CHAPTER 1

MALEIC ANHYDRIDE
1.1 INTRODUCTION
History of Maleic Anhydride was initially amalgamated in 1830s but was not
industrially manufactured till 1933.The National Aniline and Chemical Co.inc in
1933 manufactured maleic anhydride industrially for commercial purposes, by
oxidising benzene using a vanadium oxide catalyst. Maleic anhydride (MA) is
an organic compound with the molecular formula C 4H2O3. It is used widely in
the production of unsaturated polyester resins. These resins are used
primarily in fibre-reinforced plastics for boating, automobile and construction
industries. Besides that, malice anhydride can also be used to produce
several chemicals which include fumaric, malic & tartaric acid and others.
Maleic anhydride is originally in the form of white solid with an acrid odour
(Ma, 2016). MA can be conventionally manufactured through the oxidation of
benzene, n-butane, or other aromatic compounds via a fixed-bed reactor,
fluidised bed reactor, or recirculating-solids reactor, where a catalyst is utilized
to aid the reaction for optimum mass and energy usage. The type of catalyst
used for the production of maleic anhydride depends on the type of feedstock
that is used in the chemical process.
The objective of the company, to design a maleic anhydride production plant
by proposing a viable / feasible chemical process that is able to produce
maleic anhydride with a capacity of 100 metric ton per annum having a purity
of above 99%, which caters the current global maleic anhydride market
outlook. The constraints that is imposed to this company is that to design an
economical production process and meet the primary project objective which
is to produce a maleic anhydride plant with a capacity of 100 metric ton per
annum .

Figure 1.1: The molecular structure of Maleic Anhydride

(Helmenstine, 2016)

Maleic anhydride is a 5-membered ring compound. The anhydride is a stable

compound containing two acid carbonyl groups and a double bond in and
positions. Nomenclature of the compound MA is a common name given to the
compound based on naturally occurring malic acid. The compound has other
names based on nomenclature .the compound is also called 2, 5-Furandione,
dihydro-2, 5-dioxofuran, toxilic anhydride or cis-butenedioic anhydride.
(Nist.gov, 2016)

1.2 PROPERTIES AND USES

1.2.1 Physical properties
One of the physical properties of maleic anhydride is its white colour. Its smell
its highly offensive odor. Most often this odor is described as not only irritating
but also choking. With a molecular weight of 98.06g/mol, the melting point of
maleic anhydride is 52.8C. Its boiling point is 200.1 C. Besides its solubility in
water, one last property to make special note of is its density. The density of
maleic anhydride is 1.48g/cm3 (Howard, 2016)

Table 1.1: Physical Properties of Maleic Anhydride

Molecular Weight

Melting Point
Density

98.06 g/mol
o
202 C
o
52.8 C
1.48 g/cm3

Vapour Pressure

o
0.41mm Hg at 25 C

Conversion Factor
Formula

1ppm=4.0 mg/m3
C4H2O3

Physical State

Solid

Colour

White to colourless

Odour

Chocking,irritating

Boiling Point

Flash Point, C

Autoignition Temperature C
Heat Of Combustion,Kcal/mole

110
447
333.9

HeatOfFormation,solid,Kcal/mole 112.2
Heat Of Fusion,Kcal/mole

3.26

Heat Of Hydration,Kcal/mol

8.33

Heat Of Vapourisation,Kcal/mole

13.1

Dipole Moment 10-30C.m

13.2

Appearance

White solid and exists in the form of,

needles, crystals, flakes or pellets

Crystalline Form

Orthorhombic

Heat Of Neutralisation KJ/mol

126.9

Chemical properties
Maleic Anhydride C4H2O3 has attractive molecule structure in chemistry. Its reactivity of
the two carbonyl groups and the solid bond in conjugation with the two carbonyl
oxygens provide broad applications in commerce (Hermanson, 2016).Examples of
reactions which maleic anhydride are

Alkylation

Maleic Anhydride reacts with alkenes activated by - unsaturation or an adjacent

aromatic resonance to produce succinic anhydride derivatives. The reaction conditions
are 150 to 3000C and up to 2 Mpa pressure polyalkyl succinic anhydrides are prepared
under these conditions by the reaction of polyalkenes in an aqueous dispersion of
maleic anhydride, mineral oil and surfactant. N-Alkylpyrroles react with maleic
anhydride to give electrophilic substitution.

Figure 1.2: Chemical reaction of maleic anhydride in alkylation

Acid Halide Formation

Maleic Anhydride when treated with various reagents such as phthaloyl

chloride or bromide ,phosphorus pentachloride ,or thionyl chloride or thioyl
halide gives 5,5-dichloro-2furanone .Maleic anhydride reacts with carbon tetra
chloride or tetra bromide at 220C over activated carbon to form Noncyclic
maleyl chloride

Figure 1.3 :Chemical reaction of maleic anhydride in acid hallide formation

Amidation

Reaction of maleic anhydride with ammonia,primary and secondary amines

produce mono and di-amides and the reaction is known as amidation.Maleic
anhydride reacts with ammonia to form maleamic acid.It reacts with primary
amines to form amic acids that can be dehydrated to imides ,polyimides,or
isoimides depending on the reaction conditions.Amines and pyridines
decompose maleic anhydride often in a violent reaction and carbon-di-oxide is
usually a biproduct.

