OXIDATION

INTRODUCTION

Oxidation is the addition of oxygen to an organic compound or,

conversely, the removal of hydrogen.

 Reaction control is the major issue during oxidation

reactions.
 Sometimes, only partial oxidation is required for
conversion of one organic compound into another or
complete oxidation to carbon dioxide and water will
ensue.
 Dehydrogenation
 From primary alcohol to an aldehyde

 From secondary alcohol to ketone

 Introduction of oxygen atom
 From aldehyde to carboxylic acid

 From hydrocarbon to alcohol

Combination of dehydrogenation and
Oxygen introduction

 Preparation of aldehyde from hydrocarbons

 Preparation of benzoic acid from benzyl

alcohol
 Molecular condensation

 In a condensation reaction, two molecules or parts

thereof combine, releasing a small molecule.
 When this small molecule is water, it is known as a
dehydration reaction. Other possible lost molecules
include hydrogen chloride, methanol, and acetic acid.
Dehydrogenation, Oxygen introduction
and destruction of Carbon Linkage

 Oxidationof Naphthalene to Phthalic

Anhydride
Oxidation of amino compounds
 Oxidation of Sulfur compounds
 Strong Oxidation of mercaptans results in:

 Mild Oxidation of mercaptans results in:

 APPLICATIONs

 As examples of oxidation processes, two processes are

available for the manufacture of phenol, and both involve
oxidation.

 The major process involves oxidation of cumene to cumene

hydroperoxide, followed by decomposition to phenol and
acetone.

 Phenol is also made by the oxidation of toluene to benzoic

acid, followed by decomposition of the benzoic acid to
phenol.
APPLICATIONs : ( Preparation of Phenol)
APPLICATIONs : ( Preparation of Phenol)

Methyllithium
Bayer-Villager (m-CPBA) oxidation
APPLICATIONs

 Benzoic acid is synthesized by liquid-phase toluene oxidation

over a cobalt naphthenate catalyst with air as the oxidizing
agent.

 Maleic acid and anhydride are recovered as by-products of the

oxidation of xylenes and naphthalenes to form phthalic acids,
and are also made specifically by the complete oxidation of
benzene over a vanadium pentaoxide (V2O5) catalyst.

 Several oxidative routes are available to change cyclohexane

to cyclohexanone, cyclohexanol, and ultimately to adipic acid.
APPLICATIONs (Manufacturing of Acetaldehyde)

 Acetaldehyde is manufactured by one of several

possible processes:

1. The hydration of acetylene, no longer a significant

process.

2. The Wacker process, in which ethylene is oxidized

directly with air or 99% oxygen) in the presence of
a catalyst such as palladium chloride with a copper
chloride promoter
APPLICATIONs (Manufacturing of Acetaldehyde)

3. Passing ethyl alcohol over a copper or silver gauze

catalyst gives a 25 percent conversion to
acetaldehyde, with recirculation making a 90 to 95
percent yield possible

4. A process in which lower molecular weight paraffin

hydrocarbons are oxidized non-catalytically to
produce mixed compounds, among them
acetaldehyde and acetic acid.
 Oxidizing agents
The most common oxidation agent is air, but oxygen is frequently used.

Other Chemical oxidizing agents include:

 Permanganates (Neutral solution, Acid solution)

 Dichromates (Chromic acid solution)
 Hypochlorous acid and salts
 Sodium chlorite and chlorine dioxide
 Chlorates
 Peroxides
 Nitric acid and nitrogen tetraoxide
 Copper salt
 Fuming sulfuric acid
 Ozone
Oxygen as an oxidizing agent
 The oxygen of the air is the cheapest available
oxidizing agent but at the same time, perhaps the
most difficult to control.

