Oxidation

J. HENRIQUE TELES, BASF SE, Ludwigshafen, Germany

IVE HERMANS, University of Wisconsin, Madison, USA
GERHARD FRANZ, Consultant, Marl, Germany
ROGER A. SHELDON, Technische Universiteit Delft, Delft, The Netherlands

1. Introduction . . . . . . . . . . . . . . . . 1 5. Homolytic Oxidation. . . . . . . . . . 51

2. Overview of Industrial Oxidation 5.1. Historical Development; Reaction
Processes . . . . . . . . . . . . . . . . . . 2 Mechanism; Radical Reactivity . . . 51
2.1. Inorganic Chemicals Produced by 5.2. Kinetics of Autoxidation . . . . . . . 58
Oxidation . . . . . . . . . . . . . . . . . 5 5.3. Differences between Liquid- and
2.1.1. Sulfur Compounds . . . . . . . . . . . 5 Gas-Phase Autoxidations . . . . . . . 61
2.1.2. Carbon Derivatives. . . . . . . . . . . 7 5.4. Homolytic Oxidation in the Liquid
2.1.3. Nitrogen Compounds . . . . . . . . . 7 Phase . . . . . . . . . . . . . . . . . . . . 62
2.1.4. Chlorine Derivatives . . . . . . . . . . 9 5.4.1. Secondary Reactions of Radicals,
2.2. Organic Chemicals Produced by Peroxides, and other Intermediates 62
Oxidation . . . . . . . . . . . . . . . . . 10 5.4.2. Metal Catalysis in Homolytic
2.2.1. Olefins and Alkynes . . . . . . . . . . 10 Liquid-Phase Oxidation . . . . . . . 68
2.2.2. Epoxides . . . . . . . . . . . . . . . . . . 11 5.4.3. Inhibitors of Homolytic Liquid-
2.2.3. Hydroperoxides . . . . . . . . . . . . . 17 Phase Oxidation . . . . . . . . . . . . . 71
2.2.4. Alcohols . . . . . . . . . . . . . . . . . . 20 5.4.4. Special Cases of Homolytic
2.2.5. Aldehydes . . . . . . . . . . . . . . . . . 21 Oxidation . . . . . . . . . . . . . . . . . 72
2.2.6. Ketones . . . . . . . . . . . . . . . . . . . 24 5.4.5. Process Technology of Homolytic
2.2.7. Phenols and Derivatives . . . . . . . 26 Liquid-Phase Oxidation . . . . . . . 73
2.2.8. Carboxylic Acids, Saturated . . . . 29 5.5. Homolytic Gas-Phase Oxidation. . 77
2.2.9. Carboxylic Acids and Anhydrides, 5.6. Gas Explosions and Safety Data. . 78
Unsaturated. . . . . . . . . . . . . . . . 35 6. Heterolytic Oxidation . . . . . . . . . 83
2.2.10. Carboxylic Acids and Anhydrides, 6.1. Heterolytic Oxidation in the Liquid
Aromatic . . . . . . . . . . . . . . . . . . 37 Phase . . . . . . . . . . . . . . . . . . . . 83
2.2.11. Esters, Lactones, and Carbonates 41 6.2. Heterogeneously Catalyzed Gas-
2.2.12. Nitriles . . . . . . . . . . . . . . . . . . . 43 Phase Oxidation . . . . . . . . . . . . . 88
2.2.13. Compounds Containing NO 6.2.1. Oxidation Catalysts . . . . . . . . . . 88
Bonds . . . . . . . . . . . . . . . . . . . . 44 6.2.2. Process Technology of
2.2.14. Chlorinated Compounds . . . . . . . 47 Heterogeneously Catalyzed
2.2.15. Organosulfur Compounds . . . . . . 49 Oxidations . . . . . . . . . . . . . . . . . 93
3. Thermodynamics; Stability References . . . . . . . . . . . . . . . . . 96
of Hydrocarbons . . . . . . . . . . . . . 50
4. Reaction Types . . . . . . . . . . . . . . 50

1. Introduction used to prepare it makes use of a typical oxidant

The chemical term oxidation is used here both
in the sense of the take-up of oxygen by organic
and inorganic materials and also in cases when
the product contains no oxygen, but the process
such as O2. Processes like oxidative chlorina-
tions with HCl/O2 are thus included here, but
simple chlorinations are not. Biological oxida-
tions, although of considerable technical impor-
tance, are not included in this article. The same

# 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a18_261.pub2
2 Oxidation
is true for the combustion of organic material to
obtain energy, and undesired oxidations like the
corrosion of metals and the aging of polymers.
All of these are outside the scope of this article.
Atmospheric oxygen is by far the most
important and also the cheapest oxidizing
agent, since all others, for example, HNO3,
H2SO4 and SO3/H2SO4 (oleum), Cl2, MnO2,
CrO3, KMnO4, as well as H2O2 and the organic
hydroperoxides, must first be produced by
using oxygen or electric current. However,
oxidations with molecular oxygen usually
require much more elaborate catalyst and pro-
cess development to achieve the high selectivi-
ties required in industrial oxidation processes
than, for example, those with Cl2 or HNO3.
They generally also require a much higher
investment, which only becomes economically
worthwhile upon exceeding a certain minimum
capacity for a production plant. This currently
lies between 104 and 105 t/a, depending on the
product, although exceptions are not rare.
Before World War II, organic materials were
mostly oxidized with inorganic oxidizing
agents and only rarely directly with O2. The
most important products of industrial organic
chemistry at that time were pharmaceuticals
and dyes, for which only relatively small quan-
tities of organic intermediates were required.
Exceptions included phthalic anhydride, for
which the heterogeneously catalyzed gas-phase
oxidation of naphthalene was developed to an
industrial level in Germany in 1916 (BASF) and
in the USA (Bureau of Chemistry), and maleic
anhydride, which was first obtained in 1928 by
the Barret Co. in an analogous process involv-
ing the oxidation of benzene.
The age of plastics, with the mass produc-
tion of polyamides, polyesters, polyurethanes
etc., and the precursors necessary for them,
only began after World War II.
Since about the mid-1970s, ecological argu-
ments have become more frequent, especially
in academic literature, not only to explain the
decreasing importance of inorganic oxidizing
agents, but also to promote their substitution (or
even outright ban) by allegedly greener or
more sustainable oxidants [1]. However, this
discussion has often been limited to the nature
and cost of the oxidant itself, and very often it
has even been misused to simply justify
research. A truly holistic discussion, in which
not only the nature of the oxidant, but also the
workup of the product, the recycling of solvents
and catalysts, and the disposal of byproducts
and wastewater are considered, has very seldom
been done in an academic context. In an indus-
trial context, all these aspects are taken into
consideration, because they all have an impact
on the cost of production. Also, although this
may sound politically incorrect, the economics
of a process are a good indicator of its sustain-
ability and, especially for low-volume special-
ties or pharmaceuticals, old-fashioned oxidants
may still be the best choice. For commodities,
in which the raw materials often make up 80%
of the production costs, it is no surprise that the
cheapest oxidant (air) has become the most
important one.
2. Overview of Industrial Oxidation
Processes
In this chapter the main classes of industrially
relevant products which are obtained by an
oxidation reaction are briefly reviewed, but
older reviews can still be recommended, at least
from a historical point of view [2, 3]. The
individual processes and reactions are not dis-
cussed in detail, but reference is made to appro-
priate comprehensive reviews, and current
trends and challenges are pointed out. For
most of the reactions, specialized keywords
are available and appropriate reference is
made to these.
In some cases an arbitrary line had to be
drawn as to what is still considered an oxidation
or not. For instance, the reaction of tert-amyl
alcohol with H2O2 to produce tert-amyl hydro-
peroxide, the reaction of acetic acid with H2O2
to produce equilibrium peracetic acid solution,
and the reaction of cyclic ketones with H2O2 to
produce perketals are all industrially important
and could at least formally also be seen as
oxidation reactions. However, as there is no
change in the oxidation state of the organic
residue, these reactions are better classified as
nucleophilic substitutions or additions and are
not considered here. Dehydrogenations, for-
mally also oxidations, are also not covered here.
All known industrial processes which use
oxidation and have a capacity of at least 1000 t/a
are included in this overview. Although some
 Oxidation 3

agrochemicals also include an oxidation step in
their multistep synthesis, and some of these can
indeed have capacities of well over 1000 t/a,
these are not included here. The main reason is
because the production amounts of an agro-
chemical can vary widely from year to year
and capacities or synthesis methods are usually
not openly available. For instance, in the case of
Propargite, a widely used acaricide, for which
cyclohexene oxide, made by an oxidation
reaction, is a building block, the amounts used
in the USA varied from year to year between 200
t in 2010 and 2200 t in 1994 [4].
The pharmaceutical industry also uses a
plethora of oxidation reactions, but these are
mostly scaled-up laboratory methods. This sub-
ject has been thoroughly reviewed [5, 6].
An overview of all organic products indus-
trially obtained by oxidation are summarized in
Tables 1a1d. The products are arbitrarily
divided into commodities (Table 1a, products
with a capacity of more than 106 t/a), large

Table 1a. Commodity organic chemicals produced by oxidation (capacity >1
106 t/a)

Product or intermediate Capacity, 106 t/a Oxidanta Phaseb Catalystc

Terephthalic acidd 60 O2 liq homo

Ethylene dichloride 30 O2 gas hetero
Ethylene oxide 26 O2 gas hetero
Formaldehyde 20 O2 gas hetero
Cumene hydroperoxidee 17 O2 liq none
Propylene oxidef 10 Cl2 liq none
ROOH liq homo/hetero
H2O2 liq hetero
Acetylene 7 O2 gas none
Acrylonitrileg 7 O2 gas hetero
Ethylbenzene hydroperoxideh 6 O2 liq none
Acrylic acid 6 O2 gas hetero
Vinyl acetatei 5.5 O2 gas hetero
Hydrogen peroxide 5.5 O2 liq none
Phthalic anhydride 5.5 O2 gas hetero
Acrolein 5 O2 gas hetero
Cyclohexanolj 4.5 O2 liq homo
Adipic acid 4 HNO3 liq homo
Methyl nitrite 2.5 O2 liq/gas none
Epichlorohydrin 2.3 Cl2 liq none
tert-Butylhydroperoxidek 2 O2 liq none
Cyclohexanonej 2 O2 liq homo
Hydrogen cyanidel 2 O2 gas hetero
Acetaldehyde 2 O2 liq homo
gasm hetero
Maleic anhydride 2 O2 gas hetero
Methacrolein 1.2 O2 gas hetero
Methacrylic acidn 1.1 O2 gas hetero
Isophthalic acid 1 O2 liq homo
a
O2 stands for both pure oxygen and air.
b
liq: reaction in liquid phase; gas: reaction in gas phase.
c
homo: homogeneous catalyst, hetero: heterogeneous catalyst.
d
Includes ca. 3
106 t/a of dimethyl terephthalate.
e
First step in the Hock process for phenol and in the CUPO process for propylene oxide.
f
The split among the technologies is approximately 4.3
103 t/a for chlorohydrin, 4.8
103 t/a for cooxidation processes and 0.9
103 t/a for
hydrogen peroxide based processes.
g
200
103 t/a are based on propane and the remaining is based on propene.
h
First step in the SMPO process to propylene oxide.
i
The total capacity for vinyl acetate is around 7
106 t/a, but only 5.5
106 t/a are produced by oxidative acetoxylation of ethylene.
j
Combined capacity of cyclohexanol and cyclohexanone is around 7
106 t/a.
k
First step of the MTBE/PO process for propylene oxide.
l
Only oxidative processes. The total world capacity is ca. 2.5
106 t/a.
m
The gas-phase oxidation of ethanol has only a negligible contribution to the overall acetaldehyde capacity.
n
This is only the capacity share of methacrylic acid and methyl methacrylate that includes an oxidation step. The total capacity is around
3.4
106 t/a.
4 Oxidation

Table 1b. Intermediates produced by oxidation (capacity between 100 thousand and 1
106 t/a)

Product or intermediate Capacity, 103 t/a Oxidanta Phaseb Catalystc

Acetic acidd
Acetaldehyde oxidation 350 O2 liq homo
Ethane oxidation 30 O2 gas hetero
Ethylene oxidation 170 O2 gas hetero
Allyl acetate 600 O2 gas hetero
Cyclohexyl hydroperoxidee 500 O2 liq none/homo
Propionic acid and other non-a-branched acids 470 O2 liq none
10 O3 liq none
Benzoic acid 400 O2 liq homo
Butadiene 300 O2 gas hetero
Oxalic acidf 300 HNO3 liq homo
Glyoxal 250 HNO3 liq none
O2 gas hetero
2-Ethylhexanoic acid and other a-branched acids 225 O2 liq none
Alfols 200 O2 liq none
Poly(phenylene ether) 200 O2 liq homo
Epoxidized soybean and linseed oils 150 H2O2 liq homo
Trimellitic acid 150 O2 liq homo
Dimethyl carbonateg 150 O2 liq homo
But-2-ene-1,4-diol diacetateh 100 O2 liq heter
Cymene hydroperoxides 100 O2 liq none
Diisopropylbenzene dihydroperoxidei 100 O2 liq none
Cyclododecanol 100 O2 liq homo
Methyl methacrylatej 100 O2 liq hetero
a
O2 stands for both pure oxygen and air.
b
liq: reaction in liquid phase; gas: reaction in gas phase.
c
homo: homogeneous catalyst, heter: heterogeneous catalyst.
d
Only oxidation processes. Total world capacity for acetic acid is around 15
106 t/a.
e
First step in the KA-oil (cyclohexanone/cyclohexanol) process.
f
Only oxidation processes. Total world capacity for oxalic acid is around 600
103 t/a.
g
The capacity given is just for plants using the Eni oxidative carbonylation technology.
h
Intermediate in the Mitsubishi BDO/THF process.
i
Combined capacity for both meta and para isomers. First step in the Hock process for hydroquinone/resorcinol.
j
Asahi process for oxidative esterification of methacrolein. Total world capacity for methyl methacrylate is ca. 4
106 t/a.

intermediates (Table 1b, products with a
capacity between 105 and 106 t/a), specialities
(Table 1c, products with a capacity of
(20100)
103 t/a), and small specialties
(Table 1d, products with a capacity of less
than 20
103 t/a). In addition to the estimated
capacities, which are mostly obtained from
company intelligence, the tables also include
data on the oxidant used, on the phase in which
the reaction takes place (liquid or gas), and the
type of catalyst used (homogeneous, heteroge-
neous, or no catalyst at all).
The data in Tables 1a1d already make some
interesting conclusions possible. The total
capacity for organic chemicals produced by
an oxidation process is close to 250
106 t/a
or ca. 35 kg per human per year. Of this amount,
almost 98% of the capacity are commodities,
less than 2% are intermediates, less than 0.5%
are specialties, and less than 0.1% are small-
scale specialties. Overall, almost 93% of the
capacity uses air or O2 as the oxidant, which is
easy to understand because O2 is the cheapest
available oxidant. The next most important
oxidants are HNO3 and nitrogen oxides (3.6%
of the total capacity), Cl2 (2.8% of the total
capacity), alkyl hydroperoxide (2% of the total
capacity), and H2O2 (0.6% of the total capacity).
Approximately equal amounts of organic
chemicals are produced by oxidation processes
in the liquid phase and in the gas phase. This
might at first sight seem surprising, but quite a
few large commodities are produced by oxida-
tion in the liquid phase, and above all the largest
one, terephthalic acid, uses one such process.
Smaller products tend to use liquid-phase
 Oxidation 5

Table 1c. Specialties produced by oxidation (capacity of (20100)
103 t/a)

Product or intermediate Capacity, 103 t/a Oxidanta Phaseb Catalystc

Dimethyl sulfoxide 95 NO2/O2 liq none

Secondary alkane sulfonates 50 O2/hn liq none
35 Cl2/hn
Glyoxylic acid 80 HNO3 liq none
Acetonitriled 80 O2 gas heter
N,N-Dimethyl fatty amine N-oxide 75 H2O2 liq none
Benzaldehydee 70 O2 liq homo
Cyclohexanone oximef 67 H2O2 liq heter
Hydroquinone 60 H2O2 liq homo/hetero
O2 liq none
MnO2 liq none
Caprolactone 60 H2O2 liq none
m-Phthalodinitrile 60 O2 gas heter
Methanesulfonic acid 30 HNO3 liq none
25 Cl2 liq none
Oxidized polyethylene waxes 50 O2 liq none/homo
Nitroalkanes (C1-C3)g 50 HNO3 gas none
1,2-Butylene oxide 50 Cl2 liq none
1,6-Hexanediolh 50 O2 liq homo
Nicotinic acid 40 HNO3 liq none
2,6-Naphthalene dicarboxylic acid 30 O2 liq homo
Cyclododeca-4,8-diene-1-onei 30 N2O liq none
Dodecanedicarboxylic acid 25 HNO3 liq homo
Catechol 20 H2O2 liq homo/hetero
Isoprenol 20 O2 gas hetero
3-Cyanopyridine 20 O2 gas hetero
a
O2 stands for both pure oxygen and air.
b
liq: reaction in liquid phase; gas: reaction in the gas phase.
c
homo: homogeneous catalyst, hetero: heterogeneous catalyst.
d
Capacity for purified acetonitrile formed as byproduct in acrylonitrile synthesis.
e
As a byproduct in benzoic acid synthesis.
f
Only includes the capacity for the ammoximation process.
g
Total capacity from propane nitration.
h
Ex 6-hydroxycaproic acid and adipic acid byproducts formed in the cyclohexane oxidation.
i
Intermediate in the BASF N2O-based cyclododecanone process.

processes (7585% of the capacity), which
reflects the high investment costs and the
high costs for developing the required hetero-
geneous catalysts that are associated with pro-
cesses in the gas phase.
Almost half of the capacity uses heteroge-
neous catalysts, one-third uses homogeneous
catalysts, and the remaining 20% uses no cata-
lyst at all. This might also seem counter-
intuitive, because large processes are often
associated with heterogeneous catalysis and
when asked for examples of homogeneously
catalyzed processes, usually only the hydro-
formylation of olefins or the carbonylation of
methanol to acetic acid is mentioned. Actually,
many of the large commodities produced by
oxidation also use homogeneous catalysis, and
here again terephthalic acid is the most promi-
nent example, being the largest product
produced by homogeneous catalysis, far larger
than oxo products or acetic acid.
2.1. Inorganic Chemicals Produced by
Oxidation
2.1.1. Sulfur Compounds
Sulfur Dioxide.
S O2 ! SO2 1
Sulfur dioxide, SO2, is one of the most basic
inorganic chemicals, located right at the base of
the sulfur value chain (! Sulfur Dioxide). It is
formed in many combustion processes and in
ore processing as a secondary product, so it is
quite difficult to assess the world capacity. It is
6 Oxidation

Table 1d. Small-scale specialties produced by oxidation (capacity <20
103 t/a )

Product or intermediate Capacity, 103 t/a Oxidanta Phaseb Catalystc

Methyl ethyl ketone oxime 15 H2O2 liq heter

4-tert-Butyl benzaldehyde 15 e liq none
MnO2 liq none
O2 liq homo
Vanillin/ethylvanillin 10 O2 liq homo
Trimethylbenzoquinone 10 O2 liq homo
Azelaic acid 10 O3/O2 liq none
Dimethylol propionic acid 10 H2O2 liq none
Pyromellitic dianhydride 10 O2 gas heter
Cyclopentanoned 10 N2O liq none
o-Phthalodinitrile 10 O2 gas hetero
Benzonitrile 10 O2 gas hetero
Hexafluoropropylene oxide 10 O2 liq/gas none
Triethylamine N-oxide 8 H2O2 liq none
Dimethyl sulfone 8 H2O2 liq none
Cocamidopropyl N-oxides 5 H2O2 liq none
1,8-Naphthalenedicarboxylic anhydride 5 O2 gas hetero
f
1-Pentene oxide 5
Cyclododecanediols 5 O2 liq homo
Trichloroacetaldehyde hydrate 5 Cl2 liq none
Trimethyl adipic acid 4 HNO3 liq none
4-Methoxybenzaldehyde (anisaldehyde) 35 e liq none
MnO2 liq none
Crotonic acid 3 O2 liq homo
o-Chlorobenzonitrile 3 O2 gas hetero
Salicylaldehydee 3 O2 liq hetero
N-Methylmorpholine N-oxide 3 H2O2 liq none
Cyclohexene oxide 2 H2O2 liq none
Menadione 1 CrVI liq none
Biphenyl tetracarboxylic dianhydride 1 O2 liq homo
Methoxyacetic acid 1 O2 liq hetero
Furaneol 0.5 O3 liq none
a
O2 stands for both pure oxygen and air.
b
liq: reaction in liquid phase; gas: reaction in the gas phase.
c
homo: homogeneous catalyst, hetero: heterogeneous catalyst.
d
Total capacity for cyclopentanone. The fraction produced by N2O oxidation has not been disclosed.
e
Only part of it is produced by an oxidation reaction.
f
Both Cl2/water, H2O2, and peracids seem to be used commercially as oxidants by different producers.

also produced on purpose, mainly by burning
sulfur with air. Its main use is in the production
of sulfuric acid.
Sulfur Trioxide and Sulfuric Acid.
SO2 1=2 O2 ! SO3
To obtain sulfuric acid, SO2 must be oxidized
further to sulfur trioxide (SO3) (Eq. 2) before it
is absorbed in concentrated sulfuric acid to first
obtain oleum, a solution of SO3 in sulfuric acid
(! Sulfuric Acid and Sulfur Trioxide), which is
then diluted with water to obtain concentrated
sulfuric acid. Although the oxidation of SO2
with O2 to SO3 is exothermic, in the absence of
a catalyst this is a very slow reaction. The oldest
industrial processes for the production of sul-
furic acid (lead chamber process and tower
process) involved the oxidation of SO2 in the
aqueous phase with nitrogen oxides as cata-
lysts. However, this process has the dis-
2 advantage that the concentration of the
produced sulfuric acid is limited to a maximum
of 78%. For this reason, the process is not
economically competitive with the newer con-
tact process. In the contact process a heteroge-
neous catalyst based on vanadium oxide and
alkali metal sulfate (usually sodium and potas-
sium) as the promoter on a silica support is used
almost exclusively. The alkali metal sulfate
forms a melt that contains the active vanadium

complex and remains trapped in the pores of the
support, so this is actually a supported liquid-
phase-type catalyst. Standard catalysts are
active only above 400 C, but at this temperature
the equilibrium conversion of SO2 is already
below 99%. This limitation can be overcome by
technical measures like the intermediate
absorption of SO3 or by stabilizing the melt
by adding cesium salts. The development of a
catalyst that would be active at significantly
lower temperature is still a major challenge.
Considering the huge worldwide capacity
for sulfuric acid, which is estimated at ca.
350
106 t/a (as 100% sulfuric acid) a break-
through in low-temperature catalysts for the
oxidation of SO2 would have a major impact [7].
Sulfur, Elemental. Sulfur is one of the basic
raw materials of chemical industry. (! Sulfur)
It occurs naturally mainly as gypsum, calcium
sulfate, but this is of no relevance for the
industrial production of sulfur. It also occurs
as elemental sulfur, as H2S in natural gas, and as
organic sulfur compounds in oil and coal. H2S
must be removed from natural gas, because it is
both corrosive and highly toxic. Organic sulfur
compounds must also be removed from
naphtha and fuels, mostly by hydrogenative
desulfurization, which also produces H2S.
Essentially all of the H2S is oxidized to
elemental sulfur in the Claus process (Eqs. 3),
many variations of which are in commercial use.
H2 S 3=2O2 ! SO2 H2 O
3
SO2 2 H2 S ! 3 S 2 H2 O
Both steps can be conducted in one stage or
separately in two stages. In a first step H2S is
burned with air to produce SO2, no catalyst
being required. In a second step the SO2 reacts
with H2S to form elemental sulfur and water,
which can be viewed as an oxidation in which
SO2 plays the role of the oxidant. This step
requires a catalyst, and many materials have
been tested for this purpose, although vanadium
oxides are by far the most active ones. This
subject has been thoroughly reviewed [8].
The total production capacity for elemental
sulfur is estimated at around 60
106 t/a, but no
breakdown between mining output and Claus-
derived sulfur production is available.
Oxidation 7
2.1.2. Carbon Derivatives
Synthesis Gas.
Cx Hy Oz O2 ! CO H2 CO2 4
Synthesis gas, or syngas, is the common name
used for mixtures of CO, CO2, and H2 of
varying composition. These mixtures can be
obtained from almost any carbon-containing
feedstock. Usual feedstocks are natural gas,
petroleum, and coal (! Methanol, Section
5.1), but recently the production of synthesis
gas from renewable feedstocks has become a
focus of active research [9, 10]. The largest
source of syngas is the steam reforming of
methane, which is not an oxidation reaction
but actually a disproportionation. However,
syngas is also formed in partial oxidation pro-
cesses like the oxidative gasification of coal or
hydrocarbons (! Gas Production, 2. Processes)
or as a byproduct in acetylene synthesis. Syngas
is a pivotal raw material in industrial organic
chemistry and has many uses. It is used as such
for the production of methanol (estimated
world capacity in 2014: 98
106 t/a) and as a
source of H2 and CO for hydroformylation and
the production of oxo chemicals (estimated
world capacity for oxo chemicals in 2014:
14
106 t/a). Syngas can be subjected to a water
gas shift to convert CO and water to H2 and CO2
for the production of H2, which is then used for
the synthesis of ammonia and for all kinds of
hydrogenation reactions. Syngas can also be
separated into its components (Eq. 4), mostly to
produce pure CO, which is then used as a raw
material for the production of methyl formate
and pivalic acid, among others.
2.1.3. Nitrogen Compounds
NO and Nitric Acid.
4 NH3 5 O2 ! 4 NO 6 H2 O 5
Industrially, NO is produced by catalytic com-
bustion of ammonia over a suitable catalyst,
usually platinum gauze, at temperatures in the
range of 850950 C (Eq. 5). (! Nitric Acid,
Nitrous Acid, and Nitrogen Oxides, Sections
1.3.1 and 3.2). This is a highly efficient process
with very high selectivity and conversion at
8 Oxidation

very low contact times. The only drawback of
the process is the slow loss of platinum from
the catalyst at the high reaction temperatures.
However, the use of 510% rhodium can con-
siderably stabilize the catalyst and decrease
platinum losses.
Most of the NO produced worldwide is used
to manufacture nitric acid. In this process mix-
tures of NO and air are adsorbed in water,
usually at pressures between 1 and 12 bar.
This is a multistep reaction that requires no
catalyst. First, NO is oxidized by O2 to yield
NO2, which then reacts with water to a mixture
of nitric and nitrous acid. The latter dispropor-
tionates to nitric acid and NO. The overall
stoichiometry is given by the following equation.
No reliable data exist on the world capacity
for hydroxylamine, so this can only be roughly
estimated from the capacity of caprolactam,
which is by far the largest single use for
hydroxylamine. In 2008 the estimated world
capacity for hydroxylamine should thus be ca.
1.5
106 t/a (calculated as 100% NH2OH).
Hydrazine. Historically, hydrazine was first
industrially produced by the Raschig process.
This is a two-step process involving the oxida-
tion of ammonia with sodium hypochlorite to
chloramine and subsequent reaction of the
chloramine with a large excess of ammonia
(Eqs. 9) (! Hydrazine, Chap. 4).
i NaOCl NH3 ! NH2 Cl NaOH 9

4 NO 2 H2 O 3 O2 ! 4 HNO3 6 ii NH2 Cl NH3 NaOH ! NH2 NH2 NaCl H2 O

An improvement of the original Raschig

The estimated world capacity for nitric acid process was achieved by performing the
in 2011 was estimated to be around 72
106 t/a reaction in the presence of acetone (Bayer
(based on 100% HNO3) and has been stagnant Ketazine process, now operated by Lanxess)
since the late 1980s. or methyl ethyl ketone (Fisons process, which
Hydroxylamine. is no longer in use). In these processes, the
primary product is not hydrazine but a ketazine.
TS-1 In a second step the ketazine is hydrolyzed to
NH3 H2 O2 
! NH2 OH H2 O 7
produce free hydrazine and recover the ketone.
A ketazine is also the primary product of the
Hydroxylamine in the form of hydroxyl-
state-of-the-art technology. This process, devel-
ammonium sulfate is mostly produced by
oped originally by Pechiney-Ugine-Kuhlmann,
hydrogenating NO. However, the discovery
involves the reaction of H2O2 with NH3 in the
that titanium silicalite (TS-1) oxidizes NH3 to
presence of methyl ethyl ketone and a catalyst
hydroxylamine, which can be trapped in situ by
to form methyl ethyl ketazine. This ketazine is
ketones to form oximes (Eq. 7). has led to the
then hydrolyzed in a similar way as in the
development of several industrial processes for
Bayer Ketazine process to produce hydrazine
the production of oximes. These are discussed
(Eq. 10).
in more detail in Section 2.2.13.
The old Raschig process, involving the oxi-
dation of ammonium carbonate with NO and
NO2 to ammonium nitrite, reaction with SO2 to
hydroxylamine disulfonate, and subsequent
hydrolysis to hydroxylammonium sulfate, is
still in use (Eqs. 8) (! Hydroxylamine, Chap. 4).

