Chapter 2 PROCESS SELECTION AND DESCRIPTION

PROCESS SELECTION AND DESCRIPTION

2.1 PROCESS SELECTION

In this section we will discuss different methods to produce maleic anhydride and will select
the most suitable process for its production. Process for the manufacturing of MA is selected on
the basis of reactants to be oxidized for the production of MA.

So there are two processes for the manufacturing of MA:

1. By controlled air oxidation of benzene

2. By oxidation of Butane

2.1.1 ADVANTAGES OF USING BUTANE OVER BENZENE

Recent processes for the manufacture of maleic anhydride employ C4 hydrocarbons, such as
n-butane and n-butylene, as feedstock. Even existing processes originally using benzene as a
reactant are being converted to the C4 hydrocarbons due to the reasons:

1. Advantage of C4 HC over benzene is that no carbon is lost in the reaction to form MA

2. For a theoretically achievable conversion of 100%, the yield from butane is a third
greater than that from benzene.
3. From a raw material viewpoint, the relatively low purchase price of C4 is much more
attractive than the expense of benzene.
4. Benzene is a known carcinogen and one of the chemicals most stringently regulated by
the government.
5. The flammability limits for C4 HC are also lower than those for benzene, which is an
additional safety advantage of the process.
6. Benzene emissions can be eliminated by conversion to the n-butane process.

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Chapter 2 PROCESS SELECTION AND DESCRIPTION

For all of these reasons, the n-butane process has been the only MA route that is mostly using
commercially.

2.1.2 SOURCES OF BUTANE

The main sources from which butane is coming from are:

1. LPG that contains (50-85) % of n-butane.

2. C4 cut that contains maximum 60% of n-butane.

2.1.3 CATALYST SELECTION

Following are the type of catalysts that are being using in oxidation of butane:

1. Vanadium phosphorus oxide

2. Phosphotunjstic catalysts modified with vanadium–thallium.

3. Phosphorus vanadium in glycol ether solvent

But in 90% reactions, VPO catalyst is being using because of its following advantages over other
catalysts:

1. Its excellent reproducibility of the chemical and physical characteristics.

2. It exhibits improved activity for the conversion of nonaromatic hydrocarbons while

maintaining excellent selectivity to maleic anhydride.

Several routes may be used to prepare the catalyst but the route favored by industries involves
the reaction of vanadium (V) oxide and phosphoric acid to produce vanadium-phosphorus-oxide.

The reaction of V2O5 with H3PO4 to form VOHPO4.0.5H2O can be carried out an aqueous or
organic medium such as isobutyl alcohol. The two possible routs are as follow:

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Chapter 2 PROCESS SELECTION AND DESCRIPTION

Reducing agent, HCl

V2O5 + H3PO4
Water
VOHPO4O.5H2O ∆ (VO) 2P2O7
Isobutyl alcohol
V2O5 + H3PO4
Reducing agent

2.1.4 SOLVENT SELECTION

A number of options are there. Each having its advantages and disadvantages. Following
solvents are used most commonly:

1. Organic solvent like dibutyl phthalate

2. Water

3. Ester

Dibutyl phthalate is preferred due to:

1. They are chemically stable.

2. Small quantities of solvent are lost.

3. Low energy consumption because water evaporation is not required.

4. Low production of by-products.

2.2 PROCESS DESCRIPTION

Pure gaseous butane and compressed air are mixed and fed to fluidized bed reactor at
conditions of 121°C and 275kpa, where butane is oxidized in the presence of VPO catalyst to
form maleic anhydride and water. Following reactions are taking place in reactor:

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Chapter 2 PROCESS SELECTION AND DESCRIPTION

First reaction is our main reaction. The conversion of butane is 82.2%. Selectivity for each
reaction is given below respectively:

1. Maleic anhydride 70.0%

2. Carbon dioxide 1.0%

3. Acrylic acid 1.0%

4. Formic acid 1.0%

The exothermic heat of reaction is removed by jacketing the reactor to maintain isothermal
conditions. The reactor effluent is cooled and sent to absorber, where maleic anhydride is
absorbed in solvent, dibutyl phthalate, and light gases and by-products are removed from top and
send to incinerator for burning. All maleic anhydride that is absorbed in solvent with trace
amount of by-products is sent to stripper after heating the mixture which contains N2 as stripping
gas. Stripper separates solvent from bottom for recycling into solvent storage tank after
purification and top product is sent to first distillation column. As solvent has highest boiling
point from all the products, so it is separated from bottom and is recycled back to solvent storage
tank while top product is finally sent to second distillation column where pure maleic anhydride
is separated from bottom. All trace amounts of by-products are sent to an incinerator before
entering into atmosphere to avoid pollution. So in this way, we get 99.8% pure maleic anhydride.
The detailed process can be seen in the process flow diagram attached below.

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Chapter 2 PROCESS SELECTION AND DESCRIPTION

Figure 1 Process flow diagram

Table 2.1 Equipment Designations for PFD

Equipment Number Equipment Name Equipment Number Equipment Name

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Chapter 2 PROCESS SELECTION AND DESCRIPTION

Reactor R-201 Compressor C-101

Absorber T-101 Heat exchanger 1 E-101

Stripper S-101 Heat exchanger 2 E-102

Distillation Column1 D-101 Heat exchanger 3 E-103

Distillation Column 2 D-102 Heat exchanger 4 E-104

2.2.1 SOLVENT PURIFICATION

Solvent coming from stripper has some amount of maleic anhydride so it needs
purification. So for this purpose we send this stream into centrifugal separator where alkali i.e.
NAOH of (0.01-3) N solution is present as separating agent. Separation occurs on the basis of
density. Since maleic anhydride is lighter than maleic anhydride so it is separated from bottom.
Solvent with trace amount of solvent is sent to second centrifugal separator where it is washed
with washing liquid to get pure solvent ad finally recycled back to solvent storage tank. Its whole
assembly can be seen in fig. 2.

REFERENCES

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Chapter 2 PROCESS SELECTION AND DESCRIPTION

1. G. Stefani, F. Budi, C. Fumagalli, G.D. Suciu, “Fluidized bed oxidation of n-butane: a new
commercial process for maleic anhydride,” in New Developments in Selective Oxidation,
edited by G. Centi and F. Trifiró (Elsevier, Amsterdam 1990).
2. S.C. Arnold, G.D. Sucium, L. Verde, A. Neri, “Use fluid bed reactor for maleic anhydride
from butane,” Hydrocarbon Processing (September 1985).
3. G. Stefani, F. Budi, C. Fumagalli, G.D. Suciu, “Fluidized bed oxidation of n-butane: a new
commercial process for maleic anhydride,” Chimica & Industria (Milano) 72 (1990).
4. US patent # 4,143,056.
5. US patent # 5,792,722.
6. US patent # 6,960,970.

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