1. Although atmospheric oxygen is constantly reacted

with organic substances at ordinary temperature

2. The rates of the reactions are too slow, generally, to

be of any significance from the standpoint of
usefulness in chemical synthesis.
Oxygen as an oxidizing agent
 To induce molecular oxygen to react at
commercially useful rates, it is usually necessary to
provide a catalyst, to elevate the temperature, or to
use a catalyst in conjunction with elevated
temperatures.
 In many cases, the temperature must be elevated to
the point where vapour phase processes only are
practicable.
Thermodynamics
 Inoxidations reactions, especially based on elemental
oxygen, the important thermo chemical aspect is the
heat evolved.

 Equilibrium is favorable and problems are largely the

removal of heat at the desired reaction temperature
level and the limitation of the oxidation to the desired
product by avoidance of complete combustion.

 Catalysts are generally used in an effort to obtain the

oxidation reaction at as low a temperature as possible
and to direct the reaction to the desired products.
 Comparison
Liquid phase oxidation Vapor phase oxidation
 The product form will resist to
 High molecular weight complex further oxidation.
compound.
 Thermally unstable substances are
 Thermally stable substances are
involved involved
 Oxidizing agent is non volatile  Oxidizing agent is a volatile
material. material.
 Temperatures are low.  Temperatures are high.
 Catalyst may be dissolved or
suspended in finely divided form to  Solid or vapor-phase catalysts may
ensure contact with bubbles of gas be employed with air or oxygen to
containing oxygen passing through produce the desired oxidation.
liquid phase.
 Extent of oxidation may be readily
 Control is effected by limiting the
time of contact, temperature,
controlled by :
proportion of oxygen, ,or type of
 Limiting the duration of operation catalyst, or by combination of these
 Controlling the temperature factors.
 Limiting the amount of oxidizing
agent.
 liquid-phase oxidation
 In the case of liquid-phase reactions in which oxidation is
secured by means of atmospheric oxygen—for example, the
oxidation of liquid hydrocarbons to fatty acids—special
means must be provided to secure adequate mixing and
contact of the two immiscible phases of gaseous oxidizing
agent and the liquid being oxidized.

 Although temperature must be controlled and heat removed,

the requirements are not severe, since the temperatures are
generally low and the rate of heat generation controllable by
regulation of the rate of air admission.
 liquid-phase oxidation

 Heat may be removed and temperature controlled by

circulation of either the liquid being oxidized or a
special cooling fluid through the reaction zone and
then through an external heat exchanger

 Mixing may be obtained by the use of special

distributor inlets for the air, designed to spread the air
throughout the liquid.
 ACETIC ACID PRODUCTION

 The formation of acetic acid is an excellent example of liquid

phase oxidation with molecular oxygen.
 The technology of acetic acid production mainly includes
ethylene oxidizing method, butane oxidizing method, ethanol
oxidizing method, etc.
 ACETIC ACID PRODUCTION

 The concentrated acid is generally obtained by oxidation

methods from acetaldehyde that may have been formed by
the hydration of acetylene or the oxidation of ethanol.
Batch liquid phase oxidation of acetaldehyde
to acetic acid

 The oxidation usually occurs in acetic acid solution in

the presence of a catalyst and at atmospheric or
elevated pressures.
 Temperature may range upto 100 oC, depending upon
the condition, but are usually lower.
 Reaction vessel consists of aluminium-lined steel
vessel fitted with aluminum coils for heating and
cooling, inlet and outlet openings and an air distributor.
Batch liquid phase oxidation of acetaldehyde
to acetic acid

 In the operation 98-99 % of about 4500 kg

acetaldehyde previously cooled to 0-5 oC is introduced
and then 18-22 kg of manganese acetate is added either
in the form of saturated acetic acid solution or as
powder ground to pass a 200 mesh sieve.