10

Although the Pechiney-Ugine-Kuhlmann

process is already a fairly efficient process
and uses a less problematic oxidant, it is still
a two-step process with considerable complex-
ity. In view of the large number of applications
8 for hydrazine, much thought has been given to

potential single-step processes. The hydrogen-
ation of N2 and the dehydrogenative coupling
of ammonia are so thermodynamically
unfavorable that they can not be considered a
reasonable reaction to target (DGf(25 C)
159.4 and 192.2 kJ/mol respectively). The
direct oxidation of ammonia with H2O2 is
thermodynamically feasible (DGf(25 C)
159.4 kJ/mol), but hydrazine is a much stron-
ger reducing agent than NH3 and so it should be
very difficult to avoid overoxidation. Another
thermodynamically feasible route would be the
hydrogenation of N2O (DGf(25 C) 172.9
kJ/mol), but this route seems to have never been
taken into consideration and should also be very
challenging due to the kinetic inertness of N2O.
Nevertheless, hydrazine has a wide range of
applications, and the world capacity for hydra-
zine is estimated to be at least 60
103 t/a, so the
development of a one-step process for the
production of hydrazine is an attractive but
challenging target.
2.1.4. Chlorine Derivatives
Chlorine. Chlorine is one of the largest-scale
inorganic chemicals produced by oxidation.
The world capacity for the production of chlo-
rine is estimated at 77
106 t/a with several
hundred producers and production sites world-
wide. Almost the entire amount of chlorine is
produced by the electrolysis of sodium chloride
solutions in mercury, diaphragm, or membrane
cells (Eq. 11) (! Chlorine, Chaps. 5, 6, 7).
e
2 NaCl 2 H2 O ! Cl2 2 NaOH H2 11
The fixed ratio of chlorine and NaOH pro-
duced in the above processes has the drawback
that they have little flexibility to respond to
fluctuations in the demand for these two chem-
icals. For this reason, and since HCl is also
available as a byproduct in several processes
using Cl2, such as phosgene-based isocyanate
production, processes have also been developed
to oxidize HCl back to chlorine [11]. However,
such processes amount to at most 5% of the
total world capacity for chlorine. Older pro-
cesses like the Kel-Chlor process used nitric
acid as the oxidant, but this process is not used
commercially anymore [12]. Bayer Material-
Science developed an Oxygen Depolarized
Oxidation 9
Cathode (ODC) Technology for HCl electrol-
ysis [13] together with ThyssenKrupp and
UHDENORA [14] that is claimed to provide
energy savings up to 600700 kWh/t Cl2.
UHDENORA recently announced a 80
103 t/a
sodium hydroxide plant in Binzhou City,
China using this technology [15]. Bayer
announced in 2006 that it intends to build an
ODC HCl electrolysis plant at its integrated
site in Shanghai to recycle HCl from isocyanate
(MDI) production and also offers this technology
for licensing [16]. More recent developments,
for instance, from Sumitomo Chemical, use
the Deacon process, involving the catalytic
oxidation of HCl with oxygen in the gas
phase on supported Ru catalysts [17]. Bayer
announced in 2008 that it will build a plant
to recycle HCl from toluene diisocyanate
synthesis by using Sumitomos technology at
its Shanghai site [18].
Chlorate and Perchlorate. For the production
of chemicals containing chlorine in a higher
oxidation state than elemental chlorine, see !
Chlorine Oxides and Chlorine Oxygen Acids.
Two of them are discussed here, because they
are produced by dedicated oxidation processes
and also because of their importance.
Sodium chlorate (NaClO3) is produced on a
large scale by the electrolysis of sodium chlo-
ride. This is a complex reaction involving the
electrochemical oxidation of chloride to hypo-
chlorite, followed by an autoxidation of hypo-
chlorite to chlorate. The simplified pathway is
shown in Equations (12).
2 Cl ! Cl2 2 e
Cl2 H2 O HClO H Cl 12

3 HClO ! ClO
3 3 H 2 Cl
The world capacity in 2012 was estimated to
exceed 4
106 t/a. The major use of sodium
chlorate is in the on-site production of chlorine
dioxide for the elemental chlorine-free bleach
in the pulp and paper industry. The second
largest use of sodium chlorate is for the pro-
duction of sodium perchlorate by electrochem-
ical oxidation (Eq. 13).
ClO3  H2 O ! ClO4  2 H 2 e 13
The major use of sodium perchlorate is in the
production of ammonium perchlorate, which is
10 Oxidation
one of the major components in solid rocket
fuels for civil and military use. For this reason
there are no reliable data on production capaci-
ties, but it can be estimated that it is in the range
of (1020)
103 t/a.
2.2. Organic Chemicals Produced by
Oxidation
2.2.1. Olefins and Alkynes
Olefins by Oxidative Dehydrogenation.
Despite considerable research efforts [19], the
oxidative dehydrogenation of alkanes to pro-
duce lower olefins such as ethylene, propene,
butenes, and isobutene is of no commercial
relevance. Although pure dehydrogenation is
an endothermic reaction and thus requires con-
siderable energy input, neither the pure oxidative
dehydrogenation nor the autothermal oxidative
dehydrogenation, in which only part of the
hydrogen is oxidized in order to make the overall
reaction slightly exergonic, have been able to
supersede dehydrogenation (Eqs. 14).
14
Oxidative dehydrogenation can also be used
for the production of butadiene from linear
butenes. Although in the past several plants
existed to produce butadiene by oxidative
dehydrogenation of n-butane and linear butenes
(! Butadiene, Section 4.1), the surplus of
butadiene on the market has led to a shutdown
of almost all plants using oxidative dehy-
drogenation technology (using either the Petro-
Tex Oxo-D or the Phillips O-X-D process).
Butadiene is now almost exclusively isolated
from butadiene-containing streams obtained
from the steam cracking of hydrocarbons, but
recent price increases and supply constraints
may lead to a renaissance of on-purpose buta-
diene processes [20]. UOP has recently
announced that it will license the OXO-D
technology for the on-purpose production of
butadiene [21]. The basic technology itself is
quite old but has been considerably improved
[22, 23]. Currently, this technology is used in a
few plants in China with a combined capacity of
350
103 t/a. Both Mitsubishi and BASF/Linde
have announced the development and licensing
of on-purpose butadiene technology by oxida-
tion of n-butenes using Bi/Mo catalysts [24]. It
is expected that the butadiene capacity based on
such oxidative dehydrogenative technology
will grow rapidly.
Another olefin for which a process involving
an oxidation is available is styrene. Most of the
styrene is produced by dehydrogenation, but
since this reaction is highly endothermic it
must be performed in multistage reactors with
intermediate heating. As an alternative, UOP and
Lummus offer the Styrene Monomer Advanced
Reheat Technology (SMART) for licensing. In
this process, after the first dehydrogenation
stage, the hydrogen formed is selectively burned
with air in the presence of steam on an alumina-
supported platinumtin catalyst [25]. It is not
known if this process is already being commer-
cially used.
A similar situation is found in the oxidative
coupling of methane (Eq. 15). In spite of inten-
sive research efforts and the fact that only
modest yields of about 20% are deemed neces-
sary to achieve economic feasibility, this tech-
nology is still not used industrially, and the
target yield has still not been achieved [26].
2 CH4 O2 ! H2 C CH2 2 H2 O 15
It is expected that research on this subject
will continue in spite of the fact that the avail-
ability of cheap ethane from shale gas and the
conversion of a large number of naphtha crack-
ers to light feed (essentially ethane) has made
oxidative methane coupling less attractive.
Acetylene. In contrast to olefins, acetylene is
produced industrially by the coupling of meth-
ane. The reaction is strongly endothermic, but
due to the favorable entropy it becomes exer-
gonic at temperatures above 1230 C (Eq. 16).
DH298 376 kJ=mol
2 CH4 ! HC  CH 3 H2 r
16
DGr < 0 at T > 1230 C
To provide the required energy for the
reaction, part of the methane used is oxidized

in situ and thus effectively the reaction is an
uncatalyzed oxidative methane coupling. The
many different process variations are described
in detail elsewhere (! Acetylene). Although
these processes account for most of the acety-
lene produced in Europe and the USA, globally
they only make up less than 10% of the global
capacity of over 7
106 t/a. Most of the capacity
is located in China and uses calcium carbide as
the source for acetylene.
2.2.2. Epoxides
Ethylene Oxide. Ethylene oxide is now pro-
duced exclusively through the oxidation of
ethylene with O2 in the gas phase using a sil-
ver-based catalyst (Eq. 17) (! Ethylene Oxide).
17
Ethylene oxide is the second largest scale
organic chemical produced by oxidation,
with an estimated installed capacity of over
20
106 t/a in 2012. However, more than 75%
of the world capacity is not isolated as pure
ethylene oxide; instead, the crude product
mixture is immediately treated with water to
produce ethylene glycol. A typical example
of a modern EO/EG plant design is the
Dow/Union Carbide METOR technology
[27].
Much research has been devoted to the
optimization of the catalyst. Modern catalysts
use silver supported on alumina and doped with
small amounts of other metals. Depending on
the nature of the dopants, catalysts can be
divided into two types. The first type has a
somewhat lower selectivity (8082%) at high
productivity (>200 kg m3 h1), works at
lower temperatures (210230 C), and has a
longer lifetime of up to four years. The second
type has significantly higher selectivity
(8890%) but a lower productivity (<180 kg
m3 h1), works at temperatures above 230 C,
and has a shorter lifetime of at most two
years. This subject has been thoroughly
reviewed [28, 29].
Since most of the ethylene oxide is not used
as such, but is immediately transformed to
ethylene glycol, the future of ethylene oxide
technology is very dependent on the current
Oxidation 11
development of processes that directly lead to
ethylene glycol. This is especially true for the
C1-based process based on the oxidative car-
bonylation of methyl nitrite to dimethyl oxalate
und subsequent hydrogenation to ethylene
glycol. This process is discussed under
oxalic acid (Section 2.2.8) and methyl nitrite
(Section 2.2.13).
Propylene Oxide. Propylene oxide is, after
ethylene oxide, the second most important
epoxide with an estimated worldwide capacity
in 2012 of close to 10
106 t/a. In contrast to
ethylene oxide, all propylene oxide produced is
isolated as pure product and only a small part of
it, around 20%, is transformed into propylene
glycol, the major use being the production of
polyetherols as raw materials for polyurethanes
(ca. 60%). In strong contrast to ethylene oxide,
propylene oxide cannot be economically pro-
duced by direct oxidation of propene with O2
(Eq. 18). This is due to the high reactivity of
the allylic hydrogen atoms in the methyl group
of propene leading to a high percentage of
propene being oxidized by an uncatalyzed
and unselective background reaction.
18
Nevertheless, in the early 1970s a process
for the direct oxidation of propene to propylene
oxide in the liquid phase using benzene as the
solvent was developed up to the pilot-plant
scale (10 t per month). The reaction was per-
formed at 200 C and 55 bar. The yield of
propylene oxide based on propene was 45%
and the spacetime yield was 700 kg m3 h1
[30, 31]. However, due to the skyrocketing price
of oil in the mid-1970s these developments were
abandoned. Still, these values are interesting as a
benchmark for later works on the direct oxida-
tion of propene that are discussed below. The
selective catalytic epoxidation of propene with
O2 still remains one of the Holy Grails of indus-
trial research on oxidation. Many efforts have
been devoted to the development of catalysts for
this oxidation in the gas phase, mostly based on
Ag as the active metal, but the problem is still far
from being solved. For example, one of the best
catalysts known contains Ag doped with Mo, K,
Cl, and N and supported on CaCO3 [32]. The
12 Oxidation
selectivity to propylene oxide is 64% at a per-
pass conversion of propene of only 1.5% at
250 C and requires the addition of NO, CO2,
and ethyl chloride to the reactor feed. Strikingly,
the catalyzed reaction in the gas phase actually
runs at a higher temperature than the uncatalyzed
reaction in the liquid phase. The catalyzed
reaction achieves an almost 20% higher selec-
tivity, but at the price of a very low per-pass
conversion, and most of all of a very low space
time yield of only 4.5 kg m3 h1. This is more
than two orders of magnitude lower than that of
the uncatalyzed reaction.
Since the reaction with O2 is not selective
enough, it was necessary to develop processes
based on other terminal oxidants [33] (! Pro-
pylene Oxide). The oldest process for the prep-
aration of propylene oxide is the chlorohydrin
process or PCH process. In this process, shown
in Equation (19), propene reacts with chlorine
in the presence of a large excess of water to
produce a dilute aqueous solution of propylene
chlorohydrins (mostly 2-chloro-1-propanol).
This solution is then treated with a base to
generate propylene oxide, which is then iso-
lated by distillation.
19
This process is still in use and currently
accounts for about 40% of the world capacity,
but its importance is quickly decreasing
because this process is not being used in new
plants. This is both due to the environmental
problems associated with it, such as the large
amount of wastewater and the chlorinated
byproducts, and also to the high specific invest-
ment, because parallel to a propylene oxide
plant, a chlorine plant is also necessary to
deliver both the Cl2 as well as the NaOH for
the second step. Although large PCH plants in
western countries have been upgraded to cope
with waste streams in an environmentally
acceptable manner, these additional measures
just added to the already high specific invest-
ment for plants using this technology.
To overcome the problems associated with
the PCH process a whole family of cooxidation
processes was developed. The oldest of these is
the so-called MTBE/PO process (sometimes
also called TBA/PO process) which is shown
in Equation (20).
20
In the first step, isobutane is oxidized with
O2 to produce tert-butyl hydroperoxide (see
also Section 2.2.3). The hydroperoxide is
then used to epoxidize propene, wheras the
hydroperoxide is reduced to tert-butyl alcohol
(TBA). Since the market for TBA is rather
limited it was mostly transformed into methyl
tert-butyl ether (MTBE), which used to find
wide application as an oxygenate additive for
fuels. The phasing out of MTBE in the USA,
the development of more efficient cooxidation
processes and the process-inherent problems,
such as the low selectivity in the first step and
the safety problems associated with the oxida-
tion of isobutane, quickly led to a loss of
attractiveness of this process and its capacity
share never went much above 10% of the total
installed capacity. Recently, two new plants
have been announced in China which use this
technology, because in China there is still an
attractive and growing market for MTBE as a
fuel additive.
A few years after the MTBE/PO process, a
new cooxidation process took over the techno-
logical lead, the so-called SM/PO process [34],
which is summarized in Equation (21).
21
Two main factors contributed to the success
of the SM/PO process, of which several varia-
tions exist using homogeneous MoVI or hetero-
geneous Ti-on-silica catalysts: first of all, the
good selectivity in the oxidation of ethylben-
zene with O2 to the corresponding hydro-
peroxide, and second the large available

market for the coupled product styrene. In fact,
the SM/PO process actually produces more styr-
ene than propylene oxide (about 2.3 t of styrene
per tonne of propylene oxide). In times when the
styrene market is short and the prices are high,
the SM/PO process makes it possible to produce
propylene oxide at very attractive costs. How-
ever, when the styrene market is long the picture
can reverse completely. In spite of these draw-
backs, the technology was for a long time best-
in-class, and until recently about one-third of the
world capacity for propylene oxide used this
technology.
To try to mitigate the dependence on the
coupled product, Sumitomo developed a coox-
idation process that is free of coupled products
and started the first plant in 2003. This is usually
called the CUPO or CMHP process (Eq. 22).
22
The process starts from cumene, which is
first oxidized to cumene hydroperoxide (see
also Section 2.2.3). The cumene hydroperoxide
is then used to epoxidize propene to propylene
oxide by using a proprietary Ti-on-silica cata-
lyst, and is itself reduced to cumyl alcohol. The
cumyl alcohol is then hydrogenated back to
cumene. Overall the process consumes 1 mol of
O2 and 1 mol of H2 per mole of propylene oxide
formed. Although two plants using this tech-
nology are currently in operation (200
103 t/a
from Sumitomo in Japan and 200
103 t/a from
Rabigh Refining & Petrochemical in Saudi
Arabia), this cooxidation process is not consid-
ered to be the most economically attractive. In
spite of the many improvements possible by
using the easily oxidizable cumene, in particu-
lar the decreased amount of unconverted alkane
that must be recovered and recycled, this pro-
cess still suffers from high complexity that
leads to a high specific investment. It does
not suffer the burden of a coupled product,
but it also does not have the advantage that
SM/PO enjoys when the styrene market booms.
Oxidation 13
More recently, the PO technology has been
revolutionized by the introduction of the so-
called HPPO processes, in which hydrogen
peroxide (HP) is used as the oxidant.
23
The discovery of titanium silicalite-1 (TS-1)
in 1979 at Enichem [35] and the subsequent
demonstration that it is an efficient heteroge-
neous catalyst for the epoxidation of propene
using methanol as the solvent (Eq. 23) [36]
sparked a frenzy of work both in industry and
academia [37]. However, it took almost 20
years for the commoditization of hydrogen
peroxide to bring its costs of production into
a region where its use as an oxidant in the
propylene oxide production became economi-
cally attractive. The first two commercial plants
went into service almost simultaneously. Both
plants, from a BASF/Dow joint venture and
Solvay as the hydrogen peroxide supplier
(300
103 t/a in Antwerp, Belgium) and from
SKC with a technology license from Evonik/
KruppUhde and Evonik as the hydrogen perox-
ide supplier (100
103 t/a in Ulsan, South
Korea), started in late 2008. Since then, other
plants have either started production, are under
construction, or are in the planning phase. Both
the processes of BASF/Dow [38] and of Evonik/
KruppUhde [39], as well as the technology in
general [40, 41], have been recently reviewed.
Besides the technologies which are used
commercially, many others have been devel-
oped, several of them up to the pilot-plant stage.
The ultimate dream would be to be able to
epoxidize propene directly with O2. As men-
tioned above, BASF piloted the oxidation of
propene with O2 in the liquid phase in
the presence of a cobalt salt as catalyst. The
reaction had a good spacetime yield, but the
selectivity to propylene oxide was only 45%. In
addition, its purification was a major challenge,
due to the plethora of byproducts formed. Since
then many efforts have been made to improve
on this reaction. One of the directions taken was
to modify Ag catalysts to improve the selectiv-
ity in the propene epoxidation. For instance,
Arco has developed Ag catalysts doped with
Mo, K, Cl, and N and supported on calcium
14 Oxidation
carbonate [32]. By using these catalysts at
250 C and cofeeding NO, ethyl chloride, and
CO2 as promoters, a selectivity to propylene
oxide of 64% at a conversion of 1.5% was
achieved. However, the spacetime yield of
4.5 kg of propylene oxide per cubic meter of
reactor and hour is far too small for a technical
application.
Recently, Sumitomo reopened this line of
development by using copper-based catalysts
doped with Ru and Na supported on SiO2 and
also cofeeding a chlorinated compound. At
250 C and propene conversions of 59%
selectivities to propylene oxide of 4547%
were obtained [42]. Note, however, that the
uncatalyzed oxidation of propene with O2 in
the gas-phase was thoroughly investigated and
optimized, and under optimized conditions
(290 C, 5 bar) a selectivity to propylene oxide
of 62.8% at a propene conversion of 15.1% can
be achieved [43]. This means that the uncata-
lyzed reaction is still the most selective one.
Addition of a radical starter like acetaldehyde
increases the reaction rate and thus decreases
the reaction temperature. At 230 C the selec-
tivity to propylene oxide increases to 61%, but
this is still too low for a practicable technical
process [44].
Another variation of the direct oxidation of
propene, that is, one that uses O2 as oxidant and
does not require a coreductant, is the oxidative
acetoxylation of propene. It was originally
developed by Halcon in the early 1970s and
then further pursued by ChemSystems and
BASF in the late 1970s. Halcon developed a
catalytic system based on iodine or HBr and
TeO2 [45], which was able to acetoxylate pro-
pene with O2 and acetic acid to propylene
glycol diacetate. BASF developed a catalyst
based on basic titanium acetate [46], but later
joined ChemSystems to jointly develop the
TeO2/I2-based catalyst system [47, 48]. This
process had severe corrosion problems in the
oxidative acetoxylation step. After the synthe-
sis of the diacetate it had to be hydrolyzed, and
the propylene glycol transformed into propyl-
ene oxide [49]. Unfortunately, the catalysts for
the ring closure of propylene glycol to propyl-
ene oxide proved to be only moderately selec-
tive and to have only a limited lifetime, so the
process development was stopped in the early
1980s.
Besides the oxidation with O2, the oxidation
with H2O2 already became a focus of research
long before hydrogen peroxide was available in
the amount and at the price that made it attract-
ive for large-scale production of propylene
oxide. In the 1970s Bayer/Degussa [50, 51]
and Interox [52] had already independently
developed propylene oxide processes using
perpropionic acid, generated from propionic
acid and H2O2. The process was later described
in detail in the literature [53]. In addition to the
cost for H2O2, this process has serious problems
due to corrosion and additional costs due to the
decomposition of perpropionic acid to CO2 and
ethanol. The work was stopped in the mid-
1970s.
Another possible alternative to the above-
mentioned cooxidation processes is the so-
called anolon/PO process. Here cyclohexane
is oxidized with O2 in the absence of a catalyst
to produce a mixture of cyclohexyl hydro-
peroxide, cyclohexanol, and cyclohexanone.
The cyclohexyl hydroperoxide can then be
used to epoxidize propene. BASF operated a
5 t/a pilot plant in the late 1980s using homo-
geneous Mo catalysts similar to those used in
the MTBE/PO process. Later, in the mid-2000s,
ABB Lummus developed a similar process with
Ti/Si oxide catalysts similar to the ones used in
the Shell version of the SMPO process. [54].
Compared to the other cooxidation processes,
the anolon/PO process has the disadvantage
that the coupled product, cyclohexanone and
cyclohexanol, has a much smaller market than
MTBE or styrene, and so the commercial
opportunity for the realization of such a process
is much more limited.
In the early 1990s BASF also developed a
nonoxidative process for propylene oxide based
on the trimerization of formaldehyde to dihy-
droxyacetone with a thiazolium catalyst [55]
and subsequent hydrogenation to propanediol
[56]. The development was stopped in the mid-
1990s due to insufficient catalyst lifetime of the
thiazolium salts.
Another active field of research is the syn-
thesis of propylene oxide from propene, H2, and
O2. This is also sometimes called a direct
oxidation, but this often leads to confusion
with the reaction in which only O2 is used.
Sometimes it is referred to as the in situ H2O2
process, but this is also misleading, since it is

not at all clear that H2O2 is in all cases the
intermediate. Such a process would be particu-
larly interesting for a propylene oxide producer
that has no access to H2O2 technology, and so
this route has been intensely investigated by
many companies. The first report of such a
process came already in 1992 from Tosoh
[57]. It became even more attractive after the
discovery that gold catalysts were also active
for this reaction and very high selectivities of
propylene oxide based on propene were
obtained. However, the major problem is still
the low H2 efficiency. Between 70 and 90% of
the hydrogen used reacts unproductively to
produce water, and in spite of extensive
research efforts there has been little progress
in coping with this problem. The work in this
field has been reviewed [58].
Epichlorohydrin. After ethylene and propyl-
ene oxide, epichlorohydrin is the third largest
scale epoxide commercially produced. The
world capacity for epichlorohydrin is estimated
to be around 2.3
106 t/a. In contrast to propyl-
ene oxide, more than 95% of the capacity for
epichlorohydrin uses the chlorohydrin process,
a process similar to the PCH process used for
propene but with allyl chloride as the starting
material (Eq. 24) (! Epoxides).
24
Although a lot of work was put into the
development of a hydrogen peroxide-based
process, mostly in the early 2000s by Solvay
and more recently by Dow, this technology has
not yet been developed to a commercial pro-
cess. In the meantime, with the development by
Solvay of the Epicerol technology, the focus
has shifted to a process which uses glycerol as
feedstock and does not involve an oxidation.
The first plant with a capacity of 100
103 t/a
and located in Map Ta Phut, Thailand started
production in 2012 [59]. This is a remarkable
development, especially if one considers that
less than a decade ago epichlorohydrin was still
used to produce synthetic glycerol.
Butylene Oxide. Dow has produced 1-butene
oxide at least since the 1950s in a dedicated
plant in Freeport, Texas of undisclosed
Oxidation 15
capacity [60]. It is also produced by BASF in
its propylene oxide plant in Ludwigshafen,
Germany. Both companies use the chlorohydrin
technology (Eq. 25).
25
There is little information available on the
end uses of butylene oxide, but known appli-
cations are as a raw material in the production
of base oils for lubricants and for fuel additives.
The world capacity can be roughly estimated as
50
103 t/a.
Other Epoxides from Chlorohydrins. Due to
the constraints of the technology, the produc-
tion of chlorohydrins by addition of chlorine
and water to an olefin is not a general method
for producing epoxides. The process can only
be used when two conditions are met: 1) the
chlorohydrin has some solubility in water,
because otherwise an organic phase is formed
in which olefin gathers, leading to extensive
formation of chlorinated byproducts, and 2) the
epoxide must have a boiling point below that of
water or form a low-boiling azeotrope with
water.
Due to these limitations, the number of
epoxides that can be produced by the chloro-
hydrin process is rather limited. Besides 1-
butene oxide (bp 63 C), these are 2-butene
oxide (bp 5460 C), isobutene oxide (bp
51 C), 1-pentene oxide (bp 90 C), cyclopen-
tene oxide (bp 102 C, forms a low-boiling
azeotrope with water), and cyclohexene oxide
(bp 129 C, forms a low-boiling azeotrope with
water (Eq. 26)).
26
But of these, only 1-pentene oxide and
cyclohexene oxide are produced in sizeable
amounts. 1-Pentene oxide is used in the pro-
duction of 1,2-pentanediol, a building block for
16 Oxidation
the fungicide Propiconazole [61] and also as a
solvent in cosmetics. Although many different
processes have been proposed for the synthesis
of this building block [62], the hydrolysis of the
epoxide made by using the chlorohydrin pro-
cess is the dominant one. From the market size
for Propiconazole it can be estimated that the
capacity for 1-pentene oxide should be around
5
103 t/a. Cyclohexene oxide is also produced
commercially, mostly as a building block
for the synthesis of the acaricide Propargite
[63, 64]. Although many processes for the
preparation of cyclohexene oxide have been
described, the method most likely used indus-
trially is an indirect synthesis of the chlorohy-
drin by treating HCl with aqueous hydrogen
peroxide in the presence of cyclohexene. With
this method a steady low concentration of Cl2 is
generated and the formation of excessive
amounts of chlorinated products can be avoided
[65]. Isobutylene oxide and 2-butylene oxide
are also produced commercially by using the
chlorohydrin process, but with capacities well
below the 103 t/a threshold.
The limitations of this technology can be
overcome if the chlorohydrins are produced in a
different way, for instance, by OH/Cl exchange
as in the synthesis of epichlorohydrin and gly-
cidol from glycerol, or by addition of a nucleo-
phile to epichlorohydrin. These are important
processes to produce epoxides, but since these
are not oxidations, they are not discussed here.
Other Epoxides from Nonchlorohydrin Pro-
cesses. Many other epoxides are produced as
specialties using oxidation technologies other
than the chlorohydrin process. The most tech-
nically relevant is the so-called performic acid
technology. In this case epoxidation is per-
formed by performic acid formed in situ
from formic acid and aqueous hydrogen perox-
ide (Eqs. 27).
27
The method can only be successfully applied
in the synthesis of epoxides when the epoxide
to be produced has a wide miscibility gap with
water; otherwise, the epoxides will be hydro-
lyzed to the corresponding diols.
The method is used commercially in the
production of epoxidized oils, such as epoxi-
dized soybean and linseed oils, used as plasti-
cizers and stabilizers for PVC. This is by far the
largest application for this technology, with a
world capacity for epoxidized oils of around
150
103 t/a.
The same technology is also used to produce
a wide range of specialty aliphatic and cyclo-
aliphatic epoxides used, for instance, as
reactive diluents in epoxy resins. (! Epoxy
Resins, Chap. 11).
Other specialty epoxides produced using per-
acids formed in situ include epoxidized a-olefins
with 1020 carbon atoms, epoxidized b-oligoi-
sobutene, 3,4-epoxycyclohexyl methyl-3,4-
epoxycyclohexylcarboxylate, both mono- and
bis-epoxidized limonene and a-pinene oxide,
but probably none of these products reaches a
capacity above 103 t/a.
The use of performic acid formed in situ is
advantageous from a process point of view,
since the reactions can be performed in multi-
purpose batch reactors. However, from an eco-
nomic point of view it suffers from two main
disadvantages. First, it requires the use of con-
centrated hydrogen peroxide solutions, usually
70 wt%, to drive the equilibrium of performic
acid formation to the right. The second and
most serious disadvantage is that the formic
acid is usually discarded. The corrosiveness of
formic acidwater mixtures and the fact that
formic acid forms an azeotrope with water,
make the workup of aqueous formic acid eco-
nomically unattractive compared to discarding
it, especially if it still contains hydrogen
peroxide.
Hydrogen peroxide is also the terminal oxi-
dant in the Degussa process for the synthesis of
glycidol from allylic alcohol (Eq. 28) [6669].
28
The process is carried out in water as the
solvent with wolframate as the catalyst, and a
plant with a capacity of 3000 t/a was brought
into operation in 1980 in Germany [70], but a

few years later it was partly destroyed by a
severe explosion [71]. Glycidol is still produced
commercially from 1-chloro-2,3-propanediol,
but this process does not involve an oxidation.
A similar process, but on a much smaller scale,
was used for the commercial production of cis-
2,3-epoxy-1,4-butanediol as a raw material for
the production of 1,2,4-butanetriol [72].
Another commercially important epoxide is
hexafluoropropene oxide (! Fluorine Com-
pounds, Organic, Section 6.1.2). It is prepared
by oxidation of hexafluoropropene, either in the
gas phase or in solution in the absence of a
catalyst (Eq. 29) [7375].
29
There are no reliable data on the world
capacity for hexafluoropropene oxide, but con-
sidering that there are at least two major pro-
ducers (DuPont and 3M) and a large number of
applications, ranging from polymeric perfluori-
nated ethers, small building blocks such as
perfluoro(methyl vinyl ether), hexafluoroace-
tone, and hexafluoroisopropyl alcohol, and
widely used anesthetics like Sevoflurane and
Enflurane, the capacity probably exceeds
10
103 t/a.
2.2.3. Hydroperoxides
Hydrogen Peroxide. In the last 20 years hydro-
gen peroxide has grown from an expensive
specialty to a large-scale commodity. In the
mid-1990s, the world capacity for hydrogen
peroxide (based on 100% H2O2) was only
around 1.5
106 t/a and a world-scale plant
had a capacity of around (2040)
103 t/a.
With the increasing use of hydrogen peroxide
in pulp bleaching and after 2008 in the HPPO
process (see Section 2.2.2) world capacity has
now reached almost 5.5
103 t/a, with the larg-
est plant having a capacity of 390
103 t/a [76]
Although in the past other processes have
been used industrially, currently hydrogen per-
oxide is produced exclusively by the anthraqui-
none process. (! Hydrogen Peroxide) In this
process a 2-alkylanthraquinone is first hydro-
genated to the corresponding hydroquinone. In
Oxidation 17
a second step, the anthrahydroquinone is oxi-
dized with O2 to form H2O2 and regenerate the
anthraquinone, see Equation (30).
30
The oxidation of the anthrahydroquinone
with O2 does not require the use of a catalyst.
In the oldest processes the alkyl side chain in
the anthraquinone is simply ethyl, but in mod-
ern processes anthraquinones with a longer side
chain are used to increase their solubility in the
working solution. One of the big advantages of
this process, besides the safety aspects of not
having to bring H2 and O2 together in one step,
is the fact that in the extraction step a rather
concentrated (usually up to 40 wt% H2O2) is
directly obtained without need for costly con-
centration steps. This crude hydrogen peroxide
solution is, for example, directly usable in the
HPPO processes.
tert-Butyl Hydroperoxide. tert-Butyl hydro-
peroxide is produced as an intermediate in
the MTBE/PO process (see Section 2.2.2) by
oxidizing isobutane with O2. The reaction is a
radical chain oxidation performed without the
use of catalysts in order to maximize the selec-
tivity to the hydroperoxide (Eq. 31). The
reaction is typically conducted at 140 C and
a pressure of 3.5 MPa with long residence times
of around 10 h. The reaction is carried out to
less than 40% conversion, but even then the
selectivity to tert-butyl hydroperoxide is only in
the range of 5060%, the remainder being
mostly tert-butanol [77].
31
From the installed capacities for the MTBE/
PO process, a capacity of around 2
106 t/a for
tert-butyl hydroperoxide can be inferred.
18 Oxidation
Although the oxidation is not very selective,
the fact that it uses cheap isobutane as raw
material, requires no catalyst, and that tert-
butanol is also a valuable coproduct, have
established this process as the major source
of tert-butyl hydroperoxide. Part of the tert-
butyl hydroperoxide produced is worked-up
for sale, since it finds use as polymerization
starter or as a raw material for the production
of other peroxides, such as tert-butyl
peresters and dialkyl peroxides (! Peroxy
Compounds, Organic).
Cyclohexyl Hydroperoxide. Cyclohexyl
hydroperoxide is produced as an intermediate
or byproduct, depending on the process variant
used, in the oxidation of cyclohexane with O2,
but is not isolated and not available commer-
cially (! Cyclohexanol and Cyclohexanone).
Still, it plays a major role and it is estimated
that around 500
103 t/a is contained in the
product streams of cyclohexane oxidation
reactors. Most of the processes for oxidation
of cyclohexane use a soluble cobalt(II) carbox-
ylate as a catalyst in minute amounts (less than
100 ppb of metal). The reaction is carried out
between 145 and 160 C and only allowed to
proceed to a conversion in the range of 34% in
order to keep selectivity high. The main prod-
ucts of the reaction are cyclohexanol and cyclo-
hexanone with only small amounts (<10%) of
cyclohexyl hydroperoxide. In a subsequent
deperoxidation step the cyclohexyl hydro-
peroxide is decomposed to form more cyclo-
hexanol and cyclohexanone. The molar ratio of
cyclohexanol to cyclohexanone in the final
product, which is usually known as KA oil,
is around 2.
The oxidation can also be carried out
without the use of a metal catalyst. In this
case slightly higher temperatures, up to
180 C, are used to compensate for the slower
reaction. The conversion is also restricted to
34%, but in this case the main product
formed is cyclohexyl hydroperoxide. This is
then decomposed in a deperoxidation step
using a homogeneous cobalt carboxylate to
yield a product mixture almost identical to that
obtained when a catalyst is used in the oxida-
tion step. In both cases the overall selectivity
to cyclohexanol plus cyclohexanone is about
85% (Eq. 32).
32
The oxidation of cyclohexane is one of the
most intensively studied reactions with more
than 1200 patents and scientific papers, but also
one of the fields in which unsubstantiated
claims of improved selectivities abound.
Because the reaction must be stopped at low
conversions, it is not easy to determine the
cyclohexane conversion and the product selec-
tivities, so the usual procedure is to try to detect
all possible reaction products and to calculate
the selectivity of the reaction from the sum of
all observed reaction products. Unfortunately,
the oxidation of cyclohexane leads, besides the
major products cyclohexanol, cyclohexanone,
and cyclohexyl hydroperoxide, to a plethora of
byproducts [78]. Many of these byproducts,
such as hydroperoxides and carboxylic acids,
are difficult to detect, and with such a large
number of byproducts, even if each one of them
is formed in very small amounts, they add up to
non-negligible amounts. So, most of the claims
of improved selectivities have proven on closer
scrutiny to be incorrect. Even some of the
reaction pathways that have been accepted
for a long time have now been proven to be
incorrect [79, 80]. The picture becomes even
more complicated when a catalyst is involved,
and only very recently has light been shed on the
pathways for the cobalt-catalyzed reaction [81].
Ethylbenzene Hydroperoxide. Ethylbenzene
hydroperoxide, or more correctly 1-phenylethyl
hydroperoxide, is an important intermediate in
the so-called SMPO processes for the synthesis
of propylene oxide (see Section 2.2.2). Ethyl-
benzene hydroperoxide is obtained as a dilute
solution by oxidizing ethylbenzene with air at
140150 C and a pressure of 34 bar without a
catalyst (Eq. 33) [82].
33