Figure 1.4 : Chemical reaction of maleic anhydride in amidation

5

1.2.2 Uses
Maleic anhydride has two types of chemical functionality making it uniquely
useful in chemical synthesis and applications.The derivatives of maleic
anhydride has worldwide consumers and each structure has its own
commercial interest.The majority of maleic anhydride produced is used in
unsaturated polyester resin . The other fields in which maleic anhydride is
employed is in production of plasticisers and stabilizers , additives and
agricultural chemicals.

Figure 1.5: Application of maleic anhydride

Unsaturated polyester resins are the most commonly used thermoset resins in
the world. More than 2 million tonnes of unsaturated polyester resins are
utilised globally for the manufacture of a wide assortment of products,
including sanitary-ware, pipes, tanks, gratings and high performance
components for the marine and automotive industry. It is formulated from
aromatic dibasic acid such as phthalic anhydride, an unsaturated dibasic acid
such as maleic anhydride and glycol such as propylene glycol. The polyester
chains are then cross linked through the double bond with vinyl cross linking
agents such as styrene.

Reinforcement in the form of glass fibres or other reinforcement fibres

maybe added to provide the strength requirement of the end product .The
exact unsaturated polyester formulation; its cross linking agent and
reinforcement fibre are selected to optimize the performance of the end
product. The versatility in use allows unsaturated polyester resins to be used
in a myriad of composite applications. Composite parts can be made at
temperatures as low as 15C to as high as 150C depending on the
processing requirement of the application .Unsaturated polyester resins also
have excellent service temperatures. It has a good freeze-thaw resistance
and can be designed for use in many low to moderate temperature
applications ranging from refrigerated enclosures to hot water geysers.
When it comes to weight for cost comparisons, unsaturated polyester
resins are much favoured over their metallic counterparts. With the current
fuel and processing costs, the increasing prices of steel and aluminium are
pushing more fabricators to use unsaturated polyester resin composites
instead. Another major advantage is the increased productivity potential.
While metals involve the use of specific smelters, expensive tooling and
processing requirements, unsaturated polyester resins are far cheaper and
afford the use of low cost tooling. An unsaturated polyester resin can be
moulded at ambient temperature whereas metals need to be heated to well
over 2000C before they are melted and poured into mould cavities. Although
the perception is that metals are generally structurally superior, there has
been much advancement in the development of technologies for producing
higher strength composites made from unsaturated polyesters resins.
Collectively there is an ever increasing potential for unsaturated polyester
resins. Their low cost, ease of use and weight advantages make them prime
candidates for a wide variety of structural and decorative applications.

Figure 1.6: End products from maleic anhydride

Fumaric acid, succinic acid and malic acid are produced from maleic
anhydride. The primary use of fumaric acid is in manufacture of paper sizing
products and is also used as food acidulates. Malic acid is particularly
desirable acidulate in certain beverage selections, specifically those
sweetened with artificial sweetener aspartame. Lube oil additives represent
another important market segment for maleic anhydride derivatives, the
molecular structure of importance being adducts of polyalkenyl succinic
anhydrides.

Figure 1.7: Chemical reaction of Fumaric acid from maleic anhydride

Maleic anhydride is used in a multitude of applications in which a vinyl

copolymer is produced by the copolymerisation of maleic anhydride with other
molecules having a vinyl functionality.Typical copolymers are styrene
maleic ,di-isobutylene maleic ,acrylic acid maleic,butadiene maleic and C18
alpha olefin-maleic (emulsification agent and paper coating).

Figure 1.8:Chemical reaction of styrene maleic anhydride copolymer

Agricultural chemicals such as maleic hydrazide ,endothall, captan, have a wide

range of consumers.they are used for plant growth regulation,fungicides,isecticides,
and herbicides.
a) Maleic hydrazide is a synthetic compound which has a plant growth regulating
action. It is used as a foliar treatment of potatoes to prevent volunteer
formation and sprouting during storage.
b) Endothall is used as an herbicide for both terrestrial and aquatic plants. It is
used as an aquatic herbicide for submerged aquatic plants and algae in
lakes, ponds and irrigation canals
c) Captan is a general use pesticide that belongs to the phthalimide class of
fungicides. Though it can be applied on its own, Captan is often added as a
component of other pesticide mixtures.

There are many bio degradable polymers produced from maleic anhydride such as
poly aspartic acid, which is employed in water treatment,detergent builders
etc,sulfosuccinic acid esters serve as surface active agents.Alkyd resins are used as
surface

coatings.Chlorendricanhydride

compoent.Tetraydropthalic

acid

and

is

used

as

hexahydropthalic

flame

anhydride

resistant

have

resin

applications.poly malic anhydride is used as a scale preventer and corrosion inhibitor

Maleic anhydride forms polymer with mono-O-methyl oligoethylene glycol vinyl
ethers ,that are esterified for biomedical and pharmaceutical uses.

10