 Air is introduced through the distributor head, and at

the same time, steam is passed through the aluminium
coils to raise the temperature gradually to the operating
point.
Batch liquid phase oxidation of acetaldehyde
to acetic acid

 When the reaction starts, oxygen absorption from the

incoming air is almost complete, and the heat of reaction is
removed by cooling water.
 The temperature is so controlled that after 1 hr it
approximates 27oC, after 2 hr, 28-30oC and after 4 hr, 60oC.
 Reaction is completed in about 12-14 hr.
 The pressure is not allowed to exceed 5kg/cm2, nitrogen
being vented through a series of condensers attached to the
dome.
Batch liquid phase oxidation of acetaldehyde
to acetic acid

 Condensed aldehyde is returned to the kettle.

 Before being released the nitrogen is passed through water
scrubbers to remove the last of aldehyde, which is later
recovered.
Continuous liquid phase oxidation of
acetaldehyde to acetic acid

 The vented nitrogen from the reactor is sent to a scrubber where

unconverted acetaldehyde is recovered.

 The vent gases mainly consisting of Nitrogen are washed with

water in water scrubbers to remove any traces of acetaldehyde
carried by vent gases.

 The stripped crude acid (96% in strength) along with liquid from
wash column is sent to a distillation column to get pure acetic
acid from the bottom.

 Distillation is used for final concentration and purification of

acid. The yield varies from 88-95% of the theoretical.
VAPOR PHASE OXIDATION OF AROMATIC COMPOUNDS
PHTHALIC ANHYDRIDE
 Phthalic anhydride
 Phthalic anhydride was first produced by
the oxidation of naphthalene in
concentrated sulphuric acid in the presence
of mercury sulphate.
 This route was later replaced by the catalytic
vapor phase oxidation of naphthalene in air in
the presence of a vanadium oxide catalyst.
 Phthalic anhydride

 Today, naphthalene feedstock has been generally

superseded by the use of orthoxylene, with naphthalene
now providing only 16% of feedstock requirements.
 In the US all production is now from orthoxylene with
only Koppers having the facility to switch feedstocks.
 In Europe, more producers have the capability to use
naphthalene.
 Phthalic anhydride
 In the orthoxylene-based process, an air-orthoxylene
mixture is fed to a reactor containing vanadium
pentoxide with titanium dioxide-antimony trioxide
catalyst.
 Alternative catalysts include molybdenum trioxide and
calcium oxide, or manganese oxides.
REACTION CHEMISTRY
vapor-phase oxidation processes
 The vapor-phase oxidation processes result in the concentration of
reaction heat in the catalyst zone, from which it must be removed in
large quantities at high-temperature levels.

 Removal of heat is essential to prevent destruction of apparatus,

catalyst, or raw material, and maintenance of temperature at the
proper level is necessary to ensure the correct rate and degree of
oxidation.

 With plant-scale operation removal of heat constitutes a major

problem.

 With limited oxidation, however, it may become necessary to

supply heat even to oxidations conducted on a plant scale.
vapor-phase oxidation processes
 Almost without exception, the vapour phase
processes employed in the partial oxidation of
organic compounds use molecular oxygen as
the oxidizing agent, require catalyst and
elevated temperatures for operation at
industrially useful rates.
 Only certain substances are fitted for the
vapour-phase processing.
vapor-phase oxidation processes
 These must have sufficiently high vapour
pressures at the temperature requires for the
oxidation to make it possible to mix them with
air ( oxygen) and pass them in the gaseous
state over the catalyst material.
 They must be of sufficient thermal stability to
resist undesired decomposition and give rise
to products of comparable thermal stability.
FORMALIN
Formalin: A colourless solution of formaldehyde in water
 It contains:

o Formaldehyde=37%
o Methanol = 9%
o Water = 54%
 FORMALIN PRODUCTION

Catalyst: Silver or zinc oxide, iron-molybdenum-vanadium oxide

catalyst catalysts on wire gauze are used.