To keep the selectivity high, the reaction is
stopped at 78% conversion, but even at this
low conversion the selectivity to ethylbenzene
is below 85%, with 1-phenylethanol and ace-
tophenone as the major byproducts. The reactor
effluent is then flashed to concentrate the
hydroperoxide to around 1518 wt%. This
solution is then used on site for the epoxidation
of propene. The world capacity for ethylben-
zene hydroperoxide is estimated at around
6
106 t/a, but the product is only consumed
captively and is not commercially available.
Cumene Hydroperoxide. Cumene hydro-
peroxide, or more correctly 1-methyl-1-phenyl-
ethyl hydroperoxide, is an important
intermediate both in the synthesis of phenol
by the Hock process and in the CUPO process
developed by Sumitomo for the production of
propylene oxide (see Section 2.2.2). Cumene
hydroperoxide is obtained by oxidizing cumene
with air, usually in a cascade of stirred-tank
reactors or bubble columns at temperatures in
the range of 100140 C and a pressure of 67
bar and usually with small amounts of a buffer
to prevent acids from building up (Eq. 34).
Since cumene hydroperoxide, as a tertiary alkyl
hydroperoxide, is much more stable than ethyl-
benzene hydroperoxide, the oxidation can be
taken to a higher conversion with still reason-
able selectivity. Usually the conversion is lim-
ited to around 20%, leading to selectivities to
cumene hydroperoxide in the range of 9095%.
34
In the CUPO process the reactor effluent is
further concentrated to obtain a 35 wt% solu-
tion of cumene hydroperoxide, which is then
used in the epoxidation of propene. In the Hock
phenol process the cumene hydroperoxide is
further concentrated to at least 80 wt% before
being sent to the acid-catalyzed cleavage
(! Phenol).
The worldwide capacity for the production
of cumene hydroperoxide is estimated to be
around 17
106 t/a. In contrast to ethylbenzene
hydroperoxide, not all of the cumene
Oxidation 19
hydroperoxide is used captively. A relatively
small amount is used in the production of cumyl
peroxyesters and dicumyl peroxide, which are
important radical initiators.
An analogous technology is also used,
mainly by Japanese companies, to produce
cresols from cymenes. In this case mixtures
containing both the tertiary and the primary
hydroperoxide are obtained and the primary
hydroperoxide has to be selectively decom-
posed before performing the Hock cleavage
[83]. The capacity for cresols using this tech-
nology is, however, quite modest, and estimated
to be only around (100150)
103 t/a.
Diisopropylbenzene Dihydroperoxide. p-Dii-
sopropylbenzene dihydroperoxide is an inter-
mediate in the Hock-type process for producing
hydroquinone (see also Section 2.2.7). Diiso-
propylbenzene is oxidized with air in the pres-
ence of small amounts of base to obtain the
dihydroperoxide, which is isolated and
then treated with acid to induce the cleavage
(Eq. 35) (! Hydroquinone, Section 4.1).
35
An analogous process starting with m-diiso-
propylbenzene is used to produce resorcinol (!
Resorcinol, Section 4.2). The combined capac-
ity for both isomers can only be roughly esti-
mated, but should be in the range of
(100150)
103 t/a, since some of the plants
can be used to produce both products.
Other Hydroperoxides. Not many other hydro-
peroxides made by using oxidation reactions
have commercial significance. The synthesis of
tert-amyl hydroperoxide from tert-amyl alco-
hol and H2O2 is considered to be a nucleophilic
substitution and not an oxidation.
7-Hydroperoxy-3,7-dimethyloct-5-ene is an
intermediate in two different commercial syn-
theses of rose oxide. It is generated by treating
b-citronellol with singlet oxygen, which,
20 Oxidation
depending on the process, can be photo-
chemically [84] or chemically [85] generated.
The hydroperoxide is then reduced and cyclized
to obtain rose oxide (Eq. 36).
36
Percarboxylic Acids. Currently, percarboxylic
acids, mainly peracetic acid, are produced by
acid-catalyzed equilibration of the correspond-
ing carboxylic acid with concentrated H2O2,
but this reaction is better viewed as a nucleo-
philic substitution and not an oxidation
reaction. Until recently peracetic acid was still
produced by oxidation of acetaldehyde with O2,
but the last plant using this technology, Dow
Chemicals Peroxymeric Chemicals unit, was
closed down in October 2006 [86]. This
reaction is now of no commercial relevance.
2.2.4. Alcohols
Linear Even-Numbered Alcohols. Linear
even-numbered primary alcohols with a wide
distribution of chain lengths, so-called Alfols,
can be produced by a Ziegler-type process in
which ethylene is oligomerized with triethyla-
luminum. The resulting trialkyl aluminum
compounds are then oxidized with dry air to
produce aluminum trialkoxides, which are then
hydrolyzed to alcohols (Eq. 37) (! Fatty Alco-
hols, Section 2.4.1, ! Alcohols, Aliphatic,
Section 2.3.5, ! Ziegler Processes, Chap. 4).
37
This process has been steadily losing
ground, especially because it always leads to
statistical mixtures of alcohols. Currently only
Sasol is using this technology to produce linear
alcohols with an estimated capacity of around
200
103 t/a.
Alcohols from Paraffins. The oxidation of
paraffinic hydrocarbons with oxygen, either
as an unselective radical chain reaction with
traces of a metal as catalyst or as a Bashkirov
reaction in the presence of stoichiometric
amounts of boric acid, were old processes
used to prepare mixtures of aliphatic secondary
alcohols. The technology is not in use anymore
and the last plants were closed decades ago.
Cyclohexanol. The oxidation of cyclohexane
to cyclohexyl hydroperoxide, cyclohexanol,
and cyclohexanone is discussed in Section
2.2.3.
A modification of the process that leads
almost exclusively to the formation of cyclo-
hexanol, the so-called Bashkirov oxidation,
uses boric acid in the oxidation step and the
main product obtained is cyclohexyl borate
(mainly tricyclohexyloxyboroxin). In a second
step, the cyclohexyl borate is hydrolyzed to
produce cyclohexanol. The boric acid is
recovered and recycled to the oxidation step
(Eq. 38).
38
This process has the advantage that the
oxidation can be carried out to a higher conver-
sion (up to 20%, but usually the reaction is
stopped at 15% conversion) while still achiev-
ing good selectivities of around 90%. However,
most of the advantage in conversion and selec-
tivity is lost because of the additional steps of
borate hydrolysis and boric acid recovery [87,
88]. For this reason the Bashkirov oxidation is
usually viewed as less advantageous from an
economic point of view, and it accounts for only
about 3% of the total installed capacity.
The world capacity for KA oil or anolone
(the technical mixture of cyclohexanol and
cyclohexanone) is around 7
106 t/a. Of this
total capacity, approximately 5% is made by
hydrogenation of phenol and not by oxidation
of cyclohexane. This means that the total
amount of cyclohexanol produced directly in
the oxidation of cyclohexane is around
4.5
106 t/a.
From the byproducts formed in the cyclo-
hexane oxidation in the absence of boric acid,
and more exactly from the acid washing water

that contains adipic acid and 6-hydroxycaproic
acid as the main components, a considerable
amount of 1,6-hexanediol can be obtained.
For this purpose the byproducts are either
esterified and hydrogenated [89] or directly
hydrogenated [90]. The capacity for 1,6-
hexanediol from this source has been recently
increased to 50
103 t/a [91].
Cyclododecanol. While the Bashkirov process
is only of minor importance in the oxidation of
cyclohexane, in the oxidation of cyclododecane
it is the method of choice used by all the
producers (! Cyclododecanol, Cyclododeca-
none, and Laurolactam). The reason for this lies
in the higher selectivity and higher conversion
achievable by using the Bashkirov process. In
fact, these advantages more than compensate
for the disadvantages associated with the use of
boric acid, with the necessity of hydrolyzing the
primarily formed cyclododecyl borates, with
the recycling of boric acid, and most of all
with the problems associated with handling
the wastewater containing borates [92].
The total world capacity for cyclododecanol
is estimated to be around 100
103 t/a, almost
equally divided between two plants of Invista
(Victoria, Texas) and Evonik (Marl, Germany).
During the oxidation of cyclododecane in
the presence of boric acid, considerable
amounts, up to 10%, of cyclododecanediols,
are formed as byproducts [93]. These diols can
be isolated by distillation [94] and the technical
mixture containing 3540% of 1,4-, 1012% of
1,5-, and 4550% of 1,6-cyclododecanediol is
offered by Invista under the trade name C12
CD. The capacity for this product is estimated
to be around 5
103 t/a.
2.2.5. Aldehydes
Formaldehyde. Formaldehyde is the largest-
scale aldehyde produced commercially, with
an estimated worldwide capacity of around
20
106 t/a (as 100% formaldehyde). In general
there are three distinct types of processes for
the production of formaldehyde, all of which
use methanol as the feedstock and air as oxidant
(! Formaldehyde).
Two of these processes use silver as the
catalyst and are more appropriately described
Oxidation 21
as dehydrogenation processes [95]. The
dehydrogenation of methanol to formaldehyde
is an endothermic process, which severely lim-
its the thermodynamically achievable methanol
conversion. To overcome this limitation air is
also fed into the reactor, albeit in substoichio-
metric amounts. Under these reaction condi-
tions, the O2 reacts with H2 formed in the
dehydrogenation, thus providing the thermo-
dynamic driving force to achieve high methanol
conversions. Oxygen is also required to gener-
ate (sub)surface oxygen species on the Ag,
which are thought to be essential for the first
step of the catalytic cycle, which is the depro-
tonation of methanol (Eq. 39) [96, 97].
CH3 OH x =2 O2 ! H2 C O x H2 O 1  xH2 39
In the conventional silver-catalyzed process,
usually referred to as the BASF or full-conver-
sion process, O2 is used in less than 60% of the
stoichiometric amount, but conversions of
methanol in excess of 97% are achieved. The
overall yield of formaldehyde is around 90%.
In the wet gas recycling silver process, also
often referred to as the incomplete-conversion
process, even less air is used, with O2 only at
around 40% of the stoichiometric amount. The
conversion of methanol is only around 80% and
unconverted methanol must be separated and
recycled. Although the selectivity in the
reaction is slightly higher than in the full-con-
version process, the losses in methanol during
workup lead to very similar overall formalde-
hyde yields. In both of these silver-catalyzed
processes the reaction is performed in an adia-
batic manner in a short-bed reactor with very
short contact times and reaction temperatures
around 600 C. In both variants the reactor
effluent contains considerable amounts of H2.
Finally, the third process, often referred to as
the FORMOX process, is a real oxidation pro-
cess [98100]. In this process an iron molybdate
catalyst is used and the reactor feed contains O2
in approximately twice the stoichiometric
amount. The reaction can be performed at a
much lower temperature of around 300 C, but
a tube-bundle reactor must be used to remove the
heat of reaction. The conversion of methanol is
essentially complete and the selectivity to form-
aldehyde is 24% higher than in the silver-cata-
lyzed processes. However, the high costs for the
22 Oxidation
reactor put this process at a disadvantage from
the point of view of capital expenditure.
Acetaldehyde. Currently two different oxida-
tive processes are in use for the production of
acetaldehyde (! Acetaldehyde). The oldest
process, but probably the one with the brightest
future, is the oxidation of ethanol (Eq. 40),
while the Wacker oxidation of ethylene is
quickly losing ground.
CH3 CH2 OH 1=2 O2 ! CH3 CHO H2 O 40 acid. Probably less than 100
103 t/a of acrolein
The development of efficient processes
for the synthesis of acetic acid through carbon-
ylation of methanol made the synthesis of
acetic acid from acetaldehyde economically
unattractive, and many plants using the Wacker
oxidation technology were forced to close.
Presently the worldwide capacity for acetalde-
hyde is still around 2
106 t/a, but this capacity
is seriously underutilized. In fact the amount of
acetaldehyde produced worldwide has dropped
by almost 50% since the mid 1990s and is
currently estimated to be only around
1.5
106 t/a.
The increased availability of bioethanol is
leading to a resurgence of ethanol oxidation,
especially at times when oil and naphtha prices
are high. This process has the added advantage
of being quite simple and requiring only modest
capital investments, making it attractive for
small- to medium-scale plants in developing
countries having access to cheap bioethanol.
The Wacker oxidation technology, on the other
hand is burdened with severe corrosion prob-
lems and problematic waste streams. These
problems lead to high investment costs and
for this reason, only very large scale plants
are economically viable. It is thus not likely
that any new plants for acetaldehyde will be
built using this technology in the next decades.
Acrolein. Acrolein (! Acrolein and Metha-
crolein) is exclusively produced by oxidation of
propene with air in the gas phase over a bismuth
iron molybdate catalyst [101, 102], the so-
called SOHIO process (Eq. 41).
41
The reaction is run at propene conversions
above 95% and, depending on the exact catalyst
being used, a selectivity to acrolein above 90%
can be achieved. Usually, small amounts of
acrylic acid are also formed, but since the
acrolein produced is usually not isolated and
the crude stream is simply directed to a second
reactor and oxidized to acrylic acid, this is
usually not a drawback.
The world capacity for acrolein is estimated
to be around 5
106 t/a. Most of the acrolein is
not isolated but is instead used as a crude
gaseous stream for the synthesis of acrylic
are isolated and used in other processes, such as
the synthesis of glutaric aldehyde, methionine,
1,3-propanediol or tetrahydrobenzaldehyde.
Although a considerable amount of effort
has been devoted to the development of a
catalyst capable of directly oxidizing propane
to acrolein, this transformation still remains
elusive. The best catalysts known have a selec-
tivity below 30% at a propane conversion below
20% [103, 104].
Methacrolein. Methacrolein (! Acrolein and
Methacrolein) only has relevance as an inter-
mediate in the production of methyl methacrylate
and methacrylic acid (Eq. 42). Aroundthree quar-
ters of theworld capacityfor methyl methacrylate
is produced from acetone cyanohydrin, but espe-
cially in Asia, the oxidation of isobutene or tert-
butanol is an important route for making the
methacrolein used in the production of methyl
methacrylate [105].
42
An estimated 1.2
106 t/a of methacrolein is
produced in Asia in this way. As in the case of
acrolein, quite a lot of work has been devoted to
the development of a direct oxidation of iso-
butane to methacrolein, but also in this case,
known catalysts are still far from achieving
economically interesting selectivities [106].
Isoprenal (3-Methyl-3-butenal). Isoprenal is
produced industrially as an intermediate in
BASFs citral synthesis. It is made by oxidizing
isoprenol (3-methyl-3-buten-1-ol) with O2 on a
copper or silver [107109] catalyst in the gas
phase (Eq. 43).

43
BASF has published a capacity for its citral
plant in Ludwigshafen [110], and from this the
capacity for isoprenal can be estimated to be
approximately 20
103 t/a.
Benzaldehyde. Although many processes have
been proposed for the direct or indirect oxida-
tion of toluene to benzaldehyde, only two
of these have any industrial relevance [111]
(! Benzaldehyde). The older process, based
on the hydrolysis of benzal chloride, is not
considered here. The second process, the
liquid-phase oxidation of toluene with O2
(Eq. 44), is the dominant process, contributing
most of the estimated 70
103 t/a of benzalde-
hyde produced worldwide. This process is actu-
ally performed to obtain benzoic acid as the
valuable product, but the reaction also yields
considerable amounts of benzaldehyde as a
byproduct.
44
In fact, since benzaldehyde is actually more
valuable than benzoic acid, efforts have been
made to improve the yield of the byproduct
benzaldehyde [112]. This process is discussed
in more detail in Section 2.2.10.
Specialty para-substituted benzaldehydes
like 4-tert-butyl and 4-methoxy benzaldehydes
are industrially produced by the hydrolysis of
their dimethyl acetals, which are in turn pro-
duced by electrochemical oxidation of the cor-
responding toluenes (Eq. 45) [113, 114].
45
A typical example is the synthesis of 4-tert-
butyl benzaldehyde dimethyl acetal, a building
block for the Lily of the Valley scent 2-methyl-
3-(4-tert-butyl-phenyl)propanal, by electro-
chemical oxidation of 4-tert-butyltoluene.
Oxidation 23
tert-Butylbenzaldehyde is also produced
commercially by oxidizing 4-tert-butyltoluene
with manganese dioxide [115] or with air in the
presence of a Co salt and bromide as catalysts in
acetic acid [116]. These two processes lead to
the formation of mixtures of the aldehyde and
the corresponding carboxylic acid, but at least
in the case of the oxidation of 4-tert-butylto-
luene this is less of a problem, because the 4-
tert-butylbenzoic acid is itself a commercial
product. The oxidation with MnO2 is also
used commercially for the oxidation of 4-
methoxytoluene to 4-methoxybenzaldehyde,
also known as anisic aldehyde.
There are no disclosed capacities, neither for
the electrochemical [117] nor for the chemical
oxidation processes. The fact that the same
plant can be used to produce both aldehydes
makes estimates even more uncertain. How-
ever, it is estimated that the total capacity for
4-tert-butylbenzaldehyde is approximately
15
103 t/a, while the capacity for 4-methoxy
benzaldehyde is considerably smaller and in the
range of (35)
103 t/a.
Glyoxal. Glyoxal is produced commercially by
two different oxidation processes (! Glyoxal).
The oldest process, now used only by Clariant
in France, is based on the oxidation of acetal-
dehyde with nitric acid (Eq. 46). The reaction
takes place in the liquid phase at 40 C and the
yield is only around 70%. The major drawback
of this process is the consumption of nitric acid,
which is used as a stoichiometric oxidant, and
the production of an off-gas containing consid-
erable amounts of N2O.
46
In this process 375 kg of N2O is generated
per tonne of glyoxal produced [118]. Even
after a catalytic treatment of the off-gas, 65 kg
of N2O still remains unconverted and is emit-
ted into the atmosphere [119]. This process
accounts for a little under 20% of world
capacity for glyoxal, which is estimated to
be around 250
103 t/a. Most of the capacity,
both in western countries and in Asia, uses the
catalytic oxidation of ethylene glycol with air
(Eq. 47).
24 Oxidation
47
The reaction has very high requirements for
catalyst performance, because there are only
limited possibilities to purify the crude aqueous
glyoxal solution obtained [120]. Industrially,
both metallic Ag [121, 122] and Cu [123] are
used as catalysts and both show similar per-
formances. In practice, it is necessary to
achieve almost complete conversion of ethyl-
ene glycol (> 98%) and only a low selectivity to
glycolaldehyde (less than 0.5 wt%) can be
tolerated. The main side product is CO2,
together with small amounts of formaldehyde
and formic acid which must be removed by
stripping and ion exchange. The price to pay for
the high conversion required is a quite low
selectivity to glyoxal, usually in the range of
6371%, obviously leaving a lot of room for
improvement [124].
Vanillin and Ethylvanillin. The synthesis of
vanillin and ethylvanillin, with a combined
capacity of around 10
103 t/a among the larg-
est flavors/fragrances, also encompasses an
oxidation step. Vanillin is made by reaction
of guaiacol with glyoxylic acid to selectively
form 4-hydroxy-3-methoxy mandelic acid. The
mandelic acid is subsequently oxidatively
decarboxylated to vanillin in the presence of
a homogeneous metal catalyst and oxygen as
the terminal oxidant (Eq. 48) (! Flavors and
Fragrances, Section 2.6.3). This synthetic route
has now almost completely replaced the older
process involving isolation from black sulfite
pulp liquor [125].
48
Classically the reaction was performed with
a CuII salt, usually copper sulfate, as the cata-
lyst [126], but recently claims have been made
that better results can be achieved by using a
combination of two metals like CuII and CoII
[127].
Salicylic Aldehyde. Salicylic aldehyde (!
Benzaldehyde, Section 8.3) is usually produced
by the ReimerTiemann reaction of phenol,
which involves no oxidation step. Rh^one-Pou-
lenc (now Rhodia-Solvay) developed a differ-
ent process based on the oxidation of saligenin
with O2 using a Bi-modified Pt catalyst in the
presence of boric acid (Eq. 49) [128, 129].
49
There are no secure data on the world
capacity for salicylaldehyde, but it is esti-
mated to be only around 3
103 t/a. It is
also not known how much of it is produced
by the oxidation route.
2.2.6. Ketones
Acetone. Acetone is currently produced almost
exclusively as a byproduct in Hock-type pro-
cesses from the acid-catalyzed decomposition
of isopropylbenzene hydroperoxide (! Ace-
tone). The synthesis of the hydroperoxide pre-
cursor is discussed in Section 2.2.3. On a much
smaller scale, acetone is also produced from
propan-2-ol. However, the fraction of acetone
made from propan-2-ol is less than 5% of
the overall capacity for acetone and even this
small fraction of the overall capacity uses a
dehydrogenation process. The uncatalyzed oxi-
dation of propan-2-ol with O2 to give a mixture
of acetone and H2O2 was used until the mid-
1980s as a process for H2O2 production (the so-
called Shell process) but this has been super-
seded by the anthraquinone process and is not
in use anymore (Eq. 50).
50
However, the oxidation of propan-2-ol was
reconsidered by ARCO (now LyondellBasell)
as a method for generating H2O2 in situ for the
epoxidation of propene [130, 131]. However,
the additional complexity introduced by the
presence of unconverted propan-2-ol in the
H2O2 solution made this process more

complicated and less efficient than the HPPO
process using crude H2O2 from an anthraqui-
none plant. The oxidation of propan-2-ol to
acetone has thus only historical relevance.
The Wacker oxidation of propene to acetone
is also no longer in use.
Cyclohexanone. The oxidation of cyclohexane
to cyclohexyl hydroperoxide, cyclohexanol,
and cyclohexanone is discussed in Section
2.2.3. The uncatalyzed or cobalt-catalyzed oxi-
dation of cyclohexane leads to the formation of
a mixture of cyclohexanone and cyclohexanol
in a 0.5:1 ratio. However, for the production of
caprolactam pure cyclohexanone is required
and considerable effort has been devoted to
search for catalysts with a higher selectivity
to cyclohexanone. Chromium catalysts are
claimed to provide a higher selectivity to cyclo-
hexanone [132], but the rapid deactivation of
the catalyst has thus far prevented its industrial
use. Recently, the combination of cobalt and
chromium has been claimed to lead to an
increased ratio of cyclohexanone to cyclohex-
anol, up to 1.4:1, but without the deactivation
problems observed when chromium is used as
the sole catalyst [133].
The world capacity for KA oil or anolone
(the technical mixture of cyclohexanol and
cyclohexanone) is around 7
106 t/a. Of this
total capacity, approximately 5% is made by
hydrogenation of phenol and not by oxidation
of cyclohexane. This means that total amount of
cyclohexanone produced directly by the oxida-
tion of cyclohexane is around 2
106 t/a. The
additional demand is produced by the gas-
phase dehydrogenation of cyclohexanol to
cyclohexanone.
Cyclododecanone. Cyclododecanone is
mostly produced by dehydrogenation of cyclo-
dodecanol. Recently BASF developed a new
process for the production of cyclododecanone
[134] based on the uncatalyzed oxidation of cis,
trans, trans-1,5,9-cyclododecatriene with N2O
to produce a mixture of cis, trans- and trans,
cis-cyclododeca-4,8-diene-1-one in approxi-
mately 1:1 ratio [135]. In a second step, the
cyclododecadienones are then hydrogenated to
produce the desired cyclododecanone (Eq. 51).
The first plant using this process was started up
in 2009.
Oxidation 25
51
Compared to the classical process (hydro-
genation of cyclododecatriene, oxidation to
cyclododecanol and dehydrogenation to cyclo-
dodecanone), this route is shorter and requires
only one catalyst instead of three. The process
has also a higher overall yield and higher
product purity.
The world capacity for cyclododecanone is
estimated to be around 100
103 t/a, but only
one-third is produced using the N2O-based
process.
Cyclopentanone. In contrast to cyclohexanone
and cyclododecanone, industrial processes for
the synthesis of cyclopentanone do not involve
an oxidation. The classical process for cyclo-
pentanone production involves a Dieckmann
condensation of adipic acid or its methyl ester,
and is a simple and high-yield process but with
a very low atom economy. The oxidation of
cyclopentane has never been used for the pro-
duction of cyclopentanol and cyclopentanone,
although cyclopentane is available as a starting
material. This is due to the fact that at similar
conversions, the selectivity to alcohol and
ketone is 20-25% lower in the case of cyclo-
pentane than it is in the case of cyclohexane.
Recently, BASF developed and built a new
production plant for cyclopentanone based on
the uncatalyzed oxidation of cyclopentene with
N2O (Eq. 52) [134, 136].
52
The world capacity for cyclopentanone is
estimated to be around 10
103 t/a. The capac-
ity of BASFs plant, the only one using an
oxidation route, has not been disclosed.
Furaneol. Another flavor and aroma chemical
whose synthesis also includes an oxidation step
is furaneol, an important pineapple and straw-
berry aroma. It is synthesized by the reaction of
hex-3-yne-2,5-diol with ozone and subsequent
reductive work-up (Eq. 53) [137].
26 Oxidation
The hexane-2,5-diol-3,4-dione formed in the
oxidation step is then cyclized in a separate step
to form furaneol. There are no published data
on the world capacity for furaneol, but it is
estimated to be approximately 500 t/a.
2.2.7. Phenols and Derivatives
Phenol. The major process for the production
of phenol, the Hock process, also involves an
oxidation step, namely, the oxidation of cumene
with O2 to cumene hydroperoxide. This
reaction has already been discussed in Section
2.2.3. This process accounts for the vast major-
ity of the worldwide capacity of approximately
11
106 t/a for phenol (! Phenol).
Until recently, the Dow/California Research
process starting from toluene was still used
industrially. In the first step, toluene is oxidized
in the presence of a homogeneous cobalt cata-
lyst to produce benzoic acid. This step is still in
use for the production of benzoic acid, benzal-
dehyde, and benzyl alcohol and is described in
more detail in Sections 2.2.5 and 2.2.10. In the
second step, benzoic acid is oxidatively decar-
boxylated using CuII salts as catalysts to pro-
duce phenol (Eq. 54) [138].
54
The oxidative decarboxylation of benzoic
acid is a very interesting reaction, because
the OH group is actually introduced at the
carbon atom next to the one to which the
carboxyl group was attached [139]. The last
step actually consists of two steps that occur
sequentially in the same reactor. The primary
product of the oxidative decarboxylation is
phenyl benzoate, which is hydrolyzed in situ
to phenol and benzoic acid. For this reason,
magnesium salts were also commonly used as
co-catalysts to accelerate the hydrolysis step
[140].
53
The process was in use until 2010, when
DSM sold its benzoic acid plant to Emerald
and stopped operations at the oxidative
decarboxylation plant in the Netherlands
[141]. Although toluene is a cheaper raw
material than benzene (the starting material
in the Hock cumene hydroperoxide process),
the toluene-based process was not competitive
for the production of phenol.
Another phenol process that was developed
up to pilot-plant scale and was close to being
commercialized was the so-called AlphOx pro-
cess. This was developed by Solutia in cooper-
ation with the Boreskov Institute of Catalysis
[142, 143]. The process involves the oxidation
of benzene with N2O in the gas phase on a Fe-
doped ZSM-5 zeolite (Eq. 55).
55
The N2O required as oxidant would be
obtained from the off-gas of the downstream
adipic acid plant, or from a dedicated catalytic
oxidation of NH3 with O2. Solutia announced
plans to build a 150
103 t/a plant by 2003, but
the project was stopped in 2001 [144].
Recently, ExxonMobil took up the idea, first
put forward in 1954 by Rhone-Poulenc [145],
of using cyclohexylbenzene instead of cumene.
The idea was further developed by many dif-
ferent companies. Cyclohexylbenzene, which
can be produced by self-hydroalkylation of
benzene, is oxidized by air to give the tertiary
hydroperoxide as the main product. This can be
cleaved with an acid catalyst to produce a
mixture of phenol and cyclohexanone (Eq. 56).
56

