1

Physical and Chemical Properties

Table 1.1: Physical and Chemical Properties

Characteristics
Physical State
Molecular Weight

Properties
Powder
90.03 g/mol (Anhydrous)

Density

126.07 g/mol (Dihydrate)

1.90 g/cm3 (Anhydrous)

Acidity (pKa)
Flash Point
Melting Point
Boiling Point
Vapour Density
Vapour Pressure
Solubility in Water

1.653 g/cm3 (Dihydrate)

1.25, 4.14
166C
101.5C
149 160C
4.4 ( Air = 1)
< 0.001 mm Hg (20C)
143 g/L (25C)
Source: MSDS Oxalic Acid, 2015

Oxalic acid is a colourless, crystalline, toxic organic compound belonging to the

family of dicarboxylic acids. Based on table 1.1, the melting point of oxalic acid is at
101.5C specifically in form of dihydrate. It is also soluble in water, alcohol, and
ether. It occurs in the form of its metal salts (usually calcium or potassium) in many
plants (Chemicalland21, 2007).
Oxalic acid is the only possible compound in which two carboxyl groups are
joined directly, for this reason oxalic acid is one of the strongest acids in organic
compounds. Unlike other carboxylic acids, oxalic acid (and formic acid) is readily
oxidized and combine with calcium, iron, sodium, magnesium, or potassium to form
less soluble salts called oxalates. Oxalic acid and oxalates are useful as reducing
agents for photography, bleaching, and rust removal (Chemicalland21, 2007). Oxalic
acid is a normal metabolite of carbohydrates in normal quantities, e.g., Fructose,
Glycine, and Vitamin C (Amit Sethy, 2013).
1.2

ROUTES OF MANUFACTURE PRODUCT

There are mainly six methods for producing oxalic acid and the process depends upon
the raw material selected. It can be prepared from various materials such as ethylene,
ethylene glycol, propylene, lignin, molasses, sugarcane, sugars, flour, plant wastes,
formate, carbonate and bicarbonate salts etc. by using different methods. These
methods are classified in six groups, namely: (i) fusion of sawdust with caustic soda,
(ii) oxidation of olefins and glycols, (iii) radiation processing of carbonate solutions
and molasses, (iv) fermentation of carbohydrates, (v) oxidation of carbohydrates by
nitric acid, and (vi) decomposition of formates (Metin Guru et al., 2001).
The route that will be used in this project is the fifth method which is
production of oxalic acid from carbohydrates specifically sugarcane by using nitric
acid. The potential production of oxalic acid by the nitric acid oxidation of waste
cellulosic materials has long been recognized (Kirk, 1967). Most of these processes
involve the prior pre-treatment of the cellulosic material to produce a glucose solution,
which in turn is oxidized in a nitric acid or a nitric acid/sulfuric acid medium
according to the idealized reaction (Jack M. Sulllvan at al., 1983).

C6HI2O6 + 6HNO3

3H2C2O4

Glucose

Oxalic Acid

Nitric Acid

+ 6NO + 2H2O
Nitrogen
Oxide

(1)

Water

However, nitric acid is capable of effecting the simultaneous hydrolysis and

oxidation of solid cellulosic materials according to the following idealized equation
(Webber, 1934).
(C6H10O5)xH2O + (x - 1)H2O + 6xHNO3

3xH2C2O4 + 6xNO + 6xH2O

(2)

In order to make the process economically viable it is necessary to recover the oxides
of nitrogen produced during the reaction.

1.3

SOURCE OF RAW MATERIALS

The raw materials that used in this process is nitric acid, biomass (sugarcane), oxygen
gas, water, vanadium penta-oxide and aluminium oxide. Vanadium penta-oxide and
aluminium oxide will acts as catalyst in continues stirred tank reactor (CSTR) and
fluidized bed reactor respectively.

