FACULTY OF ENGINEERING

DEPARTMENT OF CHEMICAL AND ENVIRONMENTAL

ENGINEERING
UNIVERSITI PUTRA MALAYSIA

PRODUCTION OF MALEIC ANHYDRIDE FROM 1-BUTENE

LECTURER: DR. HAMDAN

PREPARED BY:
DASHINE NAIR A/P VASU

175671

IFFAH AMIRAH BT HUSSIN ALI

172719

MOHD HAFSHAM BIN ARIFIN

156403

NURUL DALILA BINTI MOHD RAMLI

174821

EXECUTIVE SUMMARY
Maleic anhydride is a versatile chemical intermediate used to make unsaturated
polyester resins, lube oil additives, alkyd resins, and a variety of other products. In 1995,
global production of maleic anhydride was estimated at 1.8 billion pounds, with an estimated
value of $700 million. Over the last five years, world consumption has increased at an
average annual rate of 5.8%, with the fastest growth occurring in Asia, where it is used as an
intermediate for production of 1,4-butanediol. Nowadays, majority of Maleic Anhydride is
produced by the oxidation of benzene. However, process economics and environmental
factors suggest that n-butane is the feedstock of the future. In comparison with the historic,
but intrinsically less efficient route for benzene, butane catalysts are less selective. One
method of improving on existing selectivity is to employ reaction engineering principles to
optimize reaction yield. This report was discussed about the production of Maleic Anhydride
from 1-butane. Basically, Maleic Anhydride is an organic compound with the formula
C2H2(CO)2O and was traditionally produced by the oxidation of benzene or other aromatic
compounds. Most maleic anhydride is produced by vapour-phase oxidation of n-butane.This
report clarified about the processes to model the catalytic oxidation of n-butane and butene
mixture to maleic anhydride (MAN) over a vanadium-phosphorus oxide (VPO) catalyst in a
fluidized bed reactor (FBR). The application and safety of handling and producing Maleic
Acid was also discussed in this topic.

DESCRIPTION OF WORK DONE

INTRODUCTION

MALEIC ANHYDRIDE
Maleic anhydride is an organic compound with the formula C 2H2(CO)2O. It is the
acid anhydride of maleic acid. It is a colourless or white solid with an acrid odour.
It is produced industrially on a large scale for applications in coatings and
polymers. The IUPAC name for maleic anhydride are Furan-2 or 5-dione. Other
name is cis-Butenedionic anhydride. Table above show the properties of maleic
anhydride.
PROPERTIES OF MALEIC
ANHYDRIDE
Molecule formula
Molar mass
Appearance
Odor
Density
Melting point
Boiling point
Solubility in water
Vapor pressure

C4H2O3
98.06 gmol1
White crystals or needles
irritating, choking
1.48 g/cm3
52.8 C (127.0 F; 325.9 K)
202 C (396 F; 475 K)
Reacts
0.2 mmHg (20C)

Structure formula for Maleic anhydride C2H2(CO)2O.

PRODUCTION
Maleic anhydride was traditionally produced by the oxidation of benzene or other
aromatic compounds. Most maleic anhydride is produced by vapour-phase
oxidation of n-butane.

1-BUTENE
1-Butene is an organic chemical compound, linear alpha-olefin (alkene), and one
of the isomers of butene. The formula is C 4H8. IUPAC name but-1-ene and other
names are ethylethylene or 1-butylene. Table show the properties of 1-butene.
PROPERTIES OF 1-BUTENE
Molecule formula
Molar mass
Appearance
Odor
Density
Melting point
Boiling point
Solubility in water
Solubility

C4H8
56.11 gmol1
Colorless Gas
slightly aromatic
0.62 g/cm3
185.3 C (301.5 F; 87.8 K
6.47 C (20.35 F; 266.68 K)
0.221 g/100 mL
soluble in alcohol, ether, benzene

Structure formula for 1-butene

MANUFACTURING
1-Butene is produced either by separation from crude C 4refinery streams or from
the deisomerization of ethylene. It is distilled to give a very high-purity product.
1-butene is used to manufacture lots of other chemical products, such as linear
low-density polyethylene (LLDPE), polypropylene resins, polybutene, butylene
oxide, and butanone.

PRODUCTION OF MALEIC ANHYDRIDE FROM 1-BUTENE

The aim of this work was to model the catalytic oxidation of n-butane and butene
mixture to maleic anhydride (MAN) over a vanadium-phosphorus oxide (VPO)
catalyst in a fluidized bed reactor (FBR).Fluidized bed reactors have been used in
MAN

production

because

of

several

advantages

presented

in

transport

phenomena when catalytic solid particles are suspended and transformed into a
fluid-like state

MAN production in a FBR presents desirable features as follows:

Prevention of localized hot spot formation via rapid mixing of the catalyst
particles, since a constant temperature is maintained throughout the bed
by using a simple heat exchanger, even though the reactant and air are
fed separately;

Use of fine particles that allow an increment in the particle contact surface
and reduction in the concentration and temperature gradients;