However, the selectivity in the oxidation of
cyclohexylbenzene without a catalyst is much
lower than the selectivity obtained in the oxida-
tion of cumene, mostly because the secondary
CH groups in cyclohexylbenzene are more
reactive than the primary CH3 groups in cumene.
This makes the use of a catalyst such as N-
hydroxyphthalimide necessary to achieve high
selectivities [146]. It remains to be seen whether
this process will achieve commercial status.
Although the direct oxidation of benzene to
phenol without production of acetone as a co-
product is still considered as a Holy Grail in
oxidation, the example of the Hock phenol
process (and also some processes for propylene
oxide) show that a coupled production can be
quite successful if there is a sufficiently large
market for both products.
Hydroquinone and Catechol. Three processes
are commercially used for the production of
hydroquinone and catechol, all of which involve
oxidations (! Hydroquinone). The oldest pro-
cess, which now accounts for less than 10% of
the world capacity and is only used by Chinese
producers, is based on the oxidation of aniline
with manganese dioxide to give benzoquinone
(! Benzoquinone). The benzoquinone is
then reduced in a separate step with iron powder
to produce hydroquinone (Eq. 57) [147].
57
Although the yield of hydroquinone is quite
good, the costs for manganese dioxide and iron
powder, the costs of disposal of the inorganic
byproducts, and the fact that this process can
only be performed in a batch manner makes it
less attractive. However, this process offers the
possibility of accessing benzoquinone, which is
a small-scale but quite high priced specialty
chemical.
The second oldest process involves the
hydroxylation of phenol with concentrated
hydrogen peroxide. This process, of which sev-
eral variations exist, always leads to the forma-
tion of a mixture of hydroquinone and catechol,
with catechol usually being the major product.
Oxidation 27
58
The most widely used method is the so-
called Rhodia process, which uses a mixture
of phosphoric and perchloric acids as catalyst
and 70 wt% aqueous hydrogen peroxide as the
oxidant, the reaction being effectively an elec-
trophilic aromatic substitution (Eq. 58) [148].
The reaction is performed in a large excess of
phenol. The phenol conversion is only around
5%, but the hydrogen peroxide is completely
converted. The combined yield of catechol and
hydroquinone is around 80% based on H2O2
and around 90% based on phenol. The main
strength of this process is its simplicity and the
fact that it is easily performed in a continuous
manner. The ratio of catechol to hydroquinone
can be to a certain extent tuned, but is usually in
the range of 1.5 to 2. This process accounts for
about one-third of the combined world capacity
for catechol and hydroquinone.
In the past, a different hydroxylation of
phenol used an FeII salt as the catalyst and
proceeded by a radical mechanism. However,
the process that had been operated by Brichi-
mica, later Enichem, in Italy had low yields and
led to the formation of substantial amounts of
tar [149]. This plant was closed and replaced in
1986 by a new plant, with a capacity of 10
103
t/a, using the newly developed TS-1-catalyzed
hydroxylation of phenol. In this process phenol
is oxidized in the presence of titanium silicalite
TS-1 as the catalyst. The catalyst allows for a
conversion of phenol as high as 30% and full
conversion of H2O2 while retaining good prod-
uct selectivities. The selectivities are claimed to
be around 94% based on phenol and 84% based
on H2O2, and catechol and hydroquinone are
produced in a ratio of approximately 1:1 [150,
151]. In spite of these excellent values, the
technology has not been able to firmly establish
itself. In 1994 Enichem sold the diphenols plant
and the catalyst production plant to Borregaard,
but in 2010 Borregaard was forced to cease
production on account of economic problems.
It finally sold the business in 2011 to the Indian
company Camlin Fine Sciences, which has now
restarted operations [152]. Interestingly, new
28 Oxidation
findings from Ube seem to indicate that Ti is not
necessarily required as an active metal in the
zeolite. Actually, H-BEA or H-BEA that has
been partly exchanged with Ca can lead, in the
presence of ketones as a cocatalyst, to similar or
even superior selectivities [153, 154]. The pres-
ence of the ketone seems to be crucial, and
indeed Ube uses a variation of the Rhodia
process in which a ketone is added as a catalyst
in its plant in Japan [155].
The above processes of phenol hydroxyl-
ation all have the problem that they always
produce a mixture of catechol and hydro-
quinone. Companies operating the phenol
hydroxylation are mainly interested in the cat-
echol, like Rhodia, which uses it as a starting
material in the production of vanillin and ethyl
vanillin. However, since the market demand for
hydroquinone is much higher than for catechol,
a modern process for the production of hydro-
quinone without the coproduction of catechol
had to be developed. This process involves the
alkylation of benzene or cumene to p-diisopro-
pylbenzene, its oxidation to the dihydroperox-
ide, and subsequent acid-catalyzed cleavage.
This process is discussed in Section 2.2.3.
The overall world capacity for hydroquinone
and catechol is estimated to be around 80
103
t/a, about three quarters of which is
hydroquinone.
Resorcinol. Two processes are currently in use
for the production of resorcinol. The older
process, which is not an oxidation, uses ben-
zene sulfonation and alkaline melt of the meta-
benzene disulfonate. The process still accounts
for almost half of the world capacity for cate-
chol, which is estimated to be around 80
103 t/
a. Due to environmental problems associated
with the disposal of byproducts, newer plants
use the Hock cleavage of the bis-hydroperoxide
derived from meta-diisopropylbenzene. This
reaction is described in Section 2.2.3.
Quinones. Only a few quinones are produced
commercially by oxidation. The parent com-
pound, benzoquinone, is obtained as an inter-
mediate in the oxidation of aniline with
manganese dioxide (Eq. 59). The benzo-
quinone is mostly used captively to produce
hydroquinone, but some is also commercially
available.
59
From the point of view of capacity, the
largest quinone is trimethylbenzoquinone.
This is one of the key building blocks for
synthetic vitamin E, with an estimated capacity
of around 10
103 t/a. The trimethyl benzo-
quinone is obtained by oxidizing 2,3,6-trime-
thylphenol with O2 in the presence of a catalyst.
Older processes used a cobalt(II) salen complex
as the catalyst and dimethyl formamide as
the solvent [156]. Although this process was
simple and gave high yields, it had the dis-
advantage that the catalyst could only be used
once, since it decomposes during the reaction.
The process is not used commercially anymore
and has been superseded by a copper(II)-
catalyzed oxidation. The oxidation is per-
formed in a biphasic system consisting of water
and an aliphatic alcohol that has a low misci-
bility with water, with O2 as the oxidant. The
catalyst consists of a mixture of CuCl2 and a
chloride of an alkali or alkaline-earth metal,
usually lithium chloride or magnesium chloride,
and remains dissolved in the aqueous phase.
The trimethylphenol and the product quinone
remain in the organic phase (Eq. 60) [157].
60
Although the copper catalyst must be used in
high concentration, its recycling is very simple:
the aqueous phase containing the copper(II)
chloride and the other chloride salts is just
separated and recycled. The losses of copper
in the organic phase are minimal and the pro-
cess is truly catalytic. In fact, the total turnovers
that can be achieved based on copper can be
extremely high, and are only limited by the
physical losses of copper(II) chloride during
workup. The relevant parameter for an indus-
trial process is not the catalyst concentration. If
a catalyst is easily recyclable, having to use
high concentrations is not a real drawback.
Unfortunately, this fact has not yet been widely

recognized in academia, not even in very recent
reviews [158].
Another quinone to which a lot of attention
has been dedicated is 2-methylnaphthoquinone
(! Naphthoquinones), also known as menadi-
one or vitamin K3. Although vitamin K3 does
not occur naturally, it can be used by higher
organisms to produce the biologically active 3-
phytyl derivatives known as vitamins K1 and
K2. Menadione is produced by oxidizing 2-
methylnaphthalene with chromium trioxide in
sulfuric acid or sodium dichromate in acetic
acid (Eq. 61) [159]. This reaction has often
been quoted as being a prominent example of
nonsustainable chemistry which should be
replaced by greener oxidation methods.
61
The use of stoichiometric amounts of CrVI
compounds as the oxidant has not yet been
displaced by other oxidation methods for a
number of reasons. First of all, the oxidation
with CrVI proceeds very selectively and leads
only to very small amounts of the undesired 5-
methylnaphthoquinone, which is very difficult
to separate from the desired menadione. After
the reaction, the mixture is treated with an
excess of sodium bisulfite to completely reduce
any remaining CrVI to CrIII. The CrIII basic
sulfate formed as a byproduct is not emitted
into the environment or even considered as
waste, but is actually a valuable byproduct
sold as a tanning agent for chrome leather.
Additionally, the world capacity for menadione
is quite small, at most 1000 t/a, and so the
overall impact on the environment is only very
small, even when compared with other sources
of CrIII in wastewaters, such as the corrosion of
stainless steel equipment.
Poly(Phenylene Ether). Poly(phenylene ether)
is a polymer obtained by oxidative polymeriza-
tion of 2,6-xylenol (! Poly(Phenylene
Oxides)). The oxidation uses an homogeneous
basic CuII chloride and an amine as ligand, for
example, N,N,N0 ,N0 -tetramethylethylenedi-
amine (TMEDA) (Eq. 62) [160].
Oxidation 29
62
The mechanism of the reaction has been
studied and reviewed [161]. Poly(phenylene
ether) and its blends with other polymers are
an important class of engineering plastics with
a wide range of applications; world capacity is
estimated to be 200
103 t/a.
2.2.8. Carboxylic Acids, Saturated
Formic Acid. Formic acid is now exclusively
produced by hydrolysis of methyl formate or by
acidification of sodium formate, but in the past
formic acid was also produced as one of the
products in the oxidative degradation of n-
butane (! Formic Acid, Section 4.2.1). The
last plant using this technology was a Celanese
plant in Pampa, Texas which went out of
operation in January 2009 [162]. The Celanese
process oxidized n-butane with oxygen in the
liquid phase at 170180 C and ca. 50 bar with a
homogeneous CoII salt as the catalyst. The
oxidation is quite unselective and produces a
mixture of acetic acid, formic acid, propionic
acid, butyric acid, methyl ethyl ketone, ace-
tone, acetaldehyde, acetone, and methanol.
Most of these products were isolated and
sold, with the exception of acetaldehyde, which
was recycled to the oxidation, where it served
as a catalyst and as an additional source of
acetic acid. The technology is now only of
historical interest.
Acetic Acid. The state-of-the-art technology
for the production of acetic acid is the carbon-
ylation of methanol, which accounts for more
than 95% of the world capacity of about
15
106 t/a (Eq. 63). In the past, however,
oxidation processes played a major role (!
Acetic Acid). As described in the previous
section, acetic acid was obtained as the main
product in the oxidative degradation of n-
butane in the liquid phase, but this technology
is not in use any longer. However, SABIC has
developed a technology for the catalytic oxida-
tion of ethane to acetic acid and is using it in its
30
103 t/a plant in Yanbu, Saudi Arabia.
30 Oxidation
63
Depending on the exact catalyst used and the
reaction conditions, only CO2 or ethylene and
CO2 are formed as byproducts, and selectivities
to acetic acid of up to 70% are claimed [163
165]. The process is probably only economical
where cheap ethane is available as a feedstock.
Showa Denko has also developed a one-step
oxidation of ethylene to acetic acid using an
heterogeneous Pd catalyst (Eq. 64) [166]. How-
ever, due to higher costs of ethylene as raw
material, as compared to methanol or
ethane, this technology has not found wide
acceptance and only one plant with a capacity
of 130
103 t/a has been built.
Before the development of methanol carbon-
ylation, the oxidation of acetaldehyde was the
major route for the production of acetic acid.
The reaction is a radical chain oxidation per-
formed in the liquid phase using small amounts
of Mn and often also Cu salts as homogeneous
catalysts.
64
Currently, after the 120
103 t/a plant of
Wacker in Germany was idled in September
2012, the only plants still using this technology
are located in Asia, mainly in China, but they
account for less than 5% of the world capacity
of acetic acid.
This technology may regain some impor-
tance with the increased availability of ethanol
from renewable resources at attractive prices.
Indeed, SEKAB in Sweden runs a 23
103 t/a
plant for acetic acid based on ethanol. They use
either cellulosic ethanol from its own pilot plant
or ethanol imported from Brazil.
Although only a modest share of acetic acid
is produced by oxidation reactions, it plays a
very important role as the solvent in the largest
oxidation process currently operated: the oxi-
dation of p-xylene to terephthalic acid (see
Section 2.2.10). Indeed, the required make-up
of solvent due to its oxidative degradation has
become one of the major uses for acetic acid
and has been studied in detail [167].
Propionic Acid and Other Carboxylic Acids
without a-Branches. In contrast to acetic acid,
for which the carbonylation of methanol is the
most important technology, the oxidation of
propionaldehyde is the major technology
for the production of propionic acid (Eq. 65)
(! Propionic Acid and Derivatives, ! Car-
boxylic Acids, Aliphatic). The Ni-catalyzed
carbonylation of ethylene is used only in one
large plant of BASF. The oxidation of propio-
naldehyde accounts for around 70% of the
world capacity of propionic acid which is esti-
mated to be around 350
103 t/a.
65
The reaction is performed in the liquid phase
and does not require a catalyst or an additive. The
same is true for all aliphatic aldehydes without
an a branch. They are all oxidized in excellent
yields without the need for a catalyst. The
reaction mechanism has been studied and the
reaction kinetics has been shown to be dependent
on the mechanism of initiation (thermal or pho-
tochemical). For the thermally induced oxida-
tion, the only relevant one from an industrial
point of view, the reaction has been shown to be
of order 1.5 in aldehyde and 0.5 in O2 [168, 169].
The global production of commercially rele-
vant non-a-branched carboxylic acids other
than propionic acid by oxidation of the corres-
ponding aldehydes with O2 is estimated at ca.
120
103 t/a, the major products being, in
decreasing order of production amounts:
3,5,5-trimethyl hexanoic acid (isononanoic
acid), n-heptanoic acid, n-valeric acid, n-
butyric acid, and n-nonanoic acid.
n-Nonanoic acid is additionally co-produced
with azelaic acid from the ozonolysis of oleic
acid (Eq. 66).
66

This technology is only used by Emery
Oleochemicals and an estimated 20 thousand
tons of oleic acid per year are cleaved in this
way.
2-Ethylhexanoic Acid and Other a-Branched
Carboxylic Acids. Although non-a-branched
aldehydes can be oxidized with O2 in excellent
yields to the corresponding non-a-branched
carboxylic acids without the use of any cata-
lysts or additives, this is no longer true of
a-branched aldehydes. In the oxidation of
a-branched aldehydes, it is necessary to use
an additive, usually a sodium or a potassium
salt like a hydroxide or the salt of the acid to be
produced, although potassium salts are usually
preferred due to their better solubility [170,
171]. Other alkali metals, magnesium, zinc,
and cadmium [172] also show a positive effect
on selectivity, albeit less pronounced. These
additives are not catalysts, since they do not
increase the rate of the oxidation and in fact
even slow the reaction to a certain extent, but
they do have a pronounced effect on the selec-
tivity. In the absence of potassium the selectiv-
ity for the oxidation of 2-ethylhexanal to
2-ethylhexanoic acid is only around 80%,
with 2-heptyl formate being formed as the
main byproduct, whereas in the presence of
potassium the selectivity to 2-heptyl formate
decreases to less than 3% and the selectivity to
2-ethylhexanoic acid increases to more than
95%. The same effect is also observed in the
oxidation of other a-branched aldehydes.
2-Ethylhexanoic acid is by far the largest
scale a-branched carboxylic acid with a
world capacity of around 200
103 t/a, the vast
majority of which is produced by oxidation
of 2-ethylhexanal with O2 (Eq. 67). Other
a-branched carboxylic acids, such as isobutyric
acid and 2-methylbutyric acid, are much smaller
in scale and make up, all together, less than
25
103 t/a.
Oxidation 31
Adipic Acid. Adipic acid, with a worldwide
capacity of ca. 4
106 t/a, is the major aliphatic
dicarboxylic acid and an important building
block for polyamides (! Adipic Acid). Indus-
trially, adipic acid is produced exclusively by
the oxidation of pure cyclohexanol or mixtures
of cyclohexanol and cyclohexanone with nitric
acid (Eq. 68). These mixtures of cyclohexanol
and cyclohexanone known as KA oil are
obtained by the oxidation of cyclohexane as
described in Section 2.2.3. Pure cyclohexanone
can also be used as a starting material if sodium
nitrite or NOx is added as starter, but since
cyclohexanone is usually the more expensive
raw material it is only used when cyclohexanol
is not available, for instance, when cyclohexa-
none is obtained by hydrogenation of phenol.
The oxidation is mechanistically quite a
complicated reaction, but it has nevertheless
an excellent yield, well above 95%. The only
organic byproduct formed in sizeable amounts
is glutaric acid which is usually also separated
and sold, either as pure glutaric acid or as a
mixture of adipic and glutaric acids.
68
The reaction uses a mixture of CuII nitrate
and ammonium vanadate as homogeneous
catalysts. During workup the catalysts are
recovered and reused, and only very small
67
amounts have to be replenished. The use of
nitric acid as the oxidant and the fact that
approximately 1 mol of NO2 and 1 mol of
N2O per mole of adipic acid produced are
formed is often pointed out as a major environ-
mental drawback of this process, especially in
academic papers [173]. However, this is a very
hind-sighted view of reality. In fact, the off-gas
from an adipic acid plant is not emitted into the
32 Oxidation
atmosphere. The off-gas is usually returned to
the nitric acid plant, where the NO2 is reoxi-
dized by air to nitric acid. The remaining N2O is
inert and must be catalytically decomposed.
Meanwhile, almost all adipic acid plants are
equipped with an off-gas treatment reactor in
which the N2O is decomposed to N2 and O2 to
minimize N2O emissions [174]. According to
the EPA, N2O emissions from adipic acid plants
in the USA in 2011 add up to less than 3% of
anthropogenic emissions of N2O [175] and less
than 1% of the combined natural and anthropo-
genic emissions of N2O [176].
Many alternative processes have been pro-
posed for the production of adipic acid, but none
of these has yet achieved better economics than
the nitric acid oxidation. One of the most prom-
ising developments was the one-step oxidation
of cyclohexane in acetic acid developed by
Rhodia [177]. The process used a mixture of
CrIII and CoII salts as homogeneous catalysts in
acetic acid as solvent at 105 C and 100 bar, and
achieved a selectivity to adipic acid of 66% at a
conversion of 11%. However, the low conversion
per pass and the high corrosivity of acetic acid
containing water led to a very high investment,
making the process economically unattractive.
In recent years the Japanese company Daicel
developed an alternative technology for the pro-
duction of adipic acid using N-hydroxyphthali-
mide as the catalyst [178]. According to a
company report [179], a pilot plant with a capac-
ity of 30 tons per year has been built, but to date
no commercial plant is using this technology.
Oxalic Acid. Oxalic acid, with a worldwide
capacity of ca. 600
103 t/a, is the second
largest scale aliphatic dicarboxylic acid. Only
about half of the total capacity is produced by
oxidation. The remaining capacity utilizes the
dehydrogenation of sodium formate to sodium
oxalate [180].
Several different oxidation processes are still
in use, but they all have in common that they use
nitric acid as the oxidant (! Oxalic Acid). The
most important process, accounting for ca. 45%
of the capacity, is the oxidation of carbohydrates,
such as sugars, hydrolyzed starches, and
molasses, with nitric acid (Eq. 69).
69
The technology is now almost exclusively
used in China and India with only one remain-
ing producer in Europe, Oxiquim SA in Spain.
Although the yield, which is only around 70%,
is not particularly good, the process is simple
and can even use agricultural waste material as
feedstock.
The second most important oxidation pro-
cess involves the oxidation of propene with
nitric acid and O2 (Eq. 70) [181].
70
The process has a high yield but has lost
most of its earlier importance because of the
disadvantage in raw material cost. It is pres-
ently only used in one plant from Clariant in
France, and contributes to less than 2% of the
worldwide oxalic acid capacity.
Small amounts of oxalic acid are also pro-
duced as a byproduct in the synthesis of glyox-
ylic acid by oxidation of glyoxal with nitric acid
(see Glyoxylic Acid).
Ube also produces oxalic acid by a three-
step process in which the first step involves the
oxidation of an alcohol, either methanol or n-
butanol, with NO and O2 to the corresponding
alkyl nitrite. This is subsequently carbonylated
with CO on a Pd catalyst to dialkyl oxalate and
finally hydrolyzed to produce oxalic acid and
regenerate the alcohol, which can then be
reused. The alkyl nitrite synthesis is described
in more detail in Section 2.2.13.
Dodecanedicarboxylic Acid. Dodecanedicar-
boxylic acid (! Dicarboxylic Acids, Aliphatic)
is the third largest scale aliphatic dicarboxylic
acid, with an estimated world capacity of ca.
25
103 t/a [182]. Two different processes, both
involving an oxidation, are used for its produc-
tion. The most important one is the oxidation of
cyclododecanol (see Section 71) with nitric
acid (Eq. 71).
71
The technology is, in principle, very similar
to that used for the production of adipic acid

from KA oil, including the catalyst used, but
with a few minor differences. Whereas in the
oxidation of KA oil the adipic acid remains in
solution during the reaction, dodecanedicar-
boxylic acid, due to its lower solubility in water,
already precipitates in the reactor. For this
reason the reactor design for the production
of dodecanedicarboxylic acid is quite different
from that of the adipic acid process.
As in the case of adipic acid, the main
byproducts are shorter-chain dicarboxylic
acids, mainly undecanedicarboxylic acid,
together with smaller amounts of shorter-chain
acids. The undecanedicarboxylic acid is not
isolated as a pure product, but the mixture of
undecane- and dodecanedicarboxylic acids
obtained from the mother liquor of the dodec-
anedicarboxylic acid crystallization is sold as
such as a corrosion inhibitor. Invista, the
worlds largest producer of dodecanedicarbox-
ylic acid sells a mixture containing ca. 40%
each of undecane and dodecanedicarboxylic
acids, ca. 8% of sebacic acid, with the remain-
der being other dicarboxylic acids with less
than ten carbon atoms, under the trade name
Corfree M1 [183].
In addition to the above technology, dodec-
anedicarboxylic acid is also produced by oxi-
dation of paraffins isolated from light wax oil.
The light wax oil is first separated by distilla-
tion to obtain the pure paraffins with chain
lengths between C11 and C16. The pure paraf-
fins are then oxidized by aerobic fermentation
with a selected strain of Candida tropicalis to
produce undecanedioic, dodecanedioic, bras-
sylic (C13), tetradecanedioic, pentadecanedioic,
or hexadecanedioic acid (Eq. 72).
72
Although the technology was originally
developed by Cognis for the conversion of
stearic acid or other saturated fatty acids to
long-chain dicarboxylic acids, it was never
used commercially for this purpose [184].
Rather, the technology was further developed
by two Chinese companies, Cathay Industrial
Biotech Ltd. and Zibo Guangtong Chemical
Co., which are now using it to produce all
Oxidation 33
the above-mentioned long-chain dicarboxylic
acids from paraffins [185].
At first glance the technology may look
quite attractive, but it has some serious draw-
backs. First, the chemical yield is rather low
because the bacteria use some of the paraffins
for growth. Although no exact numbers have
been published, the chemical yield is estimated
to be only in the neighborhood of 50%. Another
problem arises because the individual paraffins
required as raw material are not commercially
available. Producers have to use the commer-
cially available paraffin mixtures as the starting
material and first separate them by distillation,
which can be quite costly. Furthermore, the
economics of the process also critically depend
on not wasting any of the paraffins contained in
the light wax oil. This means that the process is
not attractive if only one of the long-chain
diacids is desired. However, the process will
probably continue to be used because it offers a
way to access long-chain dicarboxylic acids
that are not easily available by other routes.
Azelaic Acid. Azelaic acid is co-produced with
n-nonanoic acid (pelargonic acid) by cleavage of
oleic acid with ozone. The only producer is
Emery Oleochemicals, and an estimated
10
103 t/a of azelaic acid are produced by
this process. Alternative technologies for oxida-
tively cleaving oleic acid have been reviewed,
but in conclusion the use of ozone is still the best
method. This is particularly true if the ozonolysis
is conducted in pelargonic acid as the solvent,
because in this way the workup of the product
mixture is considerably simplified [186].
Trimethyladipic Acid. Trimethyladipic acid is
a mixture containing ca. 40% 2,2,4- and 60%
2,4,4-trimethyladipic acid (! Dicarboxylic
Acids, Aliphatic, Section 2.4.4) and is obtained
by oxidizing 3,5,5-trimethylcyclohexanol with
nitric acid without the use of a catalyst (Eq. 73)
[187]. The 3,5,5-trimethylcyclohexanol itself is
obtained by hydrogenating isophorone.
73
34 Oxidation
The trimethyladipic acid itself is not a com-
mercial product, but is used as a starting mate-
rial for trimethylhexanediamine, a cross-
linking amine sold by Evonik under the trade
name Vestamin TMD. The world capacity for
trimethyladipic acid is estimated to be around
4
103 t/a.
Glyoxylic Acid. Glyoxylic acid (! Glyoxylic
Acid) is a versatile intermediate used mainly as
a building block in the synthesis of vanillin (see
Section 74), allantoin, and several antibiotics
like amoxicillin, ampicillin, and the fungicide
azoxystrobin. The world capacity for glyoxylic
acid is estimated to be around 80
103 t/a. It is
now exclusively produced by the oxidation of
glyoxal with nitric acid (Eq. 74).
74
The yield of glyoxylic acid is only around
75% and considerable amounts of oxalic acid
are formed as over-oxidation product [188
190]. However, the oxalic acid can be easily
separated by crystallization and sold, so over-
oxidation does not represent a big economic
penalty. The reaction also produces considera-
ble amounts of N2O, approximately 200 kg
N2O per tonne of glyoxylic acid as a byproduct
[191]. Plants in developed countries are
required to install off-gas treatment units to
reduce N2O emissions. The reaction is acid-
catalyzed and thus the nitric acid plays a dual
role as both oxidant and catalyst. By using
aqueous hydrogen chloride as the catalyst,
the reaction can even be performed with cata-
lytic amounts of nitric acid and sodium nitrite
by using O2 as the terminal oxidant [192].
Although this technology has definite advan-
tages because the emissions of nitrogen oxides
are considerably reduced and O2 is a cheaper
oxidant than nitric acid, the high corrosivity of
the reaction mixture and the associated high
investment costs for the production plant have,
up to now, prevented this technology from
becoming commercial.
In the past, glyoxylic acid was also synthe-
sized by DSM Austria (formerly Chemie Linz)
by the ozonolysis of dimethyl maleate in meth-
anol (Eq. 75) [193].
75
The primary product after ozonolysis and
reductive workup was methyl glyoxylate
methyl hemiacetal, which was itself a commer-
cial product. The purified methyl glyoxylate
methyl hemiacetal was then hydrolyzed to pro-
duce the commercial 50% aqueous solution of
methyl glyoxal. Because the hemiacetal can be
purified by distillation, the glyoxylic acid
obtained by this route had the highest purity on
the market. However, after the production plant
was destroyed twice, the first time in August
2003 and again after reconstruction in August
2004, the technology was abandoned [194].
The cathodic reduction of oxalic acid using
lead electrodes that used to be widespread
among Chinese producers is not in use any-
more, because the glyoxylic acid produced by
this process was always contaminated with
lead.
Methoxyacetic Acid. Methoxyacetic acid is an
important intermediate for the synthesis of two
major fungicides: Mefenoxam [70630-17-0 and
69516-34-3] and Oxadixyl [77732-09-3]. The
worlds largest producer, WeylChem, uses the
oxidation of aqueous 2-methoxyethanol with
O2 in the presence of a Pt catalyst to synthesize
methoxyacetic acid (Eq. 76) [195].
76
Another process using nitric acid as the
oxidant has been developed, but is not used
commercially [196]. It cannot be excluded that
some of the methoxyacetic acid offered com-
mercially is derived from chloroacetic acid, but
the largest part is certainly made using the
above-mentioned oxidation process.
There are no reliable data on the world
capacity for methoxyacetic acid, but it is esti-
mated to be in the range of 500 to 1000 t/a.
Dimethylol Propionic Acid. Dimethylol pro-
pionic acid was developed as a component for
waterborne dispersions. It is made by oxidation

of dimethylol propionic aldehyde with hydro-
gen peroxide without any catalyst [197]. The
aldehyde is made by aldol condensation of
propionic aldehyde with formaldehyde (Eq. 77)
77
The oxidation leads to the formation of
dimethylol propionic acid in approximately
70% yield together with a plethora of byprod-
ucts. However, since the desired product can be
isolated by crystallization and no catalyst needs
to be separated or recycled, the overall process
is quite simple. The major challenge of the
process is actually safety. The oxidation of
aldehydes with H2O2 leads to the formation
of H2 as a byproduct [198]. Since some decom-
position of H2O2 to oxygen also takes place at
reaction temperature, the off-gas from the oxi-
dation contains both H2 and O2 and thus
requires special safety measures. The world
capacity for dimethylol propionic acid is esti-
mated to be around 10
103 t/a. An analogous
reaction was also used for the preparation of the
higher homologue dimethylol butyric acid, but
production was stopped in 2009 because of low
demand [199].
Ascorbic Acid. The classical synthesis
of ascorbic acid (! Vitamins, 7. Vitamin C
(L-Ascorbic Acid)) commonly known as the
Reichstein synthesis, also involves a chemical
oxidation step. The synthesis starts from
D-glucose, which is first hydrogenated to
D-sorbitol, which is in turn oxidized to L-sor-
bose in a fermentation with Acetobacter xyli-
nium or Acetobacter suboxidans. The L-sorbose
is then protected as the diacetonide and the
diacetone-L-sorbose is chemically oxidized to
diacetone-2-keto-L-gulonic acid (Eq. 78).
78
In the classical Reichstein process, KMnO4 is
used as the oxidant. Although KMnO4 is
Oxidation 35
industrially available and, if the resulting
MnO2 is recycled, can even have a good atom
economy [200], other oxidation systems were
developed using cheaper oxidants. The most
successful chemical oxidation system that was
used industrially was sodium hypochlorite in
combination with nickel peroxide as the catalyst,
which gives yields well above 90% [201]. How-
ever, the chemical oxidation route has now been
almost completely replaced by a fermentation
route.
Oxidized Polyethylene Waxes. Specialty
waxes are produced commercially by oxidizing
polyethylene with O2 or air (sometimes con-
taining small amounts of ozone) in the presence
[202] or absence [203, 204] of radical starters,
metal catalysts [205], or carboxylic acids [206]
at elevated temperatures, in the solid phase or in
the polymer melt (! Waxes, Section 6.1.5).
The oxidation leads to a reduction of the aver-
age molecular mass of the polymer, to a broad-
ening of the molecular mass distribution, and
to the introduction of functionality, such as
carboxyl groups.
There are no published data on the world
capacity for oxidized polyethylene waxes, but it
is estimated to be around 50
103 t/a.
2.2.9. Carboxylic Acids and Anhydrides,
Unsaturated
Acrylic Acid. Acrylic acid is currently pro-
duced exclusively by the two-step oxidation
of propene to acrolein and subsequently to
acrylic acid (! Acrylic Acid and Derivatives).
Both oxidations are performed in the gas phase
with heterogeneous catalysts. The first step, the
oxidation of propene to acrolein, is described in
Section 2.2.5.
79
The acrolein produced in the first step is
usually not isolated or purified but is instead
immediately converted in a second reactor on a
different catalyst to acrylic acid (Eq. 79). The
state of the art for the processes used by the
technology leaders has been recently reviewed
[207].
An active research topic in the last two
decades has been the one-step catalytic oxida-
tion of propane to acrylic acid (Eq. 80).
36 Oxidation
80
Despite the huge research effort, there has
been little progress in developing more selec-
tive catalysts. Although this transformation
would economically be very interesting, over-
coming the hurdle of having a yield per pass of
acrylic acid of at least 50% still remains an
elusive goal [208].
The world capacity for acrylic acid as of 2013
is estimated to be around 6
106 t/a, but capacity
is growing rapidly and new plants with an addi-
tional 1.5
106 t/a of capacity are planned to
come on stream before the end of 2015.
Methacrylic Acid and Methyl Methacrylate.
Although methyl methacrylate is a large-scale
commodity chemical with an estimated world
capacity of 3.6
106 t/a, most of the commer-
cial routes, accounting for three quarters of the
world capacity for methyl methacrylate, do not
involve an oxidation and do not have meth-
acrylic acid as an intermediate. Examples
include the acetone cyanohydrin process and
the Lucite process based on methyl propionate
and formaldehyde. Methacrylic acid (! Meth-
acrylic Acid and Derivatives) itself is a rather
small-scale specialty with a market size in the
lower single-digit thousands of tonnes per year,
but it is an important intermediate in one of the
processes for the production of methyl meth-
acrylate. The remaining quarter of the world
capacity is produced by the oxidation of meth-
acrolein. Methacrolein itself is made mostly by
oxidation (see Section 2.2.5). The different
potential routes to methacrylic acid by partial
oxidation have been reviewed [109].
The most widespread process for the oxida-
tion of methacrolein in the gas phase uses a
heteropoly compound as the catalyst (Eq. 81).
This technology accounts for an approximate
world capacity of around 1.1
106 t/a of meth-
acrylic acid.
81
A different approach has been taken by
Asahi. In the Asahi process, for which a
100
103 t/a plant was built in Japan in 1998,
methacrolein is oxidatively esterified with
methanol to directly produce methyl
methacrylate in one step. The reaction is per-
formed in the liquid phase with an intermetallic
compound of palladium and lead, Pd3Pb, as the
catalyst (Eq. 82) [209211].
82
The direct oxidation of isobutane or isobuty-
ric aldehyde in one step to methacrylic acid has
also been studied, but the selectivities and con-
versions obtained were not sufficiently attractive
for the development of a commercial process.
Maleic Anhydride. Maleic anhydride (!
Maleic and Fumaric Acid) is currently pro-
duced only by the oxidation of benzene or
n-butane in the gas phase on heterogeneous
catalysts (Eq. 83). The process based on ben-
zene is considered outdated and no new plants
have been built in the recent past. In fact,
actually a few small plants have even converted
from benzene to n-butane feed.
83
Nevertheless, the process based on benzene
still accounts for approximately half of the world
capacity. Modern plants use n-butane as a feed-
stock, and although both fluidized-bed and
fixed-bed processes have been developed, the
fixed-bed process is currently considered to be
the state of the art [212]. The catalyst used for the
oxidation of butane is based on vanadyl pyro-
phosphate. Since this is one of the few catalysts
that are known to activate alkanes, a lot of effort
has been devoted to understanding its mode of
operation, but many points have still not been
fully understood [213]. The development of this
class of catalysts and of the process itself have
been reviewed [214].
Small amounts of maleic anhydride are also
recovered as a byproduct in the production of
phthalic anhydride, but these account for less
than 1% of the world capacity of maleic anhy-
dride. This is estimated to be ca. 2
106 t/a.
Crotonic Acid. Crotonic acid (! Crotonalde-
hyde and Crotonic Acid) is, when compared to
acrylic and methacrylic acids, only a small-scale