1.3.1

Nitric Acid

Nitric acid (HNO3) is a highly corrosive mineral acid. It is colourless liquid that used
in the manufacture of inorganic and organic nitrates and nitro compounds for
fertilizers, dye intermediates, explosives and many different organic chemicals.
Table 1.2: Physical and Chemical Properties of Nitric Acid
Characteristics
Molar Mass
Appearance
Odour
Density
Melting Point
Boiling Point
Solubility in water
Vapour Pressure
Acidity (pKa)

Properties
63.01 g/mol
Colourless, yellow or red furming liquid
Acrid, Suffocating
1.5129 g/cm3
-42C
83C
Completely miscible
48 mmHg (20C)
-1.4
Source: MSDS Nitric Acid, 2015
Table 1.3: List of Nitric Acid Supplier

No
1
2
3
4

Company Names
Bis Chemicals Sdn Bhd
H.M. Supplies and Trading
Obetech Pacific Sdn Bhd
Mey Chern Chemicals Sdn Bhd

Location
Shah Alam, Malaysia
Pulau Pinang, Malaysia
Klang, Malaysia
Port Klang, Malaysia

Source: Alibaba.com
1.3.2

Oxygen Gas

Oxygen (O2) is a colourless and odourless gas. It is vital for most life forms on earth.
The main industrial application of oxygen is combustion. Many materials that do not
normally burn in air will burn in oxygen so mixing oxygen with air greatly enhances
combustion efficiency in iron and steel, non-ferrous, glass and concrete industries.

Table 1.4: Physical and Chemical Properties of Oxygen

Characteristics
Phase
Appearance
Melting Point
Boiling Point
Density

Properties
Gas
Colourless liquid, pale blue
-218.79C
-182.962C
1.429 g/L
Source: MSDS Oxygen, 2015

Oxygen is a very reactive element that easily forms compounds such as oxides.
Under standard temperature and pressure conditions two oxygen atoms join to form
dioxygen (O2), a colourless, tasteless and odourless gas. Oxygen changes from a gas
to a liquid at a temperature of 182.96C, and then can be solidified or frozen at a
temperature of -218.4C.
Table 1.5: List of Oxygen Gas Supplier
No
1
2
3

Company Names
Location
Wisdom Trillion Enterprise
Damansara, Malaysia
Maser (M) Sdn Bhd
Kenanga International, Malaysia
B.i.g Industrial Gas Sdn Bhd
Kuching, Malaysia
Source: ExportersIndia.com

1.3.3

Vanadium (V) Oxide

Vanadium (V) oxide (vanadia) is the inorganic compound with the formula V 2O5.
Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when
freshly precipitated from aqueous solution, its colour is deep orange. Because of its
high oxidation state, it is both an amphoteric oxide and an oxidizing agent. From the
industrial perspective, it is the most important compound of vanadium, being principal
precursor to alloys of vanadium and is a widely used industrial catalyst.
Table 1.6: Physical and Chemical Properties of Vanadium (V) Oxide

Characteristics
Molar Mass
Appearance
Density
Melting Point
Boiling Point
Solubility in water

Properties
181.88 g/mol
Yellow solid
3.357 g/cm3
690C
1750C
0.8 g/L at 20C
Source: MSDS Vanadium (V) Oxide, 2015

Vanadium pentoxide melts at 690C and decomposes at 1750C. V3+ is a

strong reducing agent, which sets hydrogen free with water. This shows that Vanadium
pentoxide may only rarely be applicable as sole oxidizing agent. Of interest are its
abilities to form polyoxides.

Table 1.7: List of Vanadium (V) Oxide Supplier

No
1
2
3

1.3.4

Company Names
Location
Intercontinental Chemical CO LT
Cheras, Malaysia
Jukim Chemical (M) Sdn Bhd
Kuching, Malaysia
BIS Chemical Sdn Bhd
Shah Alam, Malaysia
Source: Alibaba.com

Aluminium Oxide

Aluminium oxide is a chemical compound of aluminium and oxygen with the

chemical formula Al2O3. It is the most commonly occurring of several aluminium
oxides, and specifically identified as aluminium (III) oxide. It is commonly called
alumina, and may also be called aloxide, aloxite, or alundum depending on particular
forms or applications.
Table 1.8: Physical and Chemical Properties of Aluminium Oxide
Characteristics
Molar Mass
Appearance
Odour
Density