Oxidation:
1. Direct oxidation of methanol
2. Exothermic reaction
3. 50-60% formaldehyde form

Pyrolysis:
4. Dehydrogenation of methanol
5. Endothermic reaction
6. 40-50% formaldehyde form
 FORMALIN PRODUCTION
 Consideration of the reaction involved in the synthesis
and decomposition of methanol shows that only low
conversions to formaldehyde may be obtained by
direct catalytic decomposition of the alcohol.
 Reason is that catalyst and temperature conductive to
dehydrogenation of methanol are also conductive to
the decomposition of the formaldehyde to hydrogen
and carbon monoxide.
 Furthermore, the reaction is exothermic and heat must
be supplied.
 FORMALIN PRODUCTION
 However, if Oxygen, in the form of air, is furnished
to the reaction and the process conducted in vapour
phase in the presence of suitable catalysts,
Industrially practicable yields of formaldehyde are
obtained.
 Process is also exothermic.
Process description (CONT)

 Oxidation of methanol process appears simple , but it

requires
1. Regulation of temperature
2. Air-to-alcohol ratio
3. Time of contact to ensure continuous high yields at
high efficiency.

 The rate of feed and the air : methanol ratio are

maintained so as to make operation autothermal.
Process description (CONT)
 1 lb of pure methanol theoretically requires 26.7 cu ft of
dry air measured under standard conditions.
 Exact control of the ratio is made possible by the use of
separate, controlled stream of air and liquid methanol
introduced to a vaporizing chamber, which is supplied
with heat to vaporize the liquid.
 Cleaned dry air is supplied through a storage tank by a
compressor.
 Methanol enters the mixing chamber as liquid.
 The mixture passes immediately to the catalyst chamber
and then to recovery system.
Process description (CONT)
 Large amounts of formaldehyde have been made with a
catalyst consisting of copper arranged in the form of
gauze rolls supported in concentrically arranged bundles
of copper tube.
 Such a catalyst chamber may consist of six or eight
copper tube 24 in. long and 2 in. in diameter containing
rolled up copper gauze for about 4 to 5 in. of their
length, fitted into suitable header at each end.
 Means are provided for heating the catalyst mass at the
start of operation.
 Reaction occurs at a temperature of 400-450 oC.
Process description (CONT)
 Operation is conducted at a temperature of about 550-
600 oC in the catalyst mass.
 The rate of feed and the air : methanol ratio are
maintained so as to make operation autothermal.
 The gaseous mixture passes from the catalyst chamber
to a rectifying and recovery system where rapid
countercurrent cooling is obtained by contact with the
relatively cool aqueous formaldehyde solution that
passes down the column.
 Formaldehyde solution is withdrawn at the bottom of
the column.
Process description (CONT)
 Gases containing the vapour of unreacted methanol are
passed out of the top to a condenser where methanol is
partly removed.
 The gases from this condenser are scrubbed with water
or dilute methanol solution, for complete methanol
recovery.
 Methanol is recovered from the aqueous solution by
rectification and recovered methanol along with
obtained from the condenser is fed back to the mixing
chamber for recirculation over the catalyst.
Process description (CONT)
 Under proper oxidation conditions about 55% of
the formaldehyde results from oxidation
reaction.
 Thewater formed by reaction is not sufficient to
bring the formaldehyde solution to the 37-37.5
% by weight at which it is generally sold, so
some water must be added.
Oxidation via Dehydrogenation
 Catalytic vapor phase processes for the
dehydrogenation of iso-alcohols and side chain
aromatics are of great industrial importance.
 Examples are isopropanol to acetone and secondary
butanol to methyl and ethyl ketone respectively.
Acetone and methyl ethyl ketone
 The same plant may be used to ketonize either
isopropanol or butanol.
 Hydrogen is passed through the dry alcohol kept at
such a temperature that the hydrogen leaving the
saturator carries with it an equal volume of alcohol
vapor.
 The hydrogen flow is adjusted to evaporate 128
lb/hr of the alcohols, whichever is used.
 The mixed vapors is passed to the catalyst chamber
which consists of rows of tubes.
Conversion of secondary alcohols to ketone
Acetone and methyl ethyl ketone
 The flue gases are circulated by a fan and heat is
supplied to them by the products of combustion of
gas burner feeding into the stream, the excess gas
being bled to atmosphere.
 The rate of circulation is such that the temperature
of the flue gases does not drop by more than 5oC
during passage across the tubes. The temperature
difference between the flue gases and maximum
temperature attained in tubes is 20oC.
Acetone and methyl ethyl ketone
 The vapors leaving the catalyst chamber can
exchange heat with the incoming vapors.
 They are passed through a mild steel cooler where
about 50% of the acetone or 80% of the methyl
ethyl ketone condenses.
 Theuncondensed vapors are washed out of the
hydrogen by passage up a ring-packed tower
countercurrent to a flow of water.
Acetone and methyl ethyl ketone
 The flow of water is such to give a final
ketone concentration of 20% in water. The
issuing gas contains about 0.5% ketone
vapor and is hydrogen of over 99% purity, the
main impurity being propylene.
 Theanhydrous and wet ketones are collected
separately and redistilled.
 The 2% of alcohol undecomposed and
distilled from the ketones is returned to the
feed to the catalyst chamber.
Conversion of secondary alcohols to ketone
Production of styrene from Ethylbenzene