specialty. The successful use of many different
catalysts, both homogeneous and heterogeneous
metal catalysts, strong acids, and even uncata-
lyzed oxidations, has been claimed in the litera-
ture. It is not known with certainty which method
is actually used industrially. However, an unca-
talyzed oxidation, with or without the addition of
a pyridine derivative as moderator, seems to be
the most likely process (Eq. 84) [215, 216].
84
There are no reliable estimates available
of the world capacity of crotonic acid, because
it can also be produced in multipurpose
plants. It is unlikely that the world production
is >3000 t/a. WeylChem, together with
Eastman one of the major producers of crotonic
acid, has announced in 2000 the construction of
a 1000 t/a plant in Frankfurt, Germany, that was
due to come on stream in early 2001. This plant
is probably the largest plant worldwide for
crotonic acid.
2.2.10. Carboxylic Acids and Anhydrides,
Aromatic
Benzoic Acid. Benzoic acid (! Benzoic Acid
and Derivatives) is commercially produced by
oxidation of toluene with oxygen in the liquid
phase, usually in the presence of small amounts
of cobalt salts as a catalyst (Eq. 85). Besides
benzoic acid, benzaldehyde is also formed as
the major byproduct (see Section 2.2.5), and
benzoic acid was used in earlier days in an
oxidative decarboxylation reaction to produce
phenol (see Section 2.2.7).
85
Currently, benzoic acid is produced only as a
starting material for food preservatives, such as
Oxidation 37
sodium benzoate, or plasticizers. The world
capacity for benzoic acid is approximately
400
103 t/a.
The oxidation itself is a radical chain
reaction. Its mechanism and the differences
in mechanism between the radical chain oxida-
tion of toluene and the radical chain oxidation
of cyclohexane have recently been studied in
detail [217].
The toluic acids have a certain importance as
starting materials mostly for agrochemicals but
the overall worldwide production is probably in
the single-digit thousands of tonnes per year.
There are no dedicated plants to produce toluic
acids and the plants can probably produce all
three isomers. Both oxidations with O2, analo-
gous to the oxidation of toluene, [218] and with
nitric acid [219] have been described for the
preparation of the toluic acids, and both are
suitable for the commercial production of the
required amounts of these products.
Terephthalic Acid. Terephthalic acid (! Ter-
ephthalic Acid, Dimethyl Terephthalate, and
Isophthalic Acid) is by now the largest organic
product produced by an oxidation reaction and
also the largest-scale process using homoge-
neous catalysis.
The first process used commercially for the
production of terephthalic acid was the oxidation
of p-xylene with nitric acid, but this process has
long since been discontinued. The oldest process
still in use is the so-called Witten or Witten
Katzschmann process, which was developed
around 1953. In this multistage process p-xylene
is partially oxidized with O2 to p-toluic acid by
using cobalt as an homogeneous catalyst. The p-
toluic acid is then isolated and esterified with
methanol. The methyl p-toluate is recycled to the
oxidation reactor, where it is oxidized to
monomethyl terephthalate. The monomethyl
terephthalate is then esterified to dimethyl ter-
ephthalate and the diester is isolated and purified
(Eq. 86). A detailed description including a flow
diagram of the most modern version of this
process has been published [220, 221].
86
38 Oxidation
In spite of the several process steps and the
additional costs for the methanol, the process
is still in use because it offers some advan-
tages compared to the state-of-the-art Amoco
process discussed below. First, since neither
acetic acid nor bromide is required, the oxi-
dation reactor and the workup section can be
built from standard stainless steel and do not
require expensive, highly corrosion resistant
alloys. The second advantage is the easy puri-
fication of the dimethyl terephthalate by dis-
tillation. The major use of terephthalic acid
and dimethyl terephthalate is in the production
of polyesters like PET (with ethylene glycol)
or PBT (with 1,4-butanediol) by condensation.
Since the presence of impurities with just one
carboxyl group is the limiting factor for the
achievable molecular mass of the polymer,
very stringent specifications must be met as
to the purity of the terephthalic acid, and these
are easier to achieve by distillation of the
diester. For special applications, the diester
also offers some advantages in the poly-
condensation reaction. These advantages jus-
tify the survival of a considerable number of
plants using this technology, which still
accounts for ca. 3
106 t/a in capacity. Still,
no new plants using this technology are
expected to be built in the near future, and
the technology will eventually be completely
replaced by the Amoco process.
The Amoco process, earlier also known as
the Mid-Century process, was also developed
in the 1950s, but the first plant was only built
in 1965. The process uses a homogeneous
catalyst system consisting of a mixture of
cobalt, manganese, and bromide in acetic
acid as solvent. More recently, the catalyst
system was extended to include zirconium as
the third metal, leading to even higher cata-
lytic activities (Eq. 87). In contrast to the
Witten process, the Amoco process can
achieve the conversion of p-xylene to tereph-
thalic acid in a single step with very high
yields, but it requires highly corrosion resist-
ant construction materials. In addition, the
purification of the product to fiber grade is
much more complicated and usually involves
a hydrogenation step to allow the separation
of the 4-formylbenzoic acid formed as a
byproduct.
87
The process is one of the fastest growing,
with a total installed capacity worldwide of ca.
60
106 t/a.
The chemistry of the process has been exten-
sively reviewed [222226]. The development of
the MnCoBr catalyst system and its exten-
sion as CoMnBrZr can be seen as a major
breakthrough in oxidation chemistry. During
the oxidation, some of the acetic acid solvent
is also lost by oxidation, and at present, solvent
make-up in terephthalic acid synthesis accounts
for around one-third of the worldwide demand
for acetic acid.
Phthalic Anhydride. Phthalic anhydride (!
Phthalic Acid and Derivatives) is commercially
produced by the oxidation of o-xylene or naph-
thalene with air in the gas phase over VTi
mixed-oxide catalysts, often containing addi-
tional metals as promoters (Eq. 88) [227].
Naphthalene, which had lost much of its impor-
tance as a feedstock, is now regaining it due to
the increased availability of cheap naphthalene
from coal, especially in China.
88
The reaction is usually performed in tube-
bundle reactors with molten salts as the heat-
transfer medium. The o-xylene conversion per
pass is essentially complete and no o-xylene
recycle is required. A critical parameter for the
conversion is the formation of phthalide as a
byproduct. Since phthalide is very difficult to
separate from the phthalic anhydride, it is
essential that the catalysts form only tolerable
amounts of this intermediate. To achieve
this goal, modern processes use multilayer
catalyst beds with 25 layers of different cata-
lysts [228, 229]. The yield of phthalic anhy-
dride based on o-xylene is usually only around

80%. CO2 is formed as the major byproduct
together with 24% of maleic anhydride, which
can also be isolated as a second valuable prod-
uct. One of the most important features of the
process is that the considerable heat of reaction
is generated at a temperature of ca. 350 C and
can thus be used to produce 100 bar steam. If
this steam can be used on site, it contributes a
significant margin to the economics of the
process. This is at least one of the reasons
why the gas-phase process is still the most
economical, even if an Amoco oxidation would
lead to the formation of phthalic acid with a
yield almost 15% higher than the gas-phase
oxidation.
The world capacity for phthalic anhydride is
ca. 5.5
106 t/a.
Isophthalic Acid. Isophthalic acid (! Tereph-
thalic Acid, Dimethyl Terephthalate, and Iso-
phthalic Acid) is commercially produced by the
oxidation of m-xylene with O2 in acetic acid, by
using a mixture of homogeneous cobalt, man-
ganese, and bromide as homogeneous catalysts
(Eq. 89). The process is essentially identical to
that used for terephthalic acid and some plants
can even be used as switch plants that can
produce either product.
89
A similar process which does not require the
use of bromide and thus does not need highly
corrosion resistant construction materials was
developed in the 1970s by the Societa Italiana
Serie Acetica Sintetica (SISAS). Instead of
bromide, this process uses acetaldehyde as
the oxidation booster, which is consumed in
the process [230]. Due to the additional costs
for the acetaldehyde this process was not com-
petitive and was never used commercially.
Oxidation 39
The installed capacity for isophthalic acid is
ca. 1
106 t/a, but the plants have been under-
utilized.
Trimellitic Anhydride. Trimellitic anhydride
(! Carboxylic Acids, Aromatic, Section 4.1)
is produced by oxidation of pseudocumene
(1,2,4-trimethylbenzene) with O2 in acetic
acid and with the same catalyst system
described above for the production of tereph-
thalic and isophthalic acids (Eq. 90). Since
pseudocumene is more difficult to oxidize
and tends to form terephthalic and isophthalic
acid as undesired byproducts, it is preferable to
conduct the oxidation stagewise [231]. The
primary product of this process is the tri-
carboxylic acid, which is then transformed
into the monoanhydride in a subsequent dehy-
dration step.
90
The worldwide capacity for trimellitic anhy-
dride is estimated to be ca. 150
103 t/a.
Pyromellitic Dianhydride. Several processes
have been proposed for the production of pyro-
mellitic dianhydride (! Carboxylic Acids,
Aromatic, Section 4.2) but little information
is available to determine which process is actu-
ally commercially used [232]. The oldest pro-
cess involving the nitric acid oxidation of
durene (1,2,4,5-tetramethylbenzene) is obsolete
and has been superseded by oxidation in the gas
phase with catalysts similar to those used for the
production of phthalic anhydride [233]. Instead
of durene, other 1,2,4,5-tetraalkyl-substituted
benzenes, such as tetraethylbenzene and 2,4,5-
trimethylisopropylbenzene, have also been pro-
posed as starting materials (Eq. 91) [234].
91
40 Oxidation
The oxidation in the gas phase has the
advantage that it leads directly to the dianhy-
dride, which is the desired product, but the yield
is only around 60%. A better yield in the gas-
phase reaction, about 70%, can be achieved if
2,4,5-trimethylbenzaldehyde is used as the
starting material instead of durene [235]. Since
both durene and 2,4,5-trimethylbenzaldehyde
are derived from pseudocumene, the former by
FriedelCrafts alkylation and the latter by acid-
catalyzed carbonylation, the higher yield in the
oxidation step makes 2,4,5-trimethylbenzalde-
hyde the most attractive feedstock.
Although a considerable amount of work has
been devoted to the preparation of pyromellitic
anhydride, it is still a surprisingly low volume
specialty, with an estimated worldwide capacity
of at most 10
103 t/a.
Biphenyl Tetracarboxylic Dianhydride.
Biphenyl tetracarboxylic dianhydride is pro-
duced by oxidatively coupling dimethyl phthal-
ate by using air and a homogeneous catalyst
containing Pd, Cu, and acetylacetone to obtain
biphenyl tetracarboxylic acid dimethyl ester
[236], which is subsequently hydrolyzed and
then dehydrated to obtain the desired dianhy-
dride (Eq. 92).
92
Although both isomers are formed, the
asymmetric one shown above predominates.
The major producer is Ube Industries in Japan,
which uses the product for the production of
specialty polyimides. Although no data on
capacity have been published, it is estimated
to be at least 1000 t/a.
The symmetrical isomer is also produced
commercially, but on a much smaller scale,
by reductive coupling of 4-chlorophthalic
acid dimethyl ester [237].
Nicotinic Acid. Nicotinic acid (niacin) and its
amide (nicotinamide, niacinamide) are physio-
logically equivalent and both fall under the
general name vitamin B3. However, the acid
and the amide are produced by different
routes (! Pyridine and Pyridine Derivatives,
Section 3.7). The amide is produced by hydrol-
ysis of 3-cyanopyridine, which is itself made
by ammonoxidation of b-picoline (see
Section 93). The free acid is made by oxidation
of 2-methyl-5-ethylpyridine with nitric acid in
the so-called Lonza process [238, 239]. Nico-
tinic acid can also be made by oxidation of
b-picoline with nitric acid. BASF built a plant
in the early 1990s which used this process, but
it was closed soon afterwards due to
unfavorable economics and technical problems
(Eq. 93).
93
It is also possible to oxidize b-picoline with
O2 in the gas phase by using a mixed-oxide
catalyst [240] similar to that used in phthalic
anhydride synthesis, but the technology has
never been used commercially.
The world capacity for nicotinic acid from
oxidation of alkyl pyridines with nitric acid is
estimated to be ca. 40
103 t/a.
Naphthalene-2,6-dicarboxylic Acid. Naphtha-
lene-2,6-dicarboxylic acid is produced by the
oxidation of 2,6-dimethyl-naphthalene with O2
in acetic acid as solvent with a mixture of
Mn, Co, and bromide as catalysts in a process
similar to that used for terephthalic acid
(Eq. 94) [241].
94
Historically, naphthalene-2,6-dicarboxylic
acid was also produced by oxidation of 2,6-
diisopropylnaphthalene, which was derived
from the alkylation of naphthalene with
propene. Since the development of a viable
synthesis of 2,6-dimethylnaphthalene from o-
xylene and butadiene by Amoco, all

naphthalene-2,6-dicarboxylic acid is now pro-
duced by oxidation of 2,6-dimethylnaphtha-
lene [242].
In the early 1990s there was hope for a large
growth for naphthalene-2,6-dicarboxylic acid
because of the good barrier properties of poly
(ethylene naphthalate), but other improvements
to the barrier properties of the standard poly
(ethylene terephthalate) turned out to be more
economical. For this reason the capacity growth
remained well below expectation and the world
capacity for naphthalene-2,6-dicarboxylic acid
is estimated to be only about 30
103 t/a.
Naphthalene-1,8-dicarboxylic Anhydride.
Naphthalene-1,8-dicarboxylic acid anhydride
is produced by oxidation of acenaphtene with
O2 in the gas phase by using vanadium oxide
based catalysts (Eq. 95) [243245].
95
There are no exact data on the world capacity
for naphthalene-1,8-dicarboxylic acid anhy-
dride, but the largest producer in China disclosed
a capacity of 4500 t/a for its dedicated produc-
tion plant. However, it is estimated that the world
capacity is actually at most 5000 t/a [246].
Interestingly one of the main uses for naph-
thalene-1,8-dicarboxylic anhydride is in the pro-
duction of perylene dyes, and these also involve
an oxidation of the corresponding imide. This is
usually performed in two steps: first, a base-
catalyzed dimerization to the leuco dye, fol-
lowed by oxidation with O2 and/or H2O2 to
form the fully aromatic perylene system [247].
2.2.11. Esters, Lactones, and Carbonates
Vinyl Acetate. Vinyl acetate (! Vinyl Esters,
Section 2.2.3) is currently produced by two
different processes [248]. The major process,
which accounts for approximately 80% of the
world capacity, involves the oxidative acetox-
ylation of ethylene (Eq. 96). The remaining
Oxidation 41
capacity, mostly located in China, uses the
addition of acetic acid to acetylene.
96
The reaction is performed in the gas phase at
moderate pressures (<8 bar) and temperatures
(<200 C), uses a heterogeneous catalyst, and
gives excellent selectivities, usually greater
than 96% [249]. Interestingly, although Pd
alone can catalyze the reaction, the catalysts
used commercially also contain Au. The addi-
tion of Au leads to a very significant increase in
the catalytic activity [250]. This was the first
and remains the most important use of a gold-
containing catalyst in industry [251].
The estimated world capacity for vinyl ace-
tate is ca. 7
106 t/a, of which about 5.5
106 t/a
is produced by oxidative acetoxylation of
ethylene.
Allyl Acetate. Allyl acetate (! Allyl Com-
pounds, Section 3.2.1) is produced by oxidative
acetoxylation of propene with acetic acid in the
gas phase by using Pd catalysts similar to those
used for vinyl acetate synthesis (Eq. 97) [252].
In fact, some of the commercial plants used for
the production of allyl acetate are former vinyl
acetate plants which have been converted to
produce allyl acetate instead.
97
Compared to vinyl acetate, allyl acetate is
only a relatively small scale product, with an
estimated world capacity of ca. 600
103 t/a.
But-2-ene-1,4-diol Diacetate. A similar oxida-
tive acetoxylation process was also developed
by Mitsubishi for the synthesis of but-2-ene-
1,4-diol diacetate, but in this case the reaction is
performed in the liquid phase at ca. 100 C and
60 bar (Eq. 96) [253].
98
42 Oxidation
The process uses a Pd catalyst doped with
Te. The selectivity to the desired but-2-ene-1,4-
diol diacetate based on butadiene is only ca.
88%, with the isomeric but-1-ene-3,4-diol diac-
etate as the major byproduct.
This technology has come under consider-
able pressure recently due to the high costs
for the butadiene raw material, especially in
Asia. This has even led to the closing of
BASFs plant in Ulsan, South Korea in 2008.
Currently it is estimated that the world capac-
ity for but-2-ene-1,4-diol diacetate has fallen
to only 100
103 t/a.
Caprolactone. Caprolactone is mostly pro-
duced industrially by the BaeyerVilliger oxi-
dation of cyclohexanone with equilibrium
peracetic acid. The process was originally
developed by Daicel using 60 wt% aqueous
hydrogen peroxide as the oxidant, and shifting
the equilibrium of the peracetic acid formation
by separating the water formed by using an
entrainer like ethyl acetate [254]. To circum-
vent the necessity of thermally stressing the
unstable peracetic acid to separate water, Sol-
vay developed a similar process using 87 wt%
aqueous hydrogen peroxide as the oxidant.
Using the highly concentrated hydrogen perox-
ide shifts the equilibrium towards peracetic
acetic and the thus-obtained solution can be
used directly in the BaeyerVilliger oxidation
of cyclohexanone (Eq. 99).
99
Solvays caprolactone plant in the UK was
sold in 2007 to Perstorp. After Dows decision
to leave the caprolactone market, Perstorp and
Daicel are the only two producers using the
BaeyerVilliger oxidation technology. BASF
also produces caprolactone, but by using 6-
hydroxyhexanoic acid contained in the byprod-
uct streams of the cyclohexane oxidation as the
raw material.
Recently, efforts have been made to develop
a caprolactone process based on a catalytic
oxidation using H2O2 as the oxidant and with-
out the need to make peracetic acid, but no
commercial process has yet evolved from these
efforts [255].
The world capacity for caprolactone by oxi-
dation is estimated to be ca. 60
103 t/a.
Dimethyl Carbonate. Dimethyl carbonate (!
Carbonic Esters, Section 3.3) is an important
intermediate in the non-phosgene process for
producing polycarbonate resins (! Polycar-
bonates). In such a phosgene-free process,
dimethyl carbonate can be generated by one
of several routes, of which only one involves
an oxidation reaction [256]. It is formed as a
valuable byproduct in the carbonylation of
methyl nitrite to dimethyl oxalate (see Section
100) or on purpose by transesterification of
ethylene carbonate, itself made from ethylene
oxide and CO2, with methanol. The only
process for producing dimethyl carbonate
which involves an oxidation is the oxidative
carbonylation of methanol using copper
chloride as the catalyst, developed by Eni-
Chem and now owned by Versalis (Eq. 100)
[257].
100
The reaction is performed in the liquid
phase with CuCl2 as the catalyst in suspension
at 120 C and ca. 25 bar [258]. The reaction is
very selective, but the reaction section must be
built of highly corrosion resistant materials
like tantalum, because the combined effects of
copper ions, chloride, HCl, and oxygen leads
to severe pitting corrosion. This leads to high
costs for investment and maintenance.
For many years Eni operated a 12
103 t/a
plant using this process, but the plant was
closed in 2005 due to poor profitability. Versalis
awarded licenses for two plants using their
technology, with a combined capacity of
approximately 150
103 t/a. The largest one
in Spain from GE Plastics was still operating
in 2002, but it is not clear whether it is currently
still in operation.

2.2.12. Nitriles
Hydrogen Cyanide. Hydrogen cyanide (!
Cyano Compounds, Inorganic) is both pro-
duced on purpose and obtained as a byproduct
in the ammoxidation of propene to produce
acrylonitrile. In this section only the on-pur-
pose processes are discussed. The most impor-
tant process for the direct synthesis of hydrogen
cyanide is the Andrussow process, which
amounts to a catalytic ammoxidation of meth-
ane (Eq. 101) [259, 260].
Pt cat:
CH4 NH3 1:5 O2 ! HCN 3 H2 O 101 molybdates (MCM) or antimonates (MCA).
The reaction is performed in the gas phase
above 1000 C and near atmospheric pressure. It
uses a Pt/Rh gauze as the catalyst at very short
contact times on the order of milliseconds. The
Andrussow process accounts for approximately
half of the world capacity for hydrogen cyanide.
Hydrogen cyanide is also formed as a
byproduct in the acrylonitrile synthesis. The
amount of hydrogen cyanide formed can be
tuned to a certain extent, but it is usually at
least 10% of the acrylonitrile output or even
considerably higher in propane-based acryloni-
trile processes. The amount of hydrogen cya-
nide can be increased either by adjusting the
reaction conditions, or by co-feeding methane.
The recovery and use of hydrogen cyanide is an
important economic factor for an acrylonitrile
producer, and often HCN consumers, like for
example methyl methacrylate plants, are built
close to large acrylonitrile plants. In such cases
it can make sense to deliberately increase the
amount of hydrogen cyanide formed in order to
provide the required capacity for the down-
stream plant using it.
The hydrogen cyanide formed as a byprod-
uct in the acrylonitrile accounts for approxi-
mately one third of the world capacity. The
remaining capacity uses processes which do not
involve an oxidation, like the BMA process, the
Shawinigan or Fluohmic process, or the cleav-
age of formamide.
The total world capacity for hydrogen cya-
nide production by oxidation processes is esti-
mated to be ca. 2
106 t/a.
Acrylonitrile. Acrylonitrile (! Nitriles) is
currently almost exclusively produced by
Oxidation 43
the SOHIO process, an ammoxidation of
propene with ammonia and O2 in the gas phase
with a heterogeneous catalyst in fluidized bed
(Eq. 102).
102
A huge amount of work has been devoted to
development of more active and more selective
catalysts. The newest-generation catalysts are
based on complex multiphase, multicomponent
With such catalysts, yields of acrylonitrile based
on propene can be as high as 80% [261, 262].
Approximately 100 kg of hydrogen cyanide is
formed per tonne of acrylonitrile as a valuable
byproduct. Another important byproduct, which
can also make a substantial economic contribu-
tion to the process, is acetonitrile (see below).
A lot of development work has also been
dedicated to the development of an acrylonitrile
synthesis based on propane instead of propene.
This is economically attractive due to the lower
cost of the propane feedstock. The intensive
research work has led to the development of
MoVNb(Te,Sb)O catalysts that can give acry-
lonitrile selectivities of up to 70% based on
propane (Eq. 103) [263].
103
The first plant using propane as the feed-
stock, a 200
103 t/a plant from PTT Asahi
Chemical in Thailand, was started in 2012
but took over one year to achieve stable opera-
tion. It is said to be only economically viable
due to strongly subsidized propane prices [264].
The world capacity for acrylonitrile is
increasing rapidly and will soon exceed
7
106 t/a, of which only 200
103 t/a is based
on propane as feedstock.
Acetonitrile. Presently no dedicated process
exists for the production of acetonitrile. The
entire world consumption is satisfied by isolat-
ing the acetonitrile formed as a byproduct of
acrylonitrile. In the conventional SOHIO pro-
cess using propene as the feedstock, approxi-
mately 2530 kg acetonitrile is produced per
44 Oxidation
tonne of acrylonitrile. The process based on
propane as the feedstock produces approxi-
mately twice that amount. Especially for the
process based on propane, the isolation of
purified acetonitrile makes an important con-
tribution to the profitability. Hence, Asahi
Kasei, shortly after starting its 200
103 t/a
acrylonitrile plant in Thailand, announced a
new plant for the isolation of purified
acetonitrile in South Korea with a capacity of
11
103 t/a [265].
During the economic crisis in 2009, the
acrylonitrile plants had to be shut down or
operated at reduced capacities, leading to an
extreme shortage of acetonitrile on the market.
In the meantime, the problem can be tackled by
co-feeding ethanol to the ammoxidation reactor
in the SOHIO process, thus allowing an
increase in the production of acetonitrile with-
out having to increase the output of acrylonitrile
[266, 267].
The current world capacity for the isolation
of purified acetonitrile is estimated to be around
80
103 t/a, which is less than half of the
theoretical amount of acetonitrile formed as a
byproduct.
Phthalodinitriles. Both o-phthalodinitrile and
m-phthalodinitrile are produced commercially
by ammoxidation of the corresponding xylenes.
104
The reaction is performed in the gas phase
over a supported vanadium catalyst at temper-
atures between 400 and 500 C in a fluidized-
bed reactor or a fixed-bed reactor at ambient
pressure (Eq. 104) [268, 269]. Although both
phthalodinitriles are produced by using essen-
tially the same process, their uses are very
different. While o-phthalodinitrile is almost
exclusively used for the synthesis of phthalo-
cyanine dyes (! Phthalocyanines), m-phthalo-
dinitrile is almost exclusively hydrogenated to
m-xylylenediamine, which is mainly used for
the production of Nylon-MXD6 [270].
The estimated world capacity for o-phthalo-
dinitrile is estimated to be only ca. 10
103 t/a,
while the capacity for the m somer is consider-
ably larger at ca. 60
103 t/a [271].
Benzonitriles. The parent compound, benzoni-
trile, is produced industrially by the ammox-
idation of toluene, but compared to other
aromatic nitriles it is only a very small scale
product, with an estimated world capacity of
only ca. 5
103 t/a [272].
3-Cyanopyridine or nicotinonitrile is also
produced by ammoximation of b-picoline and
used in the production of niacin. The estimated
capacity for nicotinonitrile is around 20
103 t/a.
Other substituted benzonitriles, such as 2-
chloro and 2,6-dichlorobenzonitrile are also
produced by ammoxidation of the correspond-
ing substituted toluenes, but only 2-chloroben-
zonitrile, with an estimated world capacity of
3
103 t/a, is of industrial importance [273].
2.2.13. Compounds Containing NO Bonds
Cyclohexanone Oxime. Conventionally, cyclo-
hexanone oxime is synthesized industrially on a
very large scale (ca. 5
106 t/a) by the reaction
of cyclohexanone with hydroxylammonium sul-
fate. However, this reaction leads to the produc-
tion of considerable amounts of ammonium
sulfate as byproduct, because the sulfate must
be trapped by neutralization with ammonia.
This limitation could finally be overcome in
a process developed by Enichem, commonly
known as the ammoximation process. In this
process hydroxylamine is generated in situ by
oxidizing ammonia with hydrogen peroxide in
the presence of a titanium silicalite (TS-1) as
the catalyst (Eq. 105). The hydroxylamine
formed is immediately trapped by the cyclo-
hexanone present in solution thus preventing its
further oxidation [274].
105
The reaction is performed in wet tert-buta-
nol as the solvent with a suspended catalyst.
The process is characterized by high conver-
sions (>98% for cyclohexanone and essentially
complete for hydrogen peroxide) and high
selectivities to the oxime (99.6% based on
cyclohexanone and 89% based on hydrogen
peroxide). No information is given on the