Catalyst life is increased when hot spots are avoided;

Feed composition can be 4% butane in air compare to 1.8% in a PBR;

The reactor diameter and the compressor investment and cost utilities
could be reduced since the air rate decreases;

easier loading and unloading of the catalyst particles in a FBR than in a

PBR;

FBRs need a lower investment than PBRs, since FBRs can have double
capacity of a PBR for a large scale plant

Maleic anhydride production from a mixture of butenes and n-butane partial

oxidation catalyzed with vanadium phosphorus oxide (VPO) in a fluidized bed
reactor is modelled and simulated
The fluidized bed reactor was defined to operate in the bubbling regime of
fluidization. Under this regime, air flow rate is higher than the minimum fluidizing

flow rate. As a consequence, agitation is turbulent and solids movement is

vigorous; thus, bubbles rising are generated inside the reactor
This model considers a mass transfer among three phases (bubble, cloud-wake
and emulsion); while bubbles rise and reactants diffuse through the phases to
get in contact with the catalyst particles at the emulsion. The mass transfer flow
rate of the reactants and the products influence feedstock conversion; therefore
being required to calculate the bubble rising velocity (u b) and gas mass transfer
coefficients for each phase

(1)
(2)
(3)
(4)
(5)
(6)
Hydrodynamic model assumes that:

bubbles are uniformly distributed in the bed and have the same size
throughout the bed;

gas flow close to rising bubbles follows the Davidson model, where all
parameters are related with the bubble size;

each bubble develops a circulation of solids in the bed, with up flow

behind bubbles and down flow in the rest of the emulsion;

emulsion keeps at minimum fluid-zing conditions.

Vanadium present in VPO particles is the main oxygen transporter. The catalyst
solid surface is transformed by a vanadium reduction process when it reacts with
the hydrocarbon in the gas phase, V 5+ - V4+ (Mostoufiet al., 2001). The decrease
of the V5+:V4+ ratio makes the MAN selectivity decline (Cortelli, 2006). VPO

catalyst reduction is considered a parallel deactivation, where the reactants

become products while they deactivate the catalyst particles.

1-butene to maleic anhydride

(a) C4H8 + 3 O2 C4H2O3 + 3 H2O
(b)C4H8 + 6 O2 4 CO2 + 4 H2O

(c) C4H8 +

O2 2 C2H4O

(d)C4H8 +

O2 C4H6O + H2O

CALCULATION
The goal production of Maleic Anhydride is 40,000 tonnes / yr.
The reactor will be operating for 330 days per year and the expected production per day is

40000

tonnes 1000 kg
x
yr
tonnes
=121 212.12 kg/day
330 days

The production per hour is

kg
day
=5050.51 kg/hr
24 hr

121 212

The required flow rate of Maleic Anhydride is

5050.51 kg
x 1000 g
hr
Molar flow rate=
=14.32 mol/ s
98 g
x 3600 s
mol

The desired equation for the production of Maleic Anhydride from 1-Butene
C4H8 + 3O2 C4H2O3 + 3H20
The equation above shows the oxidation process from 1-Butene to Maleic Anhydride (MAN).
So,

Let A: 1-Butene B: Oxygen C: MAN D: Water

From the equation stated 1 mol of 1-Butene react with 3 mol of oxygen to produce 1 mol of
MAN and 3 mol of water. To produce 14.32 mol/s of MAN, 14.32mol/s of 1-Butene must be
reacted.
The goal production of 1-Butene is 90%. The amount of 1-Butene to be fed in the reactor
can be calculated as follows:

X=

F A 0F A
F A0

0.90=(

14.32mol
)/ F A 0
s

F A 0=15.91

mol
s

Operating Conditions
Target conversion, X= 0.90
Inlet Temperature = 400C (673K)
Inlet Pressure = 2.2 bars (220kPa)
Entering Volume flow rate, v= 2.78x10^-3 dm/s
Inlet flow rate of 1-Butene, FA0 = 15.91 mol/s
Inlet flow rate of Oxygen, FB0 = 55.56 mol/s
The mass of catalyst needed,

Assumptions made for the reaction: No pressure drop (P=P0 & T=T0) and it is carried out
isothermally.
v=v0= 2.78x10^-3 dm/s
CA0=FA0/v0 = 15.91/10
=1.591 mol/dm
CA = CA0 [(1-X)/ (1+X)] = CA0(1-X)

pA = CA RT = CA0(1-X)RT
= (1.591)(0.0831451)(673)(1-X)
pA = 89.03(1-X)

The reaction order of 1-Butene and the rate constant,

r = k1 x pA
k1 = 3.8075 x 105 exp (-11569/T) kmol/kcat-bar.s
At temperature of 673K
k1 = 3.8075 x 105 exp (-11569/673) kmol/kcat-bar.s
=0.01303 kmol/kcat-bar.s

Rate: -rA= k1pA

= (13.03) (89.03)(1-X)
= 1160.06 (1-X)