Properties
101.96 g/mol
White solid
Odourless
3.95 4.1 g/cm3

Melting Point
Boiling Point
Solubility in water

2072C
2977C
Insoluble
Source: MSDS Aluminium Oxide, 2015

Based on table 1.8, aluminium oxide is insoluble in water. It reacts with acids
as well as bases. The hardness of aluminium oxide makes it useful as an abrasive It is
also useful as an electrical insulator. When aluminium oxide is used in metallic
aluminium, it prevents the aluminium from weathering because it prevents the metal
from further oxidation.
Table 1.9: List of Aluminium Oxide Supplier
No
1
2
3
4

1.3.5

Company Names
Location
Everbest Technology Sdn Bhd
Kuala Lumpur, Malaysia
Ahmadraz Chem Sdn Bhd
Bintulu, Malaysia
Excellence Business Industries Supply
Pulau Pinang, Malaysia
Portal Trading
Pulau Pinang, Malaysia
Source: Alibaba.com

Sodium Hydroxide

Sodium hydroxide (NaOH), also known as lye and caustic soda is an inorganic
compound. It is a white solid and highly caustic metallic base and alkali salt which is
available in pellets, flakes, granules, and as prepared solutions at a number of different
concentrations.
Table 1.10: Physical and Chemical Properties of Sodium Hydroxide
Characteristics
Molar Mass
Appearance
Odour
Density
Melting Point
Boiling Point
Solubility in water
Vapour Pressure

Properties
39.9971 g/mol
White, waxy, opaque crystals
Odourless
2.31 g/cm3
318C
1388C
1110 g/L (20C)
< 2.4 kPa at 20C
Source: MSDS Sodium Hydroxide, 2015

At room temperature, sodium hydroxide is a white crystalline odourless solid

that absorbs moisture from the air. It is a manufactured substance. When dissolved in

water or neutralized with acid it liberates substantial heat, which may be sufficient to
ignite combustible materials. Sodium hydroxide is very corrosive. It is generally used
as a solid or a 50% solution.
Table 1.11: List of Sodium Hydroxide Supplier
No
1
2
3

1.4

Company Names
Location
Beryl Chemical Co. Ltd
Pulau Pinang, Malaysia
Raani & Dew Tradings Bhd
Johor, Malaysia
Menara Groups Bhd
Perak, Malaysia
Source: Alibaba.com

PRICE OF RAW MATERIALS

The main raw material that used in this plant is nitric acid and bagasse from
sugarcane. Commonly nitric acid supplied with the purity 68%. In this process we
need 95% purity of nitric acid to undergo the reaction. Only a certain company in
Malaysia can supply this range of purity such Yakuhin Industries (M) Sdn Bhd Ayer
Keroh, Melaka. For the sugarcane bagasse, we decided to get the supplier from MSM
Malaysia Holdings Berhad located at Perlis and Penang. MSM Perlis already do a
cultivation of sugarcane a long years ago.
1.4.1
1.4.2
1.4.3
1.4.4
1.4.5
1.4.6

Price of Nitric Acid with 95% Purity

Price of Sugarcane Bagasse
Price of Vanadium (V) Oxide
Price of Oxygen Gas
Price of Aluminium Oxide
Price of Sodium Hydroxide

1.5

PRODUCT USAGE

Oxalic acid is an essential household chemical used in various ways such as a rust
remover, a cleaning agent, on wood working, as stain lifter and as bleaching agent and
many more. At high does, oxalic acid is very dangerous but at moderate doses it is
safe for various useful functions. Oxalic acid is a natural component of plants and

vegetables such as buckwheat and rhubarb. It is available for purchase in powdered

form at your local home improvement depot. The oxalic powder is then mixed with
water to turn into a solution of oxalic acid.
1.5.1

Bleaching

Oxalic acid can be used as a bleaching agent for wood and stone. Wood, when
exposed to weather elements turn into gray. When oxalic acid is applied on an old and
graying wood floor, it brings back the wood floors natural white colour. Oxalic acid is
used in preparation for staining old wood floors. It is also used by furniture
manufacturers to lighten heavily stained areas of wood furniture as preparation for
refinishing.
1.5.2