 Styrene is prepared by dehydrogenating

ethylbenzene over a zinc oxide catalyst at
approximately 600oC.

C6H5C2H5 C6H5CH:CH2 + H2

 In addition to the main reaction, a number

of side reactions lead to the formation of
unwanted products.
Production of styrene
 The side reactions are of two main classes:
1. The cracking of ethylbenzene to give benzene, toluene,
methane, ethane etc.
2. The cracking of such hydrocarbons to carbon followed
by reaction of this carbon with the steam used as
diluent with the consequent formation of carbon
dioxides.
 Production of styrene
 Lastly, very small quantities of materials such as
stilbene and diphenyl have been detected in the
product
 For economic operations, the production of by-
products must be kept to a minimum.
 Conditions which favor thermal cracking are high
temperature and contact with ferrous metal, while the
water gas reaction is promoted by carbon formation
which results when the reactants entering the
convertor are not sufficiently diluted.
Production of styrene
 The normal diluent is steam, which should be
present in the ratio of about 1.2-1.5:1 is used.
 There is no objection to the use of higher steam
ratio other than unnecessary consumption of heat.
 The flue gas temperature is normally 100-200 oC
higher than that of the reactants so that there may
be a serious risk of thermal cracking of material
passing close to the converter tube surfaces if the
heat exchange is insufficient
Production of styrene:
 The dehydrogenation reaction is endothermic and a
considerable amount of heat has to be added to the converter
in order to maintain the reaction temperature.
 Heat is supplied by flue gases and the converter has been
designed with the object of achieving as high a rate of heat
transfer as possible between flue gases and reactants.
 The most important factor controlling successful
dehydrogenation is the type of catalyst employed.
 Production of styrene
A catalyst consisting principally of zinc oxide with the
addition of certain promoters such as alumina and
chromates has been found to be most satisfactory.

 Thecatalyst gives a conversion of about 40% per pass,

with an overall conversion efficiency of about 92%, and
has a life of about 9 months.
Process Description
 Ethylbenzene and steam are fed continuously into
an evaporator.
 The mixed vapors, after preheating in heat
exchangers are led into a converter, where
dehydrogenation of ethylbenzene to styrene occurs
in the presence of zinc-oxide based catalyst.
 The gases leaving the converter are partially cooled
in the heat exchangers referred to above and then
further cooled in a condenser system.
Process description (Cont)
 After condensation, the hydrocarbon products are separated from water,
inoculated with a stabilizer and finally separated by fractional distillation
in a series of columns where benzene and toluene are first removed;
then unreacted ethylbenzene is separated and returned to the reaction
and finally styrene is separated.

 The corresponding approximate composition of the products on the

hydrocarbon stream is
Styrene………. 40%
Ethylbenzene… 59%
Benzene,etc…… 1%