The equation used to calculate the catalyst weight,

X

W =F A 0
0

dX
'
r A
0.9

W =15.91
0

dX
1160.06 (1X )

W =1.985 x 103 kg catalyst

This shows that

1.985 x 103 kg catalyst is needed in the reactor to achieve the 90%

conversion.
Furthermore, this is an exothermic reaction. The enthalpy of the reaction is -1315 kJ/mol.
Since it is isothermal reaction, cooling water is needed to maintain the temperature to 673K.
The heat released is calculated as follow:

F
( A 0F A )( H rxn)
Q=
Q=14.32 ( 1315 )=18830.8 kW
Then, the heat released will be absorbed by the cooling water, thus, we made assumptions
as follows :
Initial temperature of cooling water : 30C
Final temperature of cooling water : 80C
The mass flow rate of water was then :

m
Cp T
Q=

18830800=m
( 4.182 ) ( 8030 )
m=90056.432

g/s=90.056 kg/ s=5403386 kg/hr

With that, we can say that the temperature of the reactor at 400C is maintained with
5403386 kg/hr of cooling water.

For the heat transfer area,

T LMTD =

T LMTD =

T 2T 1
T 2
ln
T 1

( 40080 )( 40030 )
=344.395 K
( 40080 )
ln
( 40030 )

With U= 227 W/m2.K.

Q=UA
T LMTD
18830.8 103=( 227 ) A( 344.395)

A=240.872m

To calculate the length of PBR needed when the diameter of PBR is 1.0 m,
2

dL=240.872 m

( 1.0 ) L=240.872
L=76.672 m
From all the calculations that had been made, we can conclude that the length of PBR is
76.672m and the diameter is 1.0 m. Whereas, the mass of catalyst needed to achieve 90%
conversion is

1.985 x 103 kg catalyst. To maintain the operating temperature of PBR at

400C, a continuous

5403386 kg /hr

Figure 1: Fluidized Bed Reactor Design

of cooling water must be provided.

APPLICATIONS OF MALEIC ANHYDRIDE

Around 50% of world maleic anhydride output is used in the manufacture of unsaturated
polyester resins (UPR). Chopped glass fibers are added to UPR to produce fibreglass
reinforced plastics which are used in a wide range of applications such as pleasure boats,
bathroom fixtures, automobiles, tanks and pipes. However, the UPR market reflects general
economic conditions as it is tied to the construction, automobile and marine industries.
However, BDO is made from a crude maleic anhydride which is not traded and only used for
this application. Another market for maleic anhydride is lubricating oil additives, which are
used in gasoline and diesel engine crankcase oils as dispersants and corrosion inhibitors.
There are a number of smaller applications for maleic anhydride. The food industry uses
maleic anhydride in artificial sweeteners and flavour enhancements. Personal care products
consuming maleic anhydride include hair sprays, adhesives and floor polishes.

SAFETY ISSUES REGARDING MALEIC ANHYDRIDE

This compound also poses relatively low-risk environmental hazards, an important feature
for those applications. Exposure to maleic anhydride may cause respiratory tract, eye
irritation, skin irritation and respiratory irritation. Maleic anhydride is a skin and respiratory
sensitizer. Therefore, these storage conditions should be considered during the storage of
this compound:

Keep ignition sources away - do not smoke. Product dust may form explosive air-

dust mixtures.
Keep humidity away from storage rooms.
Keep containers tightly closed. Store them in cool, dry and well ventilated places.
Hand-operated / portable fire-fighting equipment should be available in storage

rooms.
Neutral gas blanketing is required inside storage tanks.

LIST OF REFERENCES

1. Kurt Lohbeck; Herbert Haferkorn; Werner Fuhrmann; Norbert Fedtke (2005),

"Maleic and Fumaric Acids", Ullmann's Encyclopedia of Industrial
Chemistry, Weinheim:
Wiley-VCH
2. Retrieved from
http://www.academia.edu/9569277/maleic_anhydride_production
3. Samuel Danishefsky, Takeshi Kitahara, and Paul F. Schuda (1983).
"Preparation and
Diels- Alder Reaction of a Highly Nucleophilic Diene:
trans-1-Methoxyl-3- Trimethylsiloxy1,3-Butadiene and 5Methoxycyclohexan-1-one-3,4- Dicarboxylic acid Andhydride". Org.
Synth
4. Values obtained: http://users.rowan.edu/~hesketh/0906-316/Design/Team
%206.ppt

DISTRIBUTION OF EFFORT

Dashine Nair
o Presentation
Applications of maleic anhydride
Editing
o Report
Appendices
Distribution of Effort
Editing and Compiling
calculation
Iffah Amirah
o Presentation
Production of maleic anhydride
Compiling
o Report
Description of work done
calculation
Mohd Hafsham
o Presentation
Introduction to maleic anhydride and 1-butene
o Report
List of references
Nurul Dalila
o Presentation
Safety issues regarding maleic anhydride
o Report
Executive summary
FBR design

APPENDICES

Fluidized Bed Reactor