selectivity based on ammonia, but this is
expected to be higher than the selectivity based
on hydrogen peroxide, because the main side
reactions consuming hydrogen peroxide are the
overoxidation of ammonia to ammonium nitrate
(2 NH3 4H2O2 ! (NH4)NO3 5 H2O) and its
decomposition to oxygen (2 H2O2 ! 2 H2O
O2).
Enichem built a 12
103 t/a semi-commer-
cial plant in Porto Marghera, Italy [275] and
sold the technology to Sumitomo in 2000 [276].
Sumitomo closed down the plant in Italy and
built a full-scale plant with a capacity of
67
103 t/a in Japan using this technology
[277]. This plant combines the ammoximation
technology of Enichem with Sumitomos own
technology for the gas-phase Beckmann
rearrangement to achieve, for the first time, a
caprolactam process without any ammonium
sulfate as byproduct.
Degussa has developed a similar process for
the ammoximation of cyclododecanone to
cyclododecanone oxime [278], but this process
has not yet been commercialized.
Methyl Ethyl Ketone Oxime. Next to cyclo-
hexanone oxime and cyclododecanone oxime,
methyl ethyl ketone oxime is the only oxime
with significant commercial relevance. It is
used as an antiskinning agent in paints [279].
Recently, a plant for the production of
methyl ethyl ketone oxime with a capacity of
15
103 t/a using the ammoximation technol-
ogy was built in China. However, the capacity
indicated has to be taken with some caution,
because the entire market for methyl ethyl
ketone oxime has recently been estimated to
be only 6
103 t/a [280] and furthermore
because methyl ethyl ketone oxime is under
pressure because of its high volatility and its
unfavorable toxicological profile, which have
led to efforts to find substitutes [281].
In principle, the technology is similar to the
Enichem/Sumitomo technology described in
the previous section, but it uses a different
titanium zeolite as the catalyst: Ti-MWW
instead of TS-1 (Eq. 106) [282].
Oxidation 45
Nitromethane, Nitroethane, and Nitropro-
panes. A large proportion of the commercially
produced nitromethane (! Nitro Compounds,
Aliphatic) is obtained from the reaction of
dimethyl sulfate with sodium nitrite and does
not involve an oxidation reaction [283]. It is
also possible to obtain nitromethane from the
reaction of methane with nitric acid in the gas
phase (Eq. 107). In contrast to the nitration of
aromatics, which are electrophilic aromatic
substitutions, the nitration of alkanes is a radi-
cal chain reaction [284], and either nitric acid or
mixtures of NO2 and O2 can be used as the
oxidant [285]. It is not clear whether the nitra-
tion of methane is currently used commercially,
but most probably it is not.
A mixture of all possible C1C3 nitroalkanes
is produced commercially by Angus Chemicals
using the gas-phase nitration of propane [286].
107
The reaction is performed in the gas phase at
390440 C and leads to a mixture of all possi-
ble nitroalkanes. By using O2 or a halogen as
homogeneous catalyst the product distribution
can be changed within broad limits. The pro-
cess is very demanding from the safety point of
view, and the Angus plant in Sterlington, Loui-
siana was almost completely destroyed in an
accident in May 1991 [287], but it was rebuilt
and is still in operation. A second Angus plant is
in operation at its site in Germany. W. R. Grace
also operated a plant for nitroalkanes in Deer
Park, Texas using a mixed feed of propane and
ethane, but production ceased in 1992.
106
Recent development work has been dedi-
cated to increasing the selectivity to 2-nitro-
propane, which is the fastest growing and most
valuable product, mainly used in the production
of 2-methyl-2-aminopropan-1-ol. By using
46 Oxidation
lower temperatures, the selectivity to 2-nitro-
propane can be pushed to above 80% [288].
There are no published data on the capacity
of the nitroalkane plants, but this is estimated to
be ca. 50
103 t/a.
Nitrocyclohexane. DuPont developed and
operated a process for the synthesis of nitro-
cyclohexane from cyclohexane, the so-called
Nixan process, as an intermediate in a capro-
lactam process [289]. The reaction is usually
formulated as a nitration, but it is actually a
radical chain reaction, and nitric acid [290],
butyl nitrite [291], or nitric oxide [292] can be
used as oxidants (Eq. 108).
108
A nitrocyclohexane plant with a capacity of
25
103 t/a using 60% nitric acid as the oxidant
was put into operation by DuPont in Beaumont,
Texas in 1963, but it was closed shortly after in
1967 due to poor profitability. Since the closing
of the DuPont plant nitrocyclohexane has lost
commercial significance and is not produced on
a large scale anymore.
Methyl Nitrite. Methyl nitrite is a versatile
intermediate, but due to its instability it is seldom
used outside of an industrial setting and even
there, it is never isolated in pure form. In the past
it has been used on a small scale (<103 t/a) for
the oxidation of acetone to methylglyoxal
dimethyl acetal [293]. Its main use is, however,
in the indirect oxidative carbonylation of alco-
hols, whereby, depending on the reaction condi-
tions and catalyst used, dimethyl carbonate or
dimethyl oxalate can be obtained as the major
product. Although the carbonylation of methyl
nitrite to dimethyl carbonate has been exten-
sively studied, no commercial process ever
materialized and the work essentially stopped
in the mid-1990s [294]. The carbonylation of
alkyl nitrite to dialkyl oxalate has been devel-
oped by Ube, which has used this technology
since 1978 in a 6000 t/a plant for oxalic acid.
Recently, this technology is experiencing tre-
mendous growth, especially in China, since it
allows for the production of ethylene glycol from
coal-derived CO. The technology used in China
was developed at the Fujian Institute of Matter
and is similar to that developed by Ube for the
synthesis of oxalates. It uses methyl nitrite as the
key intermediate [295]. The methyl nitrite is
produced by the reaction of methanol, NO and
O2 as shown below in Equation (109).
2 MeOH 2 NO 1=2 O2 ! 2 MeONO H2 O 109
This reaction is very fast, very selective,
does not require a catalyst and can be per-
formed both in the gas and in the liquid phase.
Mechanistic work shows that the key step is a
concerted reaction between methanol and
N2O3 that, depending on the N2O3 isomer,
is computed to have an activation energy as
low as 20 kJ/mol [296].
Six plants for ethylene glycol, each with a
capacity of 200
103 t/a have come on stream
since 2009 and more are either in planning or
already under construction. Since, per mole of
ethylene glycol 2 mol of methyl nitrite are
required, the existing plants already add to a
total methyl nitrite capacity of ca. 2.5
106 t/a.
Amine N-Oxide Surfactants. N,N-Dimethyl
fatty amine N-oxides are important nonionic
surfactants which are especially valued for their
foam-stabilizing properties and widely used in
dishwashing formulations (! Surfactants,
Section 7.5). They are prepared by oxidizing
N,N-dimethyl fatty amines with aqueous hydro-
gen peroxide (Eq. 110). Both pure amines like N,
N-dimethyl lauryl amine and mixtures with
chain lengths between C12 and C18 are used
commercially to produce a wide range of prod-
ucts.
110
Usually no catalyst is required to perform
the reaction [297], but chelating agents such as
the sodium salt of ethylenediamine tetraacetic
acid can be added to suppress H2O2 decompo-
sition [298], and other additives can be used to
reduce the formation of nitrosamines as
byproducts [299, 300].
The world capacity for N,N-dimethyl fatty
amines is estimated to be ca. 75
103 t/a.
Another different class of amine N-oxide
surfactants are the cocamidopropyl amine
oxides [301]. These are prepared by treating

a fatty acid, usually a mixture of fatty acids with
chain lengths between C12 and C18 carbon
atoms, with N,N-dimethyl-1,3-propanediamine
to the corresponding amide, and subsequently
oxidizing the tertiary amino group to the N-
oxide with H2O2 (Eq. 111).
The world capacity for cocamidopropyl
amine oxides is estimated to be ca. 5
103 t/a.
Triethylamine N-Oxide. Triethylamine N-
oxide is an intermediate in the synthesis of
N,N-diethylhydroxylamine. It is obtained by
oxidizing triethylamine with aqueous hydrogen
peroxide in the presence of wolframate as
catalyst [302]. The triethylamine N-oxide
formed is then pyrolyzed to induce a Cope
elimination and form the desired N,N-diethyl
hydroxylamine and ethylene (Eq. 112).
Although there would be a considerable
potential for cost reduction if diethylamine
could be directly oxidized to the hydroxyl-
amine, this turns out to be quite a difficult
reaction. The oxidation of diethylamine with
H2O2 in the presence of a homogeneous cata-
lyst leads mainly to the formation of the corre-
sponding nitrone [303]. Heterogeneous
catalysts like TS-1 can give much better results,
but acceptable selectivities can only be
achieved at partial conversion of diethylamine
and some nitrone is always formed as a byprod-
uct [304306]. For this reason, the classical
two-step synthesis of diethyl hydroxylamine
is still the method used, not only due to its
simplicity, but also because it gives the purest
product with only minimal work-up.
The world capacity for diethylhydroxyl-
amine is estimated to be ca. 6
103 t/a, which
would put the capacity for triethylamine N-
oxide at ca. 8
103 t/a.
Oxidation 47
N-Methylmorpholine N-Oxide. N-Methyl-
morpholine N-oxide is a good solvent for cel-
lulose [307, 308] and is used in the production
of cellulose fibers such as Courtaulds Tencel.
The N-methylmorpholine N-oxide, which is
commercially available as a 50% solution in
111
water, is prepared by the uncatalyzed oxidation
of N-methylmorpholine with aqueous hydrogen
peroxide (Eq. 113) [309, 310].
113
It has been claimed that performing the
oxidation under a CO2 atmosphere leads to a
112
considerable reduction of the N-nitrosomor-
pholine content of the product.
The world market for N-methylmorpholine-
N-oxide is estimated to be ca. 3
103 t/a.
2.2.14. Chlorinated Compounds
Ethylene Dichloride. Ethylene dichloride or
1,2-dichloroethane is an intermediate in the
production of vinyl chloride, which consumes
roughly 99% of all ethylene dichloride produced
(! Chloroethanes and Chloroethylenes, Section
2.3) Two routes are currently used to produce
ethylene dichloride, for which several process
variants exist. The first one is the Lewis acid-
catalyzed addition of chlorine to ethylene, and
the second one is the oxychlorination of ethylene
with HCl and O2 [311]. Only the second route
falls under the scope of this keyword (Eq. 114).
114
48 Oxidation
The direct chlorination of ethylene with Cl2
is typically conducted in the liquid phase with
iron(III) chloride catalysts and ethylene
dichloride as solvent. In the oxychlorination
reaction, catalysts based on copper(II) chloride
supported on alumina are used. The reaction is
conducted in the gas phase in a fixed-bed or
fluidized-bed reactor [312]. Although at first
glance these appear to be unrelated processes,
they are in practice usually operated jointly to
create what is called a balanced process.
Indeed, when ethylene is chlorinated with chlo-
rine and subsequently cleaved to produce vinyl
chloride, 1 mol of HCl is also produced. In a
balanced process, this HCl is used for the oxy-
chlorination of ethylene and to produce more
ethylene dichloride. With this strategy one can
avoid the production of waste HCl, which has
little or no value. Theoretically, in a perfectly
balanced plant, half of the ethylene dichloride
output would stem from chlorination and the
other half from oxychlorination. In practice this
ratio is usually not 1:1, mainly because chlorine
is more expensive than HCl, and waste HCl is
often available from other processes, for exam-
ple from isocyanate plants. The use of the waste
HCl from other processes minimizes the con-
sumption of chlorine and contributes to the
overall economics of the process.
The worldwide capacity for ethylene
dichloride is estimated to be ca. 46
106 t/a,
of which only approximately half is produced
by oxychlorination and the other half by chlo-
rine addition.
The growth rates for this technology are
expected to be low because vinyl chloride
production will shift from ethylene to acety-
lene, especially in China, where cheap acety-
lene from coal is available. This has been made
possible by the development of new mercury-
free catalysts based on gold for the addition of
HCl to acetylene [313, 314].
Chlorobenzene. Chlorobenzene (! Chlorin-
ated Benzenes and Other Nucleus-Chlorinated
Aromatic Hydrocarbons, Section 2.2.2) is now
exclusively produced by electrophilic aromatic
chlorination of benzene, but historically the
oxychlorination of benzene with HCl and O2
was also used commercially as the first step in
the RaschigHooker phenol process. The orig-
inal oxychlorination in the Raschig process was
performed in the gas phase by using copper(II)
chloride supported on alumina as the catalyst
(Eq. 115) [315317], but many other variations
of the process, both in the liquid and the gas
phase, have been claimed [318].
115
At the peak of its commercial use in the
1960s the capacity for benzene oxychlorination
reached almost 200
103 t/a, but the develop-
ment of the cumene-based phenol process and
the decay in the demand for chlorobenzene led
to the closure of all plants using this process.
Chloroacetyl Chloride. Chloroacetyl chloride
(! Chloroacetic Acids, Section 2.6.2), an
important building block for agrochemicals,
is mostly produced by chlorination of chloro-
acetic acid with phosgene, thionyl chloride, or
PCl3. However, Dow at least still uses the
photooxidation of 1,2-dichloroethylene with
O2 in the presence of radical initiators such
as Cl2 or Br2 (Eq. 116) [319].
116
There are no reliable data on the capacity of
the chloroacetyl chloride plant that uses the
oxidation process, but it is probably not more
than 1000 t/a. In the long run and with increas-
ing availability of cheap and pure chloroacetic
acid, the oxidation process will probably not be
competitive with the chlorination route.
Trichloroacetaldehyde Hydrate. Trichloroa-
cetaldehyde hydrate (! Chloroacetaldehydes,
Chap. 4), often known as chloral hydrate, is
produced commercially either by the chlorina-
tion of acetaldehyde [320] or by the oxidation
of ethanol with chlorine (Eq. 117) [321].
Although in the past, acetaldehyde was the
preferred starting material, the ever-increasing
price of acetaldehyde and its lower availability
have caused a shift to ethanol as the preferred
feedstock. All the processes for the production
of chloral hydrate have recently been reviewed
[322].

117
The main uses of chloral hydrate are in the
synthesis of the insecticide DDT, as a pharma-
ceutical drug, and as an additive for Ni electro-
plating. The use of DDT has significantly
decreased since the 1960s, when its environ-
mental persistence was recognized and its use
drastically reduced. However, DDT is still the
insecticide of choice for emergency use in the
control of disease vectors like the Anopheles
mosquito, which transmits malaria. There are
no reliable figures available for the current
capacity for chloral hydrate, but it is estimated
to be about 5000 t/a.
2.2.15. Organosulfur Compounds
Methanesulfonic Acid. Methanesulfonic acid
(! Sulfonic Acids, Aliphatic, Section 2.6.2)
has traditionally been synthesized by the
hydrolysis of methanesulfonyl chloride. The
oldest process for the synthesis of methanesul-
fonyl chloride was the photochemical chloro-
sulfonation of methane with a mixture of SO2
and Cl2 [323, 324]. Due to the high energy
consumption, severe corrosion problems, and
the problems associated with the formation of
considerable amounts of chloromethanes as
byproducts, the process is no longer in use,
the last plant having been closed in 1993. The
photochemical sulfochlorination was super-
seded by the oxidation of methyl mercaptan
with Cl2 in the presence of aqueous HCl
(Eq. 118) [325].
CH3 SH 3 Cl2 2 H2 O ! CH3 SO2 Cl 5 HCl 118
This process is still used commercially and
is still the preferred process for the production
of methanesulfonyl chloride in spite of the large
amounts of waste HCl produced as a byproduct.
Recently, a new process that does not require
the use of chlorine as the oxidant has been
developed and commercialized by BASF.
This process also uses methyl mercaptan as
the starting material, which is oxidized in a
first step with elemental sulfur and an amine
catalyst to dimethyl disulfide. The dimethyl
disulfide is then oxidized in a second
step with nitric acid to methane sulfonic acid
(Eq. 119) [326].
Oxidation 49
amine
2 CH3 SH S! CH3 SSCH3 H2 S
CH3 SSCH3 4 HNO3 ! 2 CH3 SO3 H 3 NO NO2 H2 O
5
3 NO NO2 2 H2 O O2 ! 4 HNO3 119
2
The nitrogen oxides formed are then reoxi-
dized in a separate step with air to regenerate
nitric acid. Since in this process no N2O is
formed, the nitrogen oxides can be fully reoxi-
dized to nitric acid. The nitric acid can thus be
seen as a carrier for O2 which is effectively the
terminal oxidant in this process.
BASF has recently announced a capacity
expansion for the nitric acid-based process to
30
103 t/a [327]. There are no published capac-
ities for the chlorine-based methanesulfonic acid
process, but the capacity is estimated to be ca.
25
103 t/a.
Paraffin Sulfonic Acids. Paraffin sulfonic
acids, or more precisely their sodium salts, also
known as secondary alkane sulfonates (SASs)
are a class of easily biodegradable anionic sur-
factants (! Surfactants, Section 6.2.3). Two
different processes are commercially used for
their production, both starting from paraffin
mixtures with chain lengths between C12 and
C18. The first process is the photochemical
sulfochlorination of paraffins or Reid reaction,
with subsequent hydrolysis of the primarily
formed sulfonyl chlorides (Eq. 120) [328, 329]
120
The second process, the photochemical sul-
foxidation of paraffins, is from a mechanistic
point of view closely related to the Reid reaction,
since both are photochemically initiated radical
chain reactions and, as such, both must be
stopped at low conversion of the paraffin, usually
less than 5%, to avoid the formation of disulfonic
acids (Eq. 121). However, compared to the sul-
fochlorination, the sulfoxidation has a number of
advantages: there are no serious corrosion prob-
lems, the reaction leads in one step to the final
product and it delivers surfactants that are free of
chlorinated impurities [330].
121
50 Oxidation
Capacities for both processes have been
published [331], but since then several plants
have ceased production. Currently, the capacity
for the sulfoxidation process is only 50
103 t/a,
while the capacity for the sulfochlorination is
somewhat smaller at approximately 35
103 t/a.
Dimethyl Sulfoxide and Dimethyl Sulfone.
Dimethyl sulfoxide is presently, next to aceto-
nitrile, one of the major specialty solvents,
mainly due to its exceptional properties as a
polar aprotic solvent with a low volatility and
low toxicity (! Sulfones and Sulfoxides). All
the processes proposed in the literature for the
synthesis of dimethyl sulfoxide use the oxida-
tion of dimethyl sulfide, and many different
oxidants ranging from nitric acid to ozone,
oxygen, hydrogen peroxide, and even electro-
chemical oxidation, can be used. However,
most probably only the oxidation with NO2
is really used industrially (Eq. 122) [332, 333].
122
The NO formed can be reoxidized with O2
either in a separate step, in which case NO2 is
the oxidant, or in situ, in which case NO2 can be
used in catalytic amounts and O2 is the terminal
oxidant.
More recently, the oxidation of dimethyl
sulfide with hydrogen peroxide by using tita-
nium silicalite (TS-1) as the catalyst has
been claimed. The reaction has excellent yields,
but does not seem to be in commercial use
(Eq. 123) [334].
The production capacity for dimethyl sulf-
oxide has been growing rapidly, especially in
China, and it is now believed to be ca. 95
103 t/
a, although the output is probably considerably
lower [335, 336].
A small fraction of the dimethyl sulfoxide
produced is further oxidized to produce
dimethyl sulfone. Although there is very little
reliable information about the process used
commercially for the production of dimethyl
sulfone, it appears most likely that hydrogen
peroxide is used as the oxidant, since the
reaction is clean and easy to perform, not
even requiring a catalyst [337].
123
The capacity for dimethyl sulfone is much
lower than the capacity for dimethyl sulfoxide
and it is estimated to be only ca. 8
103 t/a.
Methyl ethyl sulfone and ethyl isopropyl
sulfones are also produced commercially, for
instance by Sumitomo Seika, probably through
the oxidation of the corresponding sulfides and
find use as electrolyte solvents, but these are
probably only small-scale specialties.
3. Thermodynamics; Stability
of Hydrocarbons
Under normal conditions in the presence of O2,
CO2 is the only thermodynamically stable car-
bon compound; at higher temperatures CO also
becomes increasingly stable. Thus, in the pres-
ence of free O2, all organic materials (living
organisms, wood, coal, oil, synthetic polymers,
solvents, etc.) are only metastable intermedi-
ates on the way to CO2. The stability of all
organic compounds in the presence of O2
and hence the yield of desired products in
oxidations therefore depends only on the
kinetics of the reaction involved, i.e., on the
prevailing conditions (temperature, effect of
high-energy radiation, nature and concentration
of catalysts or stabilizers (inhibitors) present,
presence of other reaction partners, impurities,
etc.).
Table 2 lists roughly estimated rates of
typical reactions, and the linearly extrapolated
time required for complete conversion.
4. Reaction Types
The oxidation of organic materials can be
roughly divided into two groups:
Homolytic oxidation reactions are chain
reactions of organic and inorganic compounds
with oxygen involving radicals formed by
homolytic cleavage of interatomic bonds.
Explosions and combustion reactions, ageing
of polymers and oils, and many industrial oxi-
dation reactions in the homogeneous liquid and
gas phases belong to this group. All types of

Table 2. Rates u of various oxidation reactions and linearly extrapolated time t required for complete formula conversion
u a, u b,
molecules cm3  s1 mol L1 s1
1031010 10181011
10131014 108107
1016 105
1018 103
1020 101
10 22
10
1024 103
a
Pure hydrocarbons contain ca. 6
1021 molecules per cubic centimeter.
b
1 mol/L corresponds to ca. 6
1020 molecules per cubic centimeter.
c
1 a  8760 h  3.15
107 s.
organic compounds can be subjected to radical
chain oxidation. Because many of these
reactions proceed spontaneously even at low
temperatures they are also called autoxidations.
Radicals recombine readily on surfaces.
Therefore surface enlargement is a proven tool
to stop radical reactions like explosions and
flames.
Metal ions that can transfer only one electron,
such as Co2/Co3, Mn2/Mn3, Fe2/Fe3,
and Cu/Cu2, act as catalyst in the liquid or
in the solid phase. The main function of the metal
ions is splitting of the hydroperoxides. Sub-
stances which readily form radicals, such as
phenols, many halogen compounds etc., can
act either as catalysts or inhibitors, depending
on their nature, concentration, and temperature.
Because radicals isomerize easily, and the
resulting intermediates are usually more readily
oxidizable than the starting hydrocarbons,
homolytic oxidations generally have low selec-
tivity. Only in several special cases can homo-
lytic oxidation be performed with high
selectivity. Examples include oxidation of
cumene to the corresponding hydroperoxide,
of alkyl hydroanthraquinone to alkyl anthraqui-
none and H2O2, of p-xylene to dimethyl tereph-
thalate (DMT) or terephthalic acid (TPA), of
aldehydes to acids and some other processes.
As an introduction [338341] are
recommended.
Heterolytic Oxidation Reactions. In hetero-
lytic oxidation reactions an active oxygen
compound (e.g., a peroxyacid, hydroperoxide,
Oxidation 51
tc Examples of reactions
1010103 a initial rate of uncatalyzed hydrocarbon oxidations
2 a10 weeks degradation of unstabilized plastics under irradiation
ca. 20 h industrial radical reactions
(e.g., liquid-phase oxidation and polymerization)
ca. 10 min heterolytic reactions
(e.g., epoxidation with ROOH/Mo complex)
ca. 6 s heterolytic reactions
heterogeneously catalyzed hydrocarbon oxidations
ca. 102 s heterogeneously catalyzed hydrocarbon oxidations
ca. 104 s explosions;
ion reactions
or O2) or a metal ion in its high valence state (e.
g., Pd2 or V5) oxidizes the starting material
in a two-electron transfer reaction. Normally, a
stoichiometric amount of the oxidizing com-
pound is used and a catalyst, for instance a
complex of Mo, V, Ti has to be used.
The catalyst can be dissolved homoge-
neously in a liquid or be present in solid
form. The reaction can take place in the liquid
phase or in the heterogeneous gas phase.
Examples of heterolytic oxidations in the
homogeneous liquid phase are the epoxidation
of olefins with hydroperoxides, catalyzed by
Mo complexes, and the oxidation of ethylene to
acetaldehyde by Pd2 complexes.
Examples of heterogeneous gas-phase
reactions are the oxidation of benzene or
butane/butene to maleic anhydride; and the oxi-
dation of propene with mixed-oxide catalysts
containing Mo to give acrylonitrile (or acrolein
and acrylic acid) and with Pd catalysts to give
allyl acetate.
Unlike radical autoxidations, heterolytic
oxidations proceed via defined complexes
and are therefore, in principle, very selective.
For an introduction and review see [339] and
[342]; further literature: [343349].
5. Homolytic Oxidation
5.1. Historical Development; Reaction
Mechanism; Radical Reactivity
An extensive study of the history of homolytic
oxidation is still missing. Short reviews of the
52 Oxidation
historical development of knowledge of homo-
lytic oxidation can be found, for example, in
[338, pp. 114], [340], and, with emphasis on
the development of homogeneous gas-phase
oxidation, in a publication by SHTERN [350].
The development of concepts of oxidation
began with the introduction of the phlogiston
theory in the 17th century by BECHER and STAHL
and its disproving in 1773 by LAVOISIER. The
development of theories for the oxidation of
organic materials started in 1897 with ENGLERs
proposal that the first step in the oxidation of an
olefin consists in the addition of one O2 molecule
to a CC double bond forming a four membered
ring (see Fig. 1a). Later on this theory was called
moloxide theory by STAUDINGER. Despite the
fact that a growing number of arguments could
be brought forward against the moloxide theory,
it was accepted until 1939. In this year CRIEGEE
and coworkers could unambiguously show, that
in the first stage of the oxidation of an olefin a
hydroperoxide is formed (see Fig. 1b). Already
in 1900 BAEYER and VILLIGER had isolated per-
benzoic acid as an intermediate in the oxidation
of benzaldehyde to benzoic acid.
Another problem that was difficult to under-
stand for a long time was the S-shaped slope of
the velocity curve of the oxidation of
Figure 1. Concepts of the structure of peroxides
a) Moloxide (ENGLER, MOUREU et al.); b) Hydroperoxide
[338]
Figure 2. Typical course of a slow hydrocarbon oxidation
(oxidation of a 1:1 benzene/O2 mixture in a glass flask; T
470 C, initial pressure p 600 hPa)
hydrocarbons (see Fig. 2). Since the few radi-
cals known to the late 1920s were very reactive
and therefore short lived, nearly nobody could
imagine that radicals could significantly partic-
ipate in the slow oxidation of hydrocarbons.
CHRISTIANSEN had therefore developed in 1924
the concept of an energy chain reaction with
the inclusion of a hot molecule.
In 1927 B opposed this idea with
ACKSTROM
the concept of a radical chain reaction, on the
grounds of the high quantum yield in photo-
chemical oxidations.
A mathematical solution to a similar problem
the reaction of H2/O2 mixtures was found
by SEMENOV in 1926 who based his theory on the
work of BODENSTEIN and NERNST. The latter
developed the theory of the unbranched chain
reaction taking the experimental results of
BODENSTEIN, who studied the photochemically
induced Cl2/H2 reaction in 1913 (Scheme 1). In
1926 SEMENOV first proposed the theory of the
branched chain reaction describing mathemati-
cally the pressure rise in the H2/O2 explosion
(Scheme 2, see [350353]).
In the early 1930s SEMENOV was able to prove
mathematically that the pressure rise in the
autoxidation of hydrocarbons could also be
explained using the model of a branched chain
reaction. Because of the long induction period
and the slow rise of the pressure, compared with
the very fast H2/O2-reaction, he called this
reaction degenerate branched chain reaction
(see Fig. 3 and [353, pp. 317ff and pp. 438ff]).
 Oxidation 53

Initiation Initiation

Cl2 hn ! 2 Cl (124) RH O2 ! R OOH (139)

Propagation RH O2 HR ! R HOOH R (140)

Cl H2 ! HCl H (125) RR hn ! R R (141)

H Cl2 ! HCl Cl (126) Propagation

Termination R O2 ! ROO (142)

2 H (wall) ! H2 (wall) (127) RH ROO ! R ROOH (143)

2 Cl (wall) ! Cl2 (wall) (128) ROO CC ! ROOCR2C(R2) (144)

H Cl (wall) ! HCl (wall) (129) Branching

ROOH (ROOR) ! RO OH ( OR) (145)

Scheme 1. Unbranched radical chain reaction
ROOH ROOH ! ROO H2O RO (146)

ROOH ROH ! RO H2O RO (147)

Inititiation
Termination
H2 O2 ! 2 HO (130)
R R ! RR (148)
Propagation
RO R ! ROR (149)
HO H2 ! H2O H (131)
ROO ROO ! ROOR O2 (150)
HO OH ! HOO H (132)
ROO R ! ROOR (151)
O H2 ! OH H (133)

Branching Scheme 3. Hydrocarbon oxidation (degenerate branched

radical chain reaction)
H O2 ! HO O (134)

HOO ! HO O (135) 2. The chains branch by decomposition of the

Termination alkylhydroperoxide molecule. However,
molecules react orders of magnitude more
H OH (wall) ! H2O (wall) (136)
slowly than radicals (therefore degenerate
H H (wall) ! H2 (wall) (137) chain branching). Only at high temperatures

O O (wall) ! O2 (wall) (138)
branching of chains occurs via peroxy radi-
cals in hydrocarbon oxidations. But even
Scheme 2. Branched radical chain reaction then these oxidations are not as fast as the
H2/O2-reaction (see Fig. 3 and Section 4.5).
Confirming the findings of CRIEGEE, FARMER
in 19411942 was the first to propose the chem-
ical radical chain mechanism of the homolytic
oxidation of hydrocarbons (Scheme 3).
The essential differences between the rela-
tively slow hydrocarbon oxidation and the very
fast oxygenhydrogen reaction (see Fig. 3) and
similar branched radical chain reactions are:

1. In the hydrocarbon oxidation, hydroperoxide

formation occurs prior to the branched chain
reaction. Hydroperoxide formation takes
place by an unbranched radical chain reaction
according to Reactions (142) and 3(143)
(Propagation in Scheme 3).
Figure 3. Course of a methane explosion and a hydrogen
explosion in a sealed vessel (stoichiometric mixture with
O2) [358, p. 10]
54 Oxidation

3. In large hydrocarbon radicals the energy

absorbed on dissociation is dissipated rap-
idly over the entire radical by atomic vibra-
tions. The radical thus loses a considerable
portion of reactivity. This behavior is par-
ticularly marked for radicals from aromatic
compounds and olefins in which the
unpaired electron (odd electron) is addition-
ally stabilized by the p-electron system.
4. Because of their lower reactivity these radi-
cals have a longer lifetime than the more
reactive radicals.
Figure 4. Relationship between Ea, E, Eo, and DH for
5. Because of the longer lifetime and the ability exothermic (Ea! ) and endothermic (Ea ) reactions
to rapidly dissipate energy, the large radicals
can readily recombine in binary collisions
(chain termination). The recombination of
small radicals (e.g., H H or H OH) energy of the attacking radical. The
occurs only in the much rarer three-body reactivity of CH bonds increases with
collisions or at the wall because of the decreasing bond energy:
need to remove the bond energy liberated. 2. Vinyl  phenyl < primary < secondary <
tertiary < allyl < cumyl < diallyl
Bond Strength and Radical Reactivity. Radi- 3. The first members of homologous series
cal chain reactions essentially occur through (e.g., methane, ethylene, benzene) have par-
the attack of a radical at a covalent bond such ticularly high CH bond energies and are
that an existing bond is broken and a new one correspondingly stable towards attack by
formed (Eq. 152): radicals. In alkanes the energy of the pri-
mary CH bonds decreases with increasing
R3 C  H X ! R3 C H  X  DH 152
chain length. Alkenes are either attacked at
the allylic CH bond or the radicals add to
In such homolytic substitution reactions, a
the CC double bond.
radical is more reactive the greater the value of
DH, i.e., the greater the difference between 4. The hydroxy, alkoxy, and acyloxy radicals
the bond energies according to Equation (153): can abstract a H atom from all CH bonds.
The peroxy radicals, in contrast, exhibit a
DH HX  DH CH DH kJ=mol 153 similarly high reactivity only towards CH

According to the rule of POLANYI and EVANS,

more precisely formulated by SEMENOV [353, p.
26 ff], from Equation (154):

Ea 48 0:25DH kJ=mol 154

the activation energy Ea of an exothermic

reaction is lower and the reaction faster the
greater the value of DH (see Figs. 4 and 5).
In Figure 6 dissociation energies for various
types of bond are shown. The following is
noted:
Figure 5. Dependence of the activation energy Ea on the
enthalpy of reaction DH for exothermic radical exchange
1. The attack of a radical at a CH bond takes reactions of type A  B C ! A B  C [351353]
place more easily and faster the lower the The reactions investigated by POLANYI and EVANS lie in the
energy of the bond and the greater the shaded area
 Oxidation 55

Figure 6. Dissociation energies of various bonds [353, p. 16 ff.]