Removing Stains

Oxalic acid effectively removes mustard, ink, various food stains and other types of
stains. Oxalic acid is a gentle stain remover that eats the stain but leaves the base
surfaces such as wood, intact. Oxalic acid also can remove most stains found on stone,
brick, linoleum, wood and vinyl surfaces. However, do not use oxalic acid if your
flooring is sealed as oxalic acid will eat through the finishing.
1.5.3

Removing Rusts

Oxalic acid is also used to remove rusts that are commonly found on plumbing pipes
and kitchen countertops. Although you can also use oxalic acid to remove stains from
fabrics such as linen and cotton, it will take a lot of time to remove the stains with
oxalic acid that it is better to have your fabrics dry cleaned instead. Oxalic acid is also
a major ingredient found in commercial rust removers for sinks, tubs and metal rust
stains.
1.5.4

Textile Treatment

Oxalic acid has various uses in fabric cleaning, application of dyestuff, and modifying
properties of cellulose fabrics. Rust stains, which form on fabrics during weaving and
finishing, are removed by the chelating action of oxalic acid by forming iron oxalate
which is readily washed from the fabric. In laundries, oxalic acid neutralizes excess

alkalinity. It also dissolves iron and metallic salts, which could discolor fabrics, and
kills bacteria (H. Cohen et al., 1961). In mordant wool dyeing (L. Diserens, 1948),
oxalic acid is used as a reducing or fixing agent. Oxalic acid can be used as a catalyst
for cross-linking of textile finishing agents to cellulosic fabrics in the manufacture of
permanent press fabrics (N. A. Cashen, 1974). It is also used in flame proofing for
cellulosic fabrics (L. Benisek, 1976).

1.6

PRICE OF THE PRODUCT

Table 1.X: Market price of oxalic acid in year 2015
Year (2015)
Quarter 1
Quarter 2
Quarter 3
Quarter 4

1.6.1

Price of Oxalic Acid Past Few Years

Price (RM/ton)

Price of Oxalic Acid

6000
5000
4000
RM / Ton 3000
2000
1000
0
2004

2006

2008
Year

Source: IndexMundi, 2011

1.6.2

Malaysias Oxalic Acid Import and Export

2010

2012

Malaysia's Oxalic Acid Import & Export

700
600
500
400

Tonnes/year 300
200
100
0
200420052006200720082009201020112012

Year
Import

Export

Source: IndexMundi, 2011

1.7

SUPPLY DEMAND

1.8

FUTURE MARKETING POTENTIAL

Oxalic acid have their own marketing potential not just acts as the raw material in the
certain reaction, but it also have a huge function in the scope of household, treatment
and recovery. Currently, most of the uses of oxalic acid have been focused on
household such bleaching, removing stains and selected treatment such textile
treatment.
Metal treatment is one of future marketing potential of oxalic acid. Currently
this treatment actively was developed in Japan. The process undergo where oxalic acid
is used as a metal treatment for anodizing aluminium. Oxalic acid is used as an
electrolyte, and the thin aluminium oxide layer forms on the surface of aluminium.
The coatings are hard, abrasion- and corrosion-resistant. In addition to oxalic acid,

inorganic oxalate salts are also used in colouring anodic coatings (qv) (S. John et al.,
1976).
Oxalic acid is a constituent of cleaners that are used for automotive radiators,
boilers, and steel plates before phosphating. Many of its industrial cleaning
applications are based on its acidity and reducing power which promote dissolution of
rust and formation of oxalate coatings on steel (qv). As a chelating agent, oxalic acid
forms water-soluble complexes on metal surfaces during cleaning and rinsing (S.
Werneck et al., 1972).
Besides, Japan also used oxalic acid as a catalyst in production of millet jelly.
Starch powder is heated together with oxalic acid and hydrolyzed to produce millet
jelly. Oxalic acid functions as a hydrolysis catalyst, and is removed from the product
as calcium oxalate.
1.9

BASIS OF PRODUCTION CAPACITY