bonds of hydrocarbons, alcohols, and alde- hydrocarbons these data can be applied to
hydes that lie below the tertiary CH bond the reactivity in the liquid phase without
of isobutane in the energy scale. With CH complications because in the liquid phase
bonds of compounds which lie above iso- hydrocarbon molecules interact with one
butane, these radicals react much more another only weakly and are not altered
slowly, but much more selectively (see
Section 4.4.1, Tables 9, 10).
5. Through the cleavage of the comparatively Table 3. Oxidizability, absolute chain propagation rate kp, and
chain propagation rate relative to cumene (kp)rel for various organic
weak OO bond in peroxides the highly compounds at 30 C [339, p. 19], [340, p. 35]
active HO and RO radicals are formed. p
Compound kp = 2kt  103 , kp, L (kp)rel
0.5 0.5
mol s mol1 s1
According to Figure 6 the CH bond of the n-Nonane 0.19
aldehyde group is less reactive than the allylic n-Dodecane 0.32
CH bond in olefins or the tertiary CH bond Cyclooctane 0.39
Cyclododecane 0.55
of cumene. However, in reality aldehydes are 1-Octene 0.062 1.0
much more reactive than these hydrocarbons Cyclohexene 2.3 5.4 10
because they can be oxidized at much lower 2,3-Dimethyl-2- 3.2 2.6 20
temperatures than e.g., cumene or butene (see butene
Toluene 0.014 0.24 0.28
Table 3, last line). There are three reasons for p-Xylene 0.049 0.84 0.73
this confusing phenomenon: Cumene 1.50 0.18 1.00
Tetralin 2.30 6.4 4.0
1. The data in Figure 6 originate from mea- Benzyl alcohol 0.89 2.4
Benzaldehyde 290 33 000
surements in the gas phase. In the case of
56 Oxidation
chemically until they are oxidized. But in
the case of aldehydes these data are mis-
leading, because aldehydes form addition
products with polar compounds like water,
alcohols, and acids in the liquid phase. In the
addition product the remaining CH bond
of the aldehyde group is strongly activated
by either two OH groups or one OH and one
OR group at the same C-atom.
2. Peroxyacyl radicals are much more reactive
than peroxyalkyl radicals in cleaving a CH
bond to gain a H-atom in order to stabilize to
the corresponding peroxy acids.
3. Peroxy acids decompose much faster to
radicals than alkyl hydroperoxides (see
Section 4.4.1).
Initiation; Induction Period; Peroxide Forma-
tion. Small molecules such as H2, CH4, and
NH3 normally exist as gases. Because of the
stable bonds, which necessitate high dissocia-
tion energies, and because of the weak inter-
actions between the gas molecules, these types
of molecule only react with oxygen at high
temperatures, if no catalysts or initiators are
present. At low temperatures their mixtures
with oxygen are metastable in the absence of
catalysts.
In the autoxidation of higher hydrocarbons
the situation is quite different, especially in the
liquid and solid phase. Because of inter-
molecular interactions and the relatively low
bond energies of many CC and CH bonds,
radicals are formed relatively rarely, but con-
tinually, even at low temperatures. This may
occur by reaction with O2 (Reactions (139) or
(140)) or by concentration of the thermal vibra-
tion energy into one bond (cf., the lowering of
the ignition temperature for gas explosions
from ca. 600 C for methane to ca. 200 C for
decane, see Table 15). The rate of radical
formation is increased drastically by high-
energy radiation (sunlight) and heat. In most
cases these radicals recombineabove all in
the liquid or solid phase, where the mobility of
the molecules and their fragments is severely
limited as a result of the forces of interaction
(solvent cage). However, if oxygen is present,
it competes with the simple radical
recombination (Reaction 148) because of its
diradical structure (Reaction 142). These types
of radical recombination take place without
activation energy and are therefore very fast.
This mechanism is the cause of the ageing of
organic materials in the presence of oxygen
even at low temperatures. It is also the mecha-
nism of initiation of autoxidation.
Although radical chains are continuously
initiated even at low temperatures, the reaction
does not exceed a uniform low rate as long as
more radicals are destroyed than are formed.
This is the cause of the induction period, which
is always exhibited by uncatalyzed autoxida-
tion reactions. In particular hydroperoxides
accumulate during this induction period as
active intermediates, which are formed in an
unbranched chain reaction according to
Reactions (142) and (143).
Dangerous peroxide build-up can occur in
olefin-containing liquids, since peroxy radicals
also add easily to double bonds according to
Reaction (144). Because oxygen generally
reacts much faster with the alkylperoxyalkyl
radicals formed than the olefin, copolymeric
peroxides are formed in this way. Because of
the missing OH group, these are considerably
more stable than hydroperoxides and can there-
fore accumulate in large quantities. At higher
temperatures they can decompose explosively.
Because the common reagents for peroxide
detection are mostly sensitive to hydro-
peroxide, these polyperoxides often remain
undetected. For more details, see [354357].
Hydroperoxides also accumulate in paraffins,
glycol ethers, and other nonvolatile organic com-
pounds on exposure to air. These can initiate
rapidly accelerating oxidation reactions even at
moderate temperatures. Cleaning cloths soaked
with linseed oil can even ignite at room temper-
ature. The self-ignition temperature of paraffins,
surfactants, glycol ethers, and similar substances
drops below 100 C if, for example, insulating
material with a large surface area, such as rock
wool which has been moistened with them has
been lying for a few days in the air.
The induction period can be shortened or
completely eliminated by the addition of
peroxides or other radical-forming reagents,
or through irradiation.
Termination; Inhibition. Radical chain reac-
tions can be slowed down or stopped by reduc-
ing the concentration of active intermediates,

Figure 7. Typical autoxidation curves in the absence and
presence of antioxidants [338, p. 4]
a) Absence of antioxidant; b) x parts antioxidant; c) 2 x parts
antioxidant
for instance by enhancing radical recombina-
tion reactions.
In homolytic gas- and liquid-phase oxida-
tions, solid surfaces are the most effective
radical scavengers. Fillings or packings made
from thin tubes (capillaries) or Raschig rings
are used overall in industry as flame and explo-
sion barriers, and certain inorganic dusts (e.g.,
ammonium phosphate) are among the most
effective fireextinguishing agents.
Organic antioxidants (e.g., phenols, thiols,
amines) act in different ways. Phenols, for
instance, are transformed by active radicals
into low energy radicals, which subsequently
add other active radicals forming stable prod-
ucts. Thiols are oxidized by hydroperoxides to
sulfoxides whereby the hydroperoxides are
reduced to alcohols. In these reactions the
organic antioxidants are, however, gradually
consumed. Once they have been consumed,
the autoxidation continues at the rate it would
have in the unstabilized substance (see Fig. 7);
for more details, see Section 4.4.3. An intro-
duction to organic stabilizers and antioxidants
can be found in [338]; fire and explosion pro-
tection are described in [358367].
Rise in the Reaction Rate; Final Conversion.
As soon as the peroxide concentration has
exceeded a critical value which depends
on the nature of the compound to be oxidized,
the state of aggregation, the presence or
absence of catalysts, and the temperature
Oxidation 57
the overall rate of radical formation by peroxide
decomposition (Reactions 145 to 147) begins to
exceed that of radical destruction (Reactions
148 to 151). From this point, the overall
reaction rate increases exponentially to a maxi-
mum, which is reached at an early stage of the
overall reaction.
Afterwards the reaction rate slows down to
zero. In the oxidation of hydrocarbons the
reaction normally ceases long before the start-
ing material is completely consumed. One rea-
son for this behavior is the dilution of the
reaction mixture by the end products formed,
mainly water and lower carboxylic acids such
as acetic acid, the latter being very resistant
against oxidation. In the presence of metallic
ions as catalysts, water and carboxylic acids act
as catalyst poisons because they are stronger
complexing agents than hydroperoxides (see
Section 4.4.2). Raising the temperature can
revive the reaction for a more or less short time.
High starting material conversions are, how-
ever, only rarely desired in homolytic oxidations
because the product selectivity decreases rapidly
with increasing conversion due to secondary
reactions. Frequently, starting material conver-
sions of 1030%, sometimes even only 1%, are
aimed for. (For more details see Section 4.2.)
Hydroperoxide Decomposition. The decom-
position of hydroperoxides is the main source
of radicals during the entire reaction (Scheme 3,
Reactions 145 to 147).
The thermal decomposition of peroxides has
activation energies of between 120 and 164 kJ/
mol. These are the highest activation energies
of the reactions shown in Scheme 3.
The hydroperoxide decomposition therefore
determines the temperature range for the oxi-
dation of organic compounds. Temperature
ranges for liquid-phase oxidations are as fol-
lows: aldehydes: up to 80 C; olefins and
cumene: up to 130 C; aliphatics, alkylaro-
matics, alcohols, ketones, esters: 80 to 200 C.
Since hydroperoxides, and of course also
peroxides, are also used commercially as starters
for radical chain polymerizations, a large body of
data exists on their rates of thermal decay.
Reviews on decomposition rates and activation
energies for a wide range of peroxides can be
found both in the literature [368] and in bro-
chures from peroxide producers [369371].
58 Oxidation
5.2. Kinetics of Autoxidation
Kinetic measurements, in particular with
respect to individual elementary reactions,
are associated with particular difficulties and
uncertainties in radical chain reactions because
of the great number of parallel and secondary
reactions and the normally very low concentra-
tion of the reacting compounds. Nevertheless,
many insights into the course of the reaction
could be obtained, for example, by
1. Following the pressure rise in gas-phase
oxidations
2. Investigation of the peroxide decomposition
in hydrocarbons
3. Simultaneous oxidation (cooxidation) of
different compounds
4. Oxidation in the presence of a tertiary
hydroperoxide
5. By using specific analytical methods: ESR,
chemiluminescence, and UV absorption for
radicals; liquid chromatography for hydro-
peroxides and nonvolatile compounds; gas
chromatography for the stable, volatile
products, etc., and many other methods.
The main problem is still, however, the
quantitative determination of all components
aldehydes.
present in a reaction mixture. For example,
active intermediates react further after the sam-
ple has been taken, so that the composition of
the sample changes rapidly. For low-conversion
reactions, which are required for the precise
determination of the kinetics, the sensitivity
limits of all analytical methods are quickly
reached. For a review of experimental methods
for the determination of the kinetics of radical
chain oxidations see [341], and for analytical
methods for peroxide determination see [372].
Under mild conditions (temperature
< 100 C and sufficient oxygen, i.e., for a
liquid-phase reaction: O2 partial pressure
> 10 kPa, for a gas-phase oxidation: O2 excess)
the rate of oxygen conversion is only deter-
mined by Reaction (143) in the case of the
oxidation of hydrocarbons, since Reaction
(142) is very fast and the concentration of R Butane
is very small. Equation (155) is therefore valid:
dO2 
 kp ROO RH 155 Decane
dt
Since a kinetic equilibrium (steady state) is
established very rapidly after initiation of the
radical formation and radical scavenging
reactions, and because only Reaction (150)
plays a role as a chain termination reaction at
sufficient O2 supply, Equation (156) is valid:
ui ut 2kt ROO 2 156
where ui rate of chain initiation and ut rate
of chain termination. Inserting Equation (156)
into (155) gives:
dO2  kp p
 p RH  ut 157
dt 2 kt
Equation (157) is only valid for low conver-
sions as the secondary reaction products formed
at higher conversions are generally more read-
ily oxidized thanpthe
starting hydrocarbon. The
expression kp = 2kt is referred to as the
oxidizability, since it indicates how much
faster one organic compound is oxidized than
another. Table 3 lists values for the oxidizability
as well as kp and relative kp (based on cumene)
values for various hydrocarbons. Under mild
oxidation conditions, the value of kp increases
in the following order: n-alkanes < isoalkanes
< alkylaromatics < alkenes < alkynes  styr-
ene derivatives
If, however, the oxidation rates of alkanes
are compared under more severe conditions
(temperature > 120 C) where the hydro-
peroxide decomposition determines the
reaction rate, then the order of overall oxidation
rate is as given in Table 4 and Figure 8.
It can be seen that the overall oxidation rate
increases sharply both with increasing chain
length and with decreasing branching. The
reasons for this are:
Table 4. Relative oxidation rate of various n-alkanes [373, p. 94]
n-Alkane Relative oxidation rate [mol O2
(mol alkane)1 time1]
Ethane 0.001
Propane 0.1
0.5
Pentane 1.0
Hexane 7.5
Octane 200
1380
 Oxidation 59

Figure 8. Oxidation rates of hexane isomers [mol O2 (mol alkane)1 time1] relative to 2,3-dimethylbutane [373, p. 95]

1. In the series primary ! secondary ! ter-
tiary CH bonds, the rate of formation of
the hydroperoxides increases dramatically,
but their rate of decomposition decreases
equally drastically. The secondary hydro-
peroxides are formed more slowly than ter-
tiary hydroperoxides but decompose
considerably faster, so that the lower rate
of formation is more than compensated for.
Therefore, under these conditions, hydro-
carbons with secondary CH bonds are
oxidized faster than hydrocarbons having
tertiary CH bonds.
2. The number of secondary H atoms per
molecule increases with decreasing branch-
ing. All secondary CH bonds in an alkane
are attacked equally rapidly.
Tables 58 list some literature values for
the collision factor A, activation energy Ea and
rate constant k for the initiation of the ele-
mentary reaction, peroxide decomposition
(branching), propagation, and termination
[340, 341, 351354] (Because autoxidation
is generally initiated by the decomposition
of added peroxides, peroxide decomposition
frequently is designated initiation in the
literature, which is incorrect and may lead
to confusion.)
The following points may be made:
1. According to Equation (157) the rate of O2
take-up in the initial phase of an oxidation is
only proportional to the hydrocarbon con-
centration and is independent of the O2
concentration under mild reaction
conditions.
2. The k value of Reaction (142) is estimated
to be 107 to > 109 L mol1  s1 (corre-
sponding to 1014 to > 1012 cm3 mole-
cule1  s1) at Ea  0 kJ/mol [339]. It is
orders of magnitude faster than Reaction
(143), which therefore determines the propa-
gation rate. Because of its high rate, Reaction
(142) is generally controlled in the liquid
phase under industrial conditions by O2
diffusion.

Table 5. Kinetic data for the thermal decomposition of some initiators at 80 C [340, p. 23], [341, p. 21 ff], [354, p. 95]

Initiator Solvent T,  C kd, s1 Ad, s1 Ea,d, kJ/mol

0 3 15
2,2 -Azodiisobutyronitrile benzene 7.59
10 1.6
10 129
Cyclohexyl hydroperoxide cyclohexane 150 3.1
105 1.2
1013 142
tert-Butyl hydroperoxide n-octane 150 0.90
105 1.2
1015 163
water 4.0
1012 142
Di-tert-butyl peroxide benzene 9.55
106 1.2
1014 142
Cumene hydroperoxide cumene 150 1.24
105 7.2
108 111
mineral oil 150 1.35
104 1.3
1011 121
tert-Butyl peroxybenzoate ethylbenzene 9.55
105 3.8
1014 139
n-undecane 2.34
106 7.1
1016 157
Benzoyl peroxide benzene 79.8 3.3
105 139
Dibenzoyl peroxide benzene 5.75
104 1.2
1013 120
n-octane 2.63
103 3.5
1014 121
Tetralyl hydroperoxide mineral oil 150 1.35
104 1.3
1011 121
9-Decalyl hydroperoxide decalin 150 9.9
105 8.5
1013 134

The values are only valid for highly dilute solutions. Only under these conditions is the decomposition unimolecular.
60 Oxidation

Table 6. Preexponential factors and activation energies for the initiation reactions 3(139) and 3(140) a [340, 341, 351353]

Compound Reaction mechanisma T,  C Ai,1, L mol1  s1 Ea,i,1, kJ/mol Ai,2, L2 mol2  s1 Ea,i,2, kJ/mol
3
Tetralin 140 130 3.4
10 86.7
Cyclohexane 139 8
1012 167.5
Cyclohexanol 140 8.3 67.0
Cyclohexanone 140 2.1
102 73.3
Cumene 139 120 3.5
109 113.0
o-Xylene 139 2
108 129.8
Ethanol 139 6
107 125.6
Benzaldehyde 140 5 2.5
103 48.5
a

(139): RH O2 ! R OOH ui,139, ki,139, etc.

(140): RH O2 HR ! R HOOH R ui,140, ki,140, etc.
ui,139 ki,139  [RH] [O2]; ui,140 ki,140  [RH]2  [O2];
ki,139 Ai,139  exp (Ea,i,139/R T); ki,140 Ai,140  exp (Ea,i,140/R T).

Equation (140) is probably an oversimplification because there is experimental evidence that this reaction proceeds via two or more steps
involving a complex of the type [RH . . . O2] [341, p. 20 ff.].
a
If RH consumption is proportional to the reaction rate ui, the reaction mechanism (139) is valid. With a quadratic relationship between RH
consumption and ui, the reaction mechanism (140) is valid. For more details, see [341, p. 18 ff.].

Table 7. Rate constants, preexponential factors, and activation energies for the chain-propagation reaction (143)a

Compound T,  C kp, L mol1 s1 Ap, L mol1 s1 Ea,p, kJ/mol

b
Tetralin 25 13.3 2.5
104 18.8
Tetralin 30 1.6b
Cyclohexane 60 0.53
Cyclohexane 1.5
106 35.6
Cyclohexane 75 0.34 57.8
Cyclohexanol 40 0.70
Cumene 30 0.18
Cumene 65 0.50 1.1
104 28.1
Benzaldehyde 5 1900 4.8
104 7.5
Benzaldehyde 30 33 000
a
(143): RH ROO ! R ROOH; up kp  [ROO ]  [RH]; kp Ap  exp (Ea,p/R T).
b
Data from different authors sometimes differ by more than one order of magnitude.

Table 8. Rate constants, preexponential factors and activation energies for the chain termination reaction (150)a

Compound Solvent T,  C 2kt, L mol1 s1 2 At, L mol1 s1 Ea,t, kJ/mol

HOO 30 7.60
105
Primary RCH2OO 30 107
Tetralinb Tetralin 60 2.14
107 4
107 1.7
Cyclohexaneb Cyclohexane 60 5.25
106 5.9
107 6.7
Ethylbenzeneb Ethylbenzene 60 1.90
107 1.9
107 0.0
Cumeneb Cumene 60 1.12
105 1.3
1010 32.2
Isobutaneb Isobutane 60 1.23
104 1.6
109 32.6

a
(150): ROO ROO ! ROOR O2; ut kt  [ROO ]2; kt At  exp (Ea,t/R T).
b
The compound name stands for the secondary or tertiary peroxy radical, respectively.

3. The number of repetitions of Reactions follows that:

(142) and (143) is referred to as the kinetic up kp
n pp  RH 158
chain length n. It is given by the ratio of the ut 2kt ui
propagation rate to the termination rate. With increasing rate of radical formation
Because of the stationary state ui ut, it and radical concentration, i.e., with

intensification of the reaction conditions
(e.g., by raising the temperature and/or
initiator concentration), the chain length
becomes shorter. Under mild reaction con-
ditions n can exceed 1000. Under industrial
conditions it is usually ca. 10.
4. The hydroperoxide decomposition has the
highest activation energy. The values given
are extrapolated to infinite dilution and are
therefore valid for the uncatalyzed, thermal
decomposition. Under normal oxidation
conditions (no metal catalyst, but typical
concentrations of radicals, hydroperoxides,
alcohols, acids, and other substances with an
accelerating effect), the activation energies
for the hydroperoxide decomposition are
considerably lower, especially in the liquid
phase. Nevertheless, they are still higher
than those of the other reactions. The hydro-
peroxide decomposition therefore deter-
mines the temperature range of the
oxidation.
5. With progressing oxidation an increasing
number of intermediates are formed (alde-
hydes, alcohols, ketones) that are more read-
ily oxidized than the starting hydrocarbon.
These products form, on the one hand, other
hydroperoxides and peroxy radicals, some
more labile, some more stable, and on the
other hand some of these products and their
radicals catalyze the decomposition of the
hydroperoxides.
This has several consequences:
a. The reaction rate increases until it
reaches its maximum with the appear-
ance of aldehydes.
b. The O2 uptake is accelerated to a
greater extent than the consumption
of the starting material owing to for-
mation of the more readily oxidizable
intermediates.
c. The products formed from these inter-
mediates principally lower carbox-
ylic acids are more stable to
oxidation than the starting hydrocar-
bons and, in the case of metal-cata-
lyzed autoxidations inhibit the
peroxide decomposition with increas-
ing concentration. The rate of radical
formation thus decreases gradually to
zero and the reaction stops before the
Oxidation 61
starting material is completely
consumed.
6. Aldehydes are particularly readily oxidized
(see Sections 4.1 and 4.4.1).
5.3. Differences between Liquid- and
Gas-Phase Autoxidations
In principle, autoxidations proceed with the
same mechanism in the liquid and gas phases.
However, to achieve comparable reaction rates,
the temperature in the gas phase must be
100200 C higher than in the liquid phase
because of the weaker interactions between
the molecules (in the gas phase nearly no
hydrogen bonds are formed, no metallic cata-
lysts are present, etc.).
Above 250 C paraffins increasingly react
with oxygen in a first step to olefins and
hydrogen peroxide. Hydrogen peroxide is
far more stable than alkyl hydroperoxides
against splitting of the OO bond. Addition-
ally, above 250 C peroxy radicals increasingly
do not stabilize to form hydroperoxides, but
isomerize and/or split directly to products
such as aldehydes plus RO . But these
reactions require higher activation energies
than decomposition of hydroperoxides. There-
fore, in the region 350450 C, depending on
the hydrocarbon, the reaction velocity
decreases with increasing temperature (region
of negative temperature coefficient). At higher
temperatures the reaction rate rises again with
temperature.
The effect of material and heat transport is of
considerable importance for the different path-
ways followed by homolytic oxidations in the
liquid or gas phase.
In the liquid phase, heat transfer is good and
the oxidation rate is mostly limited by oxygen
transport from the gas phase. In the gas phase
mass transfer does not limit the oxidation rate
but heat transfer is poor due to the low mass of
the gas. The oxidation reaction can therefore
readily turn into a thermal explosion due to
insufficient heat removal.
More details on gas phase oxidation are
given in Section 4.5. A detailed account of
the differences between gas- and liquid-phase
oxidations can be found in, for example [341,
pp. 442495].
62 Oxidation

5.4. Homolytic Oxidation in the Liquid
Phase
5.4.1. Secondary Reactions of Radicals,
Peroxides, and other Intermediates
It is only possible here to go briefly into the
secondary reactions of the intermediates and
radicals that are important for the understand-
ing of radical chain oxidations by means of
selected examples. For further information see
[372, 374].
Reactions of Alkyl and Aralkyl Radicals.
The most important reactions of these radicals
are:
1. Addition of O2 (Reaction 142).
2. Recombination with other radicals (termi-
nation Reactions 148, 149, 151).
3. Addition to CC double bonds.
4. Isomerizations (Reactions 159 to 162).
Because Reaction (142) is so rapid, even a
low O2 concentration (O2 partial pressure in the
gas phase 25 kPa) is sufficient to make the
concentration of hydrocarbon radicals so small
that they can practically no longer participate in
recombination reactions.
In industry, however, oxidation reactions are
mostly run with O2 off-gas concentrations near
to zero. The upper part of the bubble column is
thus deficient in O2, so that the concentration of
hydrocarbon radicals increases, and radical
recombination reactions can occur in this region.
Thus in practically all industrial autoxidations
radical trapping products formed according to
Reactions (148) to (151) are found.
The addition of alkyl radicals to CC dou-
ble bonds occurs in olefin oxidations and acts as
an initiation reaction for radical polymerization
in the oxygen-deficient regions of the bubble
column.
Radicals that are stabilized by p-electron
systems isomerize very readily; examples
include Reactions (159) to (162):

159

Yield 100%;
no polymeric peroxide

160

Yield 100% polyperoxide;

no hydroperoxide

161

Yield 100% hydroperoxide

162

Table 9. Relative rate of Reaction (143) as a function of the
nature of the attacked CH bond
RH CH prim. sec.
2-Methylpentane urel 1 30
Reaction (162) involves a doubly activated
CH2 group as is present in, for example, lino-
lenic acid derivatives. Double bond systems of
this type isomerize almost completely during
oxidation to give conjugated double bonds.
With an adequate O2 supply they reactlike
all olefinsto form copolymeric peroxides.
With a deficiency of O2 they react to give
homopolymers (principle of self-drying oil
paints).
Reactions of Peroxy Radicals. The most
important reaction of the peroxy radical is H
abstraction (Reaction 143). The relative rates of
attack of ROO on primary, secondary, and
tertiary CH bonds and on CH bonds which
have another substituent (OH, OOH) on the
same C atom are given in Tables 9 and 10. For
example, alkylperoxy radicals react with the
primary, secondary, and tertiary CH bonds in
2-methylpentane in the ratio 1/30/300.
The OOH substituent in the hydroperoxide
activates the aH atom towards H abstraction
Table 10. Relative rate of Reaction 3(143)  as a function of the
substituent X at the same carbon atom bearing the attacked CH
bond
XRH X: H OOH
urel: 1 9.5
Ethylbenzene-X [(1-X,1-phenyl)
ethane]
urel: 1 13
n-decyl-X
Reaction (143) R  H ROO ! R ROOH
Oxidation 63
by the chain carrying peroxy radicals. Taking
cyclohexane autoxidation as a case study,
tert. peroxy radicals react 50 times faster with
the hydroperoxide (i.e., the primary propaga-
300
tion product) than with the parent hydrocarbon
[79]. The abstraction product (i.e., CyaH
OOH) is not stable and promptly dissociates
to cyclohexanone plus HO [375]. The
hydroxyl radical rapidly goes on to abstract
an H atom from the cyclohexane substrate,
producing water and an alkyl radical. Both
steps combined are exothermic by 209 kJ/mol,
causing a rapid increase of the local tempera-
ture by several hundred degrees. This local-
ized hotspot affects the further fate of the
solvent encapsulated radicals. Indeed, either
the species just diffuse away from each other,
or the R radical reacts with the nascent
CyOOH to form alcohol and an alkoxy radical.
Although the latter reaction features an appre-
ciable barrier compared to the diffusive sepa-
ration, the local high temperature makes this
OH abstraction possible. As such, the consec-
utive copropagation of the primary hydro-
peroxide produces both ketone and alcohol.
This mechanism was verified for a number of
different substrates and readily explains the
experimental trend in alcohol-to-ketone ratio:
substrates that form (resonance) stabilized
alkyl radicals feature a lower alcohol-to-
ketone ratio as the barrier of the R plus
ROOH reaction increases [79, 216, 376].
The OH substituent in alcohols also acti-
vates the a-H atom towards H-abstraction by
peroxy radicals. Although slower than for the
corresponding hydroperoxde, this copropaga-
tion leads to the formation of a-hydroxylper-
OH oxy radicals after the addition of O2. These
12 radicals can eliminate HO2 radicals in an
equilibrated reaction [377] that have an inhib-
iting effect on autoxidations, as they terminate
diffusion controlled with peroxy radicals
[378].
Because of their comparatively low
reactivity the ROO radicals can accumulate
in detectable concentrations (unlike, for exam-
ple, HO , R , RO ). In the oxidation of cumene,
6.3
radical concentrations of up to 8
105 mol/L,
corresponding to 5
1016 molecules/cm3, were
detected by ESR. Peroxy radicals therefore
frequently recombine, for example by
Reactions (163, Russel reaction) and (164).
64 Oxidation
163
164
Lacking H atoms at the C atom that binds the
peroxy group, tertiary ROO radicals cannot be
stabilized in the same simple way as primary
and secondary peroxy radicals (see Reaction
163). They generally recombine to give tetr-
oxides, which subsequently decompose form-
ing very stable di-tert-alkyl peroxides
(Reaction 164) or tert-alkoxy radicals. The
latter may either form tertiary alcohols or
decompose further with cleavage of the carbon
framework to form ketones, aldehydes, alkanes,
or other decomposition products:
165
Because reactions of type (165) have high
activation energies, the overall reaction of the
recombination of tertiary ROO radicals pro-
ceeds in general with high activation energy
(see Table 8).
Rate constants and activation energies for
the recombination of primary, secondary, ter-
tiary, and allylic ROO radicals are listed in
Table 8. The oxidation rate is inversely propor-
tional to these chain termination rate constants
(see Eq. 157). Therefore, under mild conditions
(ca. 100 C) autoxidations of primary and sec-
ondary CH bonds are slower than those of
tertiary CH bonds, not only because of their
higher bond energies but also because of the
higher recombination rates of primary and sec-
ondary ROO radicals.
In contrast, hydrocarbons with allylic CH
bonds such as ethylbenzene and tetralin are
oxidized faster than those with tertiary CH
bonds. Nevertheless, because of the higher
recombination rates of allylic ROO radicals,
addition of the corresponding hydrocarbons
does not enhance, but strongly hinders the
autoxidation of tertiary CH bonds under
mild conditions. For example, the rate of oxi-
dation of cumene is reduced by two thirds by
the addition of 3% tetralin because the rapidly
formed tetralyl peroxy radicals capture the
cumyl peroxy radicals, which are formed
more slowly. Ethylbenzene has an analogous
effect.
Peroxy radicals also add readily to CC
double bonds, forming either epoxides and
alkoxy radicals (Twigg mechanism) [379
381], or polyperoxides and their decomposition
products (epoxides, aldehydes, alcohols, and
ketones) (Mayo mechanism).
166
Reactions of Hydroperoxides. The stability of
hydroperoxides depends on (1) the structure,
(2) the surrounding medium, and (3) the active
components in this medium.
For aliphatic hydroperoxides, the stability
decreases in the order: tertiary > secondary
> primary. Electron-withdrawing groups
(CN, COOR) have a destabilizing effect,

and methyl groups a stabilizing one. Hydro-
peroxides in which the HOO-group is in a
position a to a double bond or an aromatic ring
(resonance stabilization) are fairly stable.
Because CH bonds in such a-positions are
weakened due to the resonance stabilization of
the incipient radical, these types of hydro-
peroxide are formed at lower temperatures
than others, and can be obtained in high yields
(e.g., cumene hydroperoxide).
Table 5 lists kinetic data for the mono-
molecular decomposition of peroxide in highly
dilute solution (see Reaction 145).
In the presence of substrates with weak
CH bonds, the peroxide decomposition can
be enhanced as shown in Reaction (167).
ROOH R0 -H ! RO H2 O R0 167
This has important consequences for autoxi-
dation reactions that yield products with signif-
icantly weaker CH bonds, such as
cyclohexanone in the case of cyclohexane
autoxidation [80]. Indeed, this enhanced
bimolecular initiation with a secondary reaction
product leads to an exponential increase in the
apparent initiation rate constant and explains
the autocatalytic nature of autoxidations.
Because of their acidic character, peroxya-
cids catalyze their own decomposition much
more strongly than the alkyl hydroperoxides
(Eq. 168):
168
The acyloxy radicals formed are more
reactive than the alkyl peroxy radicals. They
can react in different ways (Eqs. 169 and 170):
169
Oxidation 65
170
Normally, Reaction (169) is the preferred
one. But if there are not sufficient molecules
with active CH bonds available, that can be
attacked by the acyloxy radical in order to
stabilize the radical as a carboxylic acid,
Reaction (170) becomes important (formation
of CO2). Reaction (170) seems to be important
also in the case of aromatic acyloxy radicals.
There the odd electron is attracted by the
p-electron system of the aromatic ring which
leads to radical isomerization, and subse-
quently splitting into a phenyl radical and CO2.
Cleavage by Mineral Acids. Mineral acids
protonate peroxides and thus induce their
decomposition. The best known example is
the Hock rearrangement of cumene hydro-
peroxide to give phenol and acetone (Eq. 171):
171
Another industrially important example is
the oxidation of p-xylene to terephthalic acid,
catalyzed by CoBr2 in acetic acid. Oxidations
of alkylaromatics in which mineral acids such
as HBr can be formed only proceed at a satis-
factory rate if it is ensured that the concentra-
tion of the mineral acid remains low. Otherwise,
phenol, which acts as an oxidation inhibitor,
may be formed by acidic hydroperoxide
cleavage.
66 Oxidation

Reactions with Bases. Bases react with pri-
mary and secondary hydroperoxides as follows
(PRITZKOW believes that these findings are arte-
facts, caused by very small impurities of metal
salts in the bases) (Eq. 172):
Reactions with Ketones. In polar solvents,
hydroperoxides readily add to ketones. The
resulting perketals are labile and decompose
readily, forming a variety of products
(Eq. 178):

172
ROOH B ! ROO B  H

Chain reaction (Eqs. 173 and 174):

ROO ROOH ! RO O2 ROH 173

RO ROOH ! ROH ROO 174

178
In secondary dialkyl peroxides, the CH
bond at the same atom as the peroxy group is
attacked (Eq. 175):

Peroxy acids react with ketones with CC

bond cleavage to give esters or lactones
(BaeyerVilliger reaction) (Eq. 179).
175

Bases have practically no effect on tertiary

dialkylperoxides.
Reactions with Olefins. In the absence of epox-
idation catalysts (e.g., Mo complexes) hydro-
peroxides predominantly react with olefins
according to (Eq. 176):
176
whereas peroxy acids mostly give epoxides
very selectively in a nonradical reaction (Eq.
177) (Prilezhaev reaction; see Section 5.1)
179
Reactions with Aldehydes. Peroxy acids add to
aldehydes more readily than to ketones, form-
ing the corresponding aldehyde monoperesters.
Cleavage of these compounds gives the corre-
sponding acids. This cleavage is selectively
catalyzed by Mn2/Mn3 ions (see Section
4.4.2) In the oxidation of aldehydes to acids
almost the entire acid is formed via this path-
way (Eq. 180):

177

180
 Oxidation 67

Reactions of Alkoxy Radicals. The alkoxy
radicals formed in the decomposition of hydro-
peroxides are very reactive. However, only
primary alkoxy radicals appear to react pre-
dominantly by abstraction of hydrogen atoms to
form alcohols. Secondary and, above all, ter-
tiary alkoxy radicals react predominantly by
CC cleavage to give aldehydes or ketones,
together with small amounts of alcohols
(Eqs. 181183).
proceeds via intermediate aldehydes and ace-
tals to give the corresponding acids and esters.
The autoxidation of secondary alcohols pro-
ceeds through a-hydroxyperoxy radicals
(Reaction 178) that yield the corresponding
ketone upon elimination of HO2 (Eq. 185).

181

185

The ketones formed are further oxidized via

the a-hydroperoxyketones (Eq. 186):

182

183

186

The CC cleavage reactions (Reactions 182

and 183) are very important in autoxidation
because the carbon chain degradation proceeds
mostly by these mechanisms. In case of
Aldehydes form addition products with
cyclohexane oxidation, significant amounts
polar compounds in the liquid phase. In the
of cyclohexoxy radicals are formed in the
addition product the CH bond of the aldehyde
co-propagation of the hydroperoxide. A frac-
group becomes strongly activated by two polar
tion of those radicals decompose to v-formyl
groups (see Section 4.1, and Table 10, where
radicals (i.e., CH2(CH2)4CHO). These species
the activation of the CH bond by one polar
are the most significant cause of ring-opened
substituent is shown) (Eqs. 187190):
byproducts in this industrially important
process [382].
In olefin oxidations, alkoxy radicals also add
to CC bonds (Eq. 184) [380]:

187

184

Oxidation of Alcohols, Aldehydes, and 188

Ketones. The oxidation of primary alcohols
68 Oxidation
189
190
The acyl radicals formed initially can
decompose forming an alkyl radical and CO
if there is an oxygen deficiency (Reaction 60) or
can also recombine to give diketones (Reaction
190: synthesis of diacetyl from acetaldehyde).
Carbon monoxide and carbon dioxide are
formed in autoxidation almost exclusively by
decomposition of acyl and acyloxy radicals.
The presence of CO in the reaction waste gas
5.4.2. Metal Catalysis in Homolytic Liquid-
Phase Oxidation
Homolytic liquid-phase oxidation is influenced
by many metal ions, but only metals that can
occur in two valence states of approximately
equal stability in the oxidation medium can act
catalytically. These are above all Co2/Co3
and Mn2/Mn3. Ionic pairs such as Cu/Cu2
and Fe2/Fe3 are important only in special
cases.
The catalytic activity of these metals is
based on the acceleration of peroxide decom-
position by lowering the activation energy
(Eqs. 192194)
Metal catalysis (Ea 4050 kJ/mol):
(at an order of magnitude of  0.1 vol%) is thus
a sensitive indicator of oxygen deficiency in
autoxidations.
Cooxidation Cooxidation is the simultaneous
oxidation of several substances. The cooxida-
tion of aldehydes and olefins to produce
epoxides (and acids) is particularly well known
(Eq. 191):
191
as is the cooxidation of p-xylene and par-
aldehyde or methyl ethyl ketone in acetic
acid to give terephthalic acid and acetic acid
(Toray, Olin-Matheson).
As is apparent from the preceding sections,
practically every autoxidation becomes a coox-
idation soon after initiation. Planned cooxida-
tion has achieved great importance, e.g., for
elucidating reaction mechanisms and determin-
ing the relative reactivity of homologous
species.
192
193
194
Because alkyl hydroperoxides are strong
oxidants, Reaction (193) is only important in
the decomposition of pure hydroperoxides, i.e.,
at low conversions. At higher conversions the
metal ions in the higher valence state are pref-
erably reduced by aldehydes, because
aldehydes are strongly reducing compounds
(Eqs. 195 and 196):
195
196
Mn2/Mn3 catalyze the decomposition of
hydroperoxides in the same way as cobalt ions.
Although Mn3 is considerably less active than
Co3, manganese is of great importance in the
homolytic oxidation of hydrocarbons to acids,
because it selectively catalyzes the splitting of
 Oxidation 69

the addition product of peracids and aldehydes In the oxidation of p-xylene to TPA the
(the aldehyde monoperester) into two mole- peroxy anion can alternatively react to form
cules of acid. the corresponding aldehyde (Eq. 200):
Prior to decomposition, the hydroperoxides
have to form complex compounds with the
metal ions. Therefore, the rates of these redox
reactions depend strongly on the medium.
In the series: alkyl hydroperoxide < alcohol
< water  acid, the hydroperoxides are the
weakest complexing agents. Therefore, alco-
hols, but in particular water and acids, act as
catalyst poisons by competing with the hydro-
peroxides for the metal ion complex sphere. If
these compounds are present in appreciable
amountsthat is the case in nearly every nor-
mal oxidationCo2/3 has to be added in
fairly high concentrations, e.g., in polar media 200
0.051 wt% and in nonpolar media 1500 ppm
(ca. 104105 mol/L).
Because water and acids act as catalyst (AcO acetate anion)
poisons, water and acids formed during the
reaction should be stripped off to as low con- The decomposition of dialkyl peroxides is
centrations as possible. Acids, which cannot be accelerated by Fe3, Cu, and complex com-
stripped off, will slow down the oxidation rate pounds of Mo6, W6, V6 and Ti4 (see
long before the hydrocarbon starting material is Section 5.1). Co2/3 and Mn2/3 decompose
consumed. In the special case of oxidation of p- dialkyl peroxides only under conditions which
xylene to DMT, the acid intermediate is esteri- are not relevant to autoxidation.
fied in order to achieve conversion of the Peroxy acids are decomposed analogously
second methyl group as. to alkyl hydroperoxides (Eq. 201):
The precise molecular mechanism of per-
oxide activation by cobalt complexes is not yet
fully understood. Recent experimental and
theoretical work suggests, at least in nonpolar
hydrocarbon environment, a slightly modified 201
mechanism (Reactions 197199) in which
Reaction 199 would be rate-determining.
Reaction 197 and 198 are computationally
predicated to be both fast due to spin catalysis, Because peroxy acids are stronger oxidizing
i.e., two-state-reactivity is suggested to signif- agents and much weaker reducing agents than
icantly lower the barrier of both steps [81]. At hydroperoxides, reduction of Co3 ions only
higher catalyst concentrations, the CoIII- occurs with aldehydes according to Reactions
OOR intermediate could alternatively form (195 and 196).
an inert dimeric complex with free CoII
species (i.e., termination), explaining a
Effect of the Catalyst and the Medium. The
remarkable catalystinhibitor transition,
metal ions have a major influence on the course
observed at higher cobalt concentrations.
of the reaction, as the following examples show.

CoII ROOH ! CoIII-OH RO (197)

The oxidation of acetaldehyde can be con-
CoIII-OH ROOH ! CoIII-OOR H2O (198) trolled to give considerable amounts of diacetyl
or acetic anhydride besides acetic acid, depend-
CoIII-OOR ! CoII ROO (199) ing on the nature and concentration of the
70 Oxidation

catalyst. In both cases the production of CO, esterification of the p-methylbenzoic acid (hin-
CO2, and CH4 is enhanced, too. drance by the acid formed) (Eqs. 206 and 207):
Oxidation in acetic acid with catalytic quan-
tities of Mn gives acetic acid.
Addition of catalytic quantities of copper
acetate to the Co2/3 catalyst leads to forma-
tion of acetic anhydride in addition to acetic 206
acid (Eqs. 201 and 202):

202

207

Single-stage oxidation of both methyl

203
groups succeeds in acetic acid in the presence
of 5001000 ppm Co and Mn acetate and either
a peroxy acid-forming cooxidizing agent such
as paraldehyde or acetaldehyde (Toray, East-
man-Kodak), or with Br ions as radical sources
(Mid-Century/Amoco).
The Cu cations seem to stabilize the acyl
Whereas the peroxy acid formed in the
cations and anions and the peroxyacyl radicals.
Toray or Eastman-Kodak process overcomes
Oxidation in the presence of large quantities
the low oxidizability of the second methyl
of manganese(III) acetate gives diacetyl, acetic
group, which is due to the carboxyl group, in
acid (and CO, CO2, CH4) (Eqs. 204 and 205):
the Mid-Century/Amoco process Co3 and the
Br radical act as abstractors for protons or H
atoms, respectively (Eq. 208):

204

205

Oxidation of p-xylene: pure p-xylene is mainly 208

oxidized to p-methylbenzoic acid in the pres-
ence of 100200 ppm Co and up to 100 ppm Mn
acetate in a normal radical chain reaction at
140180 C and 10 bar. The greater part of the The intermediate 4-carboxybenzaldehyde is
second methyl group can only be oxidized after rapidly oxidized further to give the acid.
 Oxidation 71

Table 11. Relative activity of various metal ions in the The effect of phenols and aromatic amines is
decarboxylation of carboxylic acids particularly well known. Because of their weak
Metal ion Relative activity OH and NH bonds, they readily transfer H
4
atoms to radicals. The resulting phenoxy or
Ce 1
Ag2 2
arylamino radicals are extremely unreactive
Pb4 20 due to resonance stabilization and, in the
Co3 100 case of 2,6-disubstituted phenols, because of
Mn3 500 the strong steric hindrance. The radical chain
reaction is thus interrupted, as shown in
Reaction (210):

Nevertheless, the removal of residual aldehyde

is the major problem in the purification of the
crude terephthalic acid (TPA), which crystal-
lizes out rapidly due to its insolubility in the
reaction medium and occludes small amounts
of aldehyde, which are thus protected from
further oxidation. Amoco solved this problem
by hydrogenating the carboxybenzaldehyde
with palladium as catalyst.
In the cooxidation process, only ca. 0.2 t
acetic acid per ton TPA are formed although the
cooxidant must be present in at least a stoichi-
ometric ratio.
210
In the Mid-Century/Amoco process 0.05 t
acetic acid are consumed per ton TPA.
One reason for the low yield and high loss of X Alkyl; not alkoxy
acetic acid is its metal-ion-catalyzed An inhibitor molecule can thus capture two
decarboxylation (Reaction 209). The methyl radicals. The relative efficiency of the inhibi-
radical formed is transformed to methanol tors depends strongly on the substituents
and finally to methyl acetate, which is the (Table 12).
largest by product in this process.
The decarboxylating activities of some
metal ions are listed in Table 11. The reaction Table 12. Relative inhibitor effect of trialkylphenolsa on the
(209) is fast above 140 C. oxidation of crude oil [338, p. 50]

R1 R2 R3 Relative inhibitor effect

H H Me 10
tert-Bu tert-Bu tert-Bu 36
209 Me Me tert-Bu 46
tert-Bu tert-Bu sec-Bu 80
tert-Bu tert-Bu Me 100
Me Me Me 118
tert-Bu tert-Bu Ethyl 125
tert-Bu tert-Bu n-Bu 140
Me tert-Bu Me 170
5.4.3. Inhibitors of Homolytic Liquid-Phase
Oxidation

Inhibitors are substances that hinder the forma-

tion of the active intermediates (radicals,
hydroperoxides, catalysts) or lower their con-
centration by complexing, decomposing, or
trapping them. 
2,6-Di-tert-butyl-4-methylphenol 100
72 Oxidation
Whereas phenols and amines mainly capture
radicals, organic sulfides and thiols usually
react with hydroperoxides as follows (Eq. 211):
211
For this reason mixtures of organic sulfides
and phenols or amines have a stronger inhibit-
ing effect than the individual components
(inhibitor synergism).
The inhibiting effect of an excessively high
metal concentration has already been men-
tioned (see Section 4.4.2). Compounds that
form metal complexes can also act as inhibitors
if the number of donor centers corresponds to
the coordination number of the metal. For
example, disalicylidene-1,2-propylenediamine
is added to gasoline in concentrations of
108 mol/L because it forms stable complexes
with metals, thus preventing them from cata-
lyzing autoxidation.
Disalicylidine-1,2-propylenediamine
It is noteworthy that phosphates, especially
di- and triphosphates, appear to inhibit radical
chain oxidation. Pyrophosphates and in partic-
ular dihydrogenpyrophosphates are used as sta-
bilizers for aqueous hydrogen peroxide,
whereby they inhibit its radical chain decom-
position, mostly by effectively chelating tran-
sition metals that otherwise would catalyze the
reaction. They are not only the most effective
fire-extinguishing powders (in the form of
ammonium hydrogen phosphate), and, as pyro-
phosphate (P2 O2
7 ), a component of many het-
erogeneous gas-phase oxidation catalysts, but
are also components of important building
blocks of all living cells in the nucleotides
and nucleic acids. In what way they interfere
with the radical chain oxidation has apparently
not yet been investigated.
For an introduction to autoxidation and the
effect of inhibitors and stabilizers, in particular
with reference to the protection of polymers
from oxidative aging, see [338].
5.4.4. Special Cases of Homolytic Oxidation
Boric-Acid-Modified Alkane Oxidation (!
Alcohols, Aliphatic). The oxidation of hydro-
carbons in the presence of suspended metaboric
acid, known since 1928, appears to be a border-
line case between homolytic and heterolytic
oxidation. Secondary alcohols are preferably
formed with unchanged carbon frameworks
(selectivity > 80%), together with ketones
and diols. In the presence of olefins, epoxides
are also formed in considerable yields.
The way of action of the boric acid is not
clear yet. Until the 1970s it was believed that
boric acid reacts only with the alcohol to form
boric ester, which are very resistant to further
oxidation. Later on epoxides were found, that
are formed during the oxidation of olefins in the
presence of boric acid. This led to the assump-
tion that the boric acid already catalyzes the
decomposition of the hydroperoxides. But,
because in the oxidation of paraffins the ratio
of secondary alcohols to ketones is very high
(nearly no Russell reaction), it seems very
likely that the boric acid reacts directly with
the peroxy radicals to the corresponding boric
esters and hydroperoxy radicals.
After oxidation, the alcohols must be liber-
ated from the boric esters by hydrolysis. Only
one OH group of the boric acid reacts with the
alcohol to give the ester (Eqs. 212214).
212
213
214
 Oxidation 73

In Reactions (213) and (214) the protons of the Chain propagation

boric acid depicted in parentheses do not
behave like normal protons. They do not take
part in esterification.
Alkyl aromatics cannot be oxidized in this
way because boric acid also catalyzes the Hock
cleavage to give phenols, which inhibits further
oxidation shortly after initiation.

Paraffin Sulfonation (! Surfactants). A fur- 216

ther special case is the paraffin oxidation pro-
cess in the presence of SO2. Of several
variations, two are carried out industrially.

Sulfochlorination (Reed Process). Sulfur diox-

ide and chlorine are introduced into the paraffin
at 2535 C in the presence of UV radiation.
The reaction proceeds by a radical chain mech- Decomposition of peracid
anism with alkylsulfonyl chloride (i.e., chlor-
osulfonic acid) as the final product.
The kinetic chain length is 40005000. The
conversion is limited to 30% to minimize
further oxidation to di- and polysulfonic
acids. 217

Sulfoxidation (LightWater Process). If SO2

and O2 (in a molar ratio of 2:1 to 10:1) are
passed through an n-alkane in the presence of
UV radiation at 2040 C, alkyl persulfonic acid
is initially formed in a radical chain reaction. In
pure paraffin, the persulfonic acid reacts further
to give dark colored products. If water is added
to the alkane, the reaction is slower and for each
mole alkyl sulfonic acid an equivalent quantity
of sulfuric acid is formed. However, the product
remains colorless because the water extracts the
alkylpersulfonic acid and catalyzes its reaction
with SO2 to give alkylsulfonic acid and sulfuric
acid. The alkane conversion is limited to ca.
1% to keep the undesired polysulfonation low
(Eqs. 215217).
Initiation
215
Remarkably, SO2 adds faster to the alkyl
radical than O2. Excess of SO2 is therefore
important. The reactivity of the alkylpersul-
fonyl radical formed by subsequent addition
of oxygen is similar to that of the alkylperoxy
radical. The sulfonic acid group is thus situated
predominantly at carbon atoms in the middle of
the chain.
Aromatics, olefins, and branched-chain par-
affins inhibit the reaction.
5.4.5. Process Technology of Homolytic Liq-
uid-Phase Oxidation
The various starting materials (liquefied
petroleum gas, low-boiling aldehydes to
high-boiling, long-chain paraffins, alkylhy-
droanthraquinone etc.) and the widely differ-
ing products (from H2O2 to terephthalic acid)
also require differing conditions (temperature,
pressure, solvents, reactor material). Some
74 Oxidation

general rules may be given, which are valid for Apart from the O2 partial pressure, the rate
most radical chain oxidations. of O2 transport from the gas to the liquid phase
depends only on the area of the phase boundary
Reaction Parameters, Reactor Geometry, surface, i.e., the bubble size. Therefore, the gas
Operation. The aim of industrial reactions is must be divided into the smallest bubbles pos-
to produce as much product as possible per unit sible on entry into the reactor and these must be
time and reactor volume. Because the mass prevented from coalescing into larger bubbles
flow of the educts, reaction temperature, and while they rise up the liquid column.
catalyst concentration can be chosen freely If turbulence is too severe and there is
within limits, these parameters are normally consequent coalescence, large gas bubbles are
maximized to give high throughput and produc- formed and the oxygen cannot pass into the
tion numbers. Consequently, O2 transport from liquid phase quickly enough. Oxygen then
the gas to the liquid phase becomes the rate- appears in the waste gas, although the oxidation
determining step, often at the expense of lower suffers from an O2 deficiency.
product selectivity. This is even worsened by The gas velocity based on the reactor cross-
the fact that for safety reasons the O2 content of section should thus clearly lie below 0.02 m/s.
the off-gas is usually kept near to 0 vol%, At higher velocities turbulence arises in the
resulting in O2 deficiency in the upper part bubble column that promotes coalescence of
of the bubble column. the gas bubbles.
To test whether an oxidation is controlled by The height of the liquid phase in the reactor
O2 transport, it is sufficient to increase the O2 above the air inlet must be adapted to the rate of
pressure and to see if the reaction rate subse- O2 take-up. It can be determined in pilot experi-
quently rises. According to Equation (157) if ments (see below). Generally 46 m should be
there is an adequate O2 supply the reaction rate sufficient. The volume required for the neces-
is independent of the O2 concentration and thus sary throughput should be obtained by increas-
of the O2 transport. The solubility of O2 in ing the cross-section of the reactor (tanks
organic solvents is only ca. 102 mol/L (see instead of columns). In industry, for historical
Table 13). reasons, most oxidation reactors in operation
are much higher (up to 30 m and more with
liquid heights of 8 to more than 20 m). The
Table 13. Solubility of oxygen in organic compounds at 1 bar reaction pressure should be chosen in a range
[385, p. 1 ff] where boiling of liquids is avoided because the
Solvent T,  C O2 concentration, a vapor formed would enlarge the gas bubbles
103 mol/L and lower the O2 concentration in the bubbles,
Benzene 20 9.1 0.204
thus hinder oxygen transport.
Benzene 60 9.6 0.216 Reactors for radical chain reactions must
Toluene 20 5.3 0.119 have the smallest possible surface to volume
p-Xylene 26 8.3 0.118 ratio because of the undesired radical
p-Xylene, tech. 23 7.2 0.162
p-Xylene, tech. 80 8.0 0.179
recombination that always occurs at the walls.
p-Xylene, tech. 100 8.6 0.192 Apart from necessary built-in devices, like
Isooctane 20 13.9 0.312 sieve plates for gas redispersion and cooling
Isooctane 50 14.6 0.327 tubes, packings and devices with large surface
Dodecane 25 8.25 0.185
Methanol 20 10.5 0.235
areas should not be used in the reaction section.
Ethanol 20 6.4 0.143 However, in the gas space above the bubble
Acetone 20 9.6 0.215 column packings with large surface areas are
Cyclohexanol 116 9.5 0.213 recommended to suppress gas explosions.
Cyclohexanone 100 10 0.224
Benzaldehyde 5 4 0.090
Oxidation can be operated as a batch or
Decanal 5 4 0.090 continuous process. In a continuous process

the residence time spectrum is broadened, as
a cm3 O2 (STP) cm3 bar1.

The determination of O2 solubility requires a long time for
part of the fresh starting material is carried
equilibrium to be reached. Hence, the values for readily oxidizable straight out again because of the generally
substances such as aldehydes are probably too low. strong back-mixing. Accordingly, part of the

product remains longer in the reactor and is
overoxidized. The selectivity is thus lower than
in batch processes. For this reason many large-
scale oxidations are still performed batchwise
even today. The selectivity in continuous oxi-
dations can generally be improved by using
baffles (sieve plates, etc.), which convert the
reactor into a bubble column cascade and lower
back-mixing.
Reactor Materials; Corrosion. The choice of
reactor materials is determined by the reaction
medium and conditions (temperature, pressure,
etc.). Most base metals and alloys are only
protected from chemical attack by a dense,
tightly adhering layer of oxide (passivation).
These materials (Al alloys, Ti, stainless steel)
are generally stable towards oxidizing media,
but are readily attacked by reducing media (see
Fig. 9).
Because many heavy metal ions also have a
catalytic effect, aluminum and its alloys are
recommended for the oxidation part under
moderate conditions of temperature and pres-
sure. For higher temperatures and pressures,
stainless steel is recommended. Stainless steel
is, however, rapidly attacked by halide ions
even in an oxidizing medium. Therefore, for
example, for the Mid-Century process reactors
coated with titanium or Hastelloy C must be
used.
Figure 9. Corrosion resistance of various materials
The effective corrosion resistance of each material in an
acid environment is that portion of the chart below each bar
(with kind permission of Gulf Publishing Comp., taken
from Hydrocarbon Processing, June 1979, p. 214).
Oxidation 75
Copper can inhibit many oxidations even in
extremely low concentrations. Because copper
is contained in fine dispersions in some lubri-
cating agents and slip additives, particular
attention should be paid to such substances in
the case of initiation problems.
In all parts of a plant in which O2 is absent,
i.e., where reducing conditions prevail, special
care must be taken to ensure that the reactor
material and the temperature are mutually com-
patible. For example Material no. 4571 (V4A E;
US specification: SS 316 Ti) is rapidly attacked
by acetic acid in the absence of O2 above
140 C. In the presence of O2 it is stable towards
the acid up to and above 160 C.
The corrosivity of organic materials
increases with the acidity, reducing capacity,
and capacity for complex formation. Besides
formic acid, hydroxyacids such as lactic and
glycolic acids are the most corrosive.
Oxidation on Laboratory and Pilot Plant
Scale. An apparatus is shown in Figure 10
which is suitable for most laboratory scale
homolytic oxidations. Some aspects to which
attention should be paid are as follows:
Figure 10. Laboratory apparatus for liquid-phase oxidation
of high-boiling compounds
a) Thermostats; b) Gas metering; c) Cold traps; d) Off-gas
cooler; e) Water separator; f) Gas sampling; g) O2 analysis;
h) CO/CO2 analysis; i) Gas meter
76 Oxidation
Reactor dimensions:
Laboratory Pilot plant
Diameter, cm >5 > 30
Height, cm > 30 up to 800
In larger pilot reactors back-mixing can be
limited by the incorporation of, for example,
sieve plates.
Reactor Material. In the laboratory, glass
should be used if possible (so that the reaction
can be observed). With metals, oxygen-free
zones should be avoided because of possible
corrosion, possibly by O2 purging.
Reaction temperature is the most important
parameter; constant temperature can best be
achieved by using two heating circuits: one
at the desired reaction temperature for heating
the jacket and one for inner cooling which is
kept 1050 C below the reaction temperature.
The size and shape of the cooling circuit
depend on the reaction and dimensions of the
reactor. Cooling tubes should be arranged ver-
tically and sufficiently far from one another and
from the wall to minimize disturbances to the
gas distribution.
Gas distribution is the second most important
parameter. Tubes with small holes or frits made
of glass, Teflon, or metal are the most suitable.
For metal reactors, the frits should be tested
periodically in glass vessels under conditions
similar to those of the reaction.
Oxygen Content of the Off-gas. At 0% oxygen
content the experimental results are uncertain
because the size of the O2 deficiency zone is
unknown. If higher O2 contents are permitted in
the off-gas, the necessary safety measures must
be adhered to very precisely (see Section 4.6).
A water separator is important in the oxidation
of nonpolar substances and is recommended for
other substances if water is formed as a separate
phase.
Gas Sampling. The O2, CO, and CO2 content
in the off-gas should be continually monitored
if possible; attention should be paid to volatile
substances (e.g., H2, CH4, CH3CHO). The gas
sampling vessel should be purged with at least
ten times the volume of the vessel to obtain
correct values.
Course of a Liquid-Phase Homolytic Oxida-
tion. Batch and continuous oxidation reactions
can be initiated as follows. The carefully
cleaned reactor is charged with the starting
material and the catalyst under nitrogen purg-
ing, the pressure is adjusted to the required
value, and the mixture heated to the initiation
temperature. Then air or O2 is introduced and, if
necessary, an initiator added. The start of the
reaction can be detected by the decrease in the
O2 content of the off-gas and a rise in the
reaction temperature. From this time onwards
the O2 supply is increased in such a way that the
O2 content in the off-gas does not exceed a
critical limit, for instance 5%. The acceleration
of the reaction to maximum velocity usually
occurs rapidly (within 10 to 30 min). The heat
of reaction must be removed and the desired
reaction temperature regulated. With proper
layout, the temperature of the cooling medium
and the control function of the valve in the
cooling circuit can be adjusted on installation of
the system such that the oscillations of the
reaction temperature are maintained below
0.1 C. For batch oxidations, the temperature
of the cooling circuit must gradually approxi-
mate the reaction temperature towards the end
of the reaction, to avoid excessive temperature
fluctuations or breakdown of the oxidation
process. In continuous oxidations, charging
of starting material and removal of the product
begin after the required conditions have been
established.
Applicability of the Results from Laboratory
and Pilot Plant to Full Plant Scale. Scale-up
problems are mainly caused by the following
factors:
1. The laboratory and pilot plant reactors often
have too small a diameter relative to their
height. Because the rising gas bubbles
entrain liquid, a downward streaming in
the rest of the liquid is always produced,
predominantly at the wall of the reactor. The
resulting turbulence leads to rapid coales-
cence of the gas bubbles in reactors that are
too narrow. Thus the exchange area becomes

much smaller and the reaction appears to be
slower than it is.
2. The O2 content of the off-gas is kept near
0% (for further explanation, see above).
Results that are representative for full plant
scale are only obtained with reactors which are
of the same height as large-scale reactors and
have a diameter such that the gas velocity
remains well below 0.02 m/s (diameter 30
cm minimum).
5.5. Homolytic Gas-Phase Oxidation
Homolytic gas-phase oxidations are all com-
bustion processes and gas explosions that take
place in free gas space without heterogeneous
catalysts. Examples include the combustion of
heating oil and natural gas for the production of
heat and energy and the rapid combustion of
gasoline and diesel in internal combustion
engines. Thus the homolytic gas-phase oxida-
tion is one of the most important chemical
reactions with respect to the amounts of mate-
rials consumed.
Mechanism. In principle up to 250 C homo-
lytic gas-phase oxidations proceed by the same
mechanism as liquid-phase oxidations (see
Section 4.3).
However, whereas oxygen transport from
the gas to the liquid phase generally limits
the rate of the overall reaction in a controlled
liquid-phase oxidation, no comparable restric-
tion exists in the gas phase. In the liquid phase
the reaction temperature can be held constant at
low levels by simple means. The rise in tem-
perature is inversely proportional to the mass of
the reaction mixture, and the heat of reaction is
quickly transported to the walls of the cooling
tubes by convection of the liquid. For reactions
in the homogeneous gas phase, the temperature
difference for adequate heat removal must be
much greater because of the small mass. If the
reaction is not limited by the quantity of fuel or
oxygen, and the reaction space is not kept very
small and well cooled, temperatures of over
1000 C can occur in gas-phase oxidations,
whereby heat transfer to the surroundings
occurs mostly by radiation.
Oxidation 77
Because the intermolecular interactions, in
particular through hydrogen bond formation,
are considerably weaker in the gas phase than in
the liquid phase due to the greater inter-
molecular distances, in the absence of catalysts,
hydroperoxide decomposition can only occur
thermally. Because the activation energy for
thermal hydroperoxide decomposition is high
(see Section 4.4.2), gas-phase oxidations only
proceed at the same rate as a comparable liquid-
phase oxidation at considerably higher temper-
atures. However, because heat removal is poor,
an initiated gas-phase oxidation accelerates
considerably faster than a corresponding liq-
uid-phase oxidation and can readily become a
thermal explosion.
Up to ca. 250 C, hydroperoxides predomi-
nate as the first neutral intermediates. Between
ca. 300 and 450 C, isomerization and decom-
position of the peroxy radicals to give alde-
hydes and other fragments becomes faster than
hydroperoxide formation. Thus above ca.
420450 C practically no more alkyl hydro-
peroxides are formed, and aldehydes and alco-
hols together with olefins and H2O2 are the
primary neutral intermediates.
The decomposition of peroxy radicals, usu-
ally with preceding isomerization, has a higher
activation energy than the hydroperoxide
decomposition. Therefore, in the transition
range between 320 and 450 C, the overall
reaction rate of gas-phase oxidation decreases
with increasing temperature (region of negative
ratetemperature coefficients), and subse-
quently rises more sharply than before.
Catalysis and Inhibition. Gas-phase oxida-
tions are catalyzed by radical-forming sub-
stances (halogens and their compounds, NO/
NO2, nitro compounds, volatile peroxides, phe-
nols, and amines) and also by high-energy
radiation and cracking or dehydrogenation cat-
alysts on the reactor walls.
In the gas phase, radical-forming sub-
stances generally only act catalytically if
they are added in very low concentrations.
In higher concentrations (sometimes even in
the ppm range), the radicals formed act as
radical scavengers for the more reactive
hydrocarbon radicals. The mechanism
of action of halogen compounds as fire-
extinguishing agents and as flameproofing
78 Oxidation

agents in plastics, and that of tetraethyl lead 2. Carbon black (rubber filler and strength-
used as an antiknock agent in gasoline up to ener) by combustion of oil or natural gas
the 1980sis based on this radical trapping. with a substoichiometric amount of oxygen
Chain termination by recombination of (see ! Carbon, Section 6.4).
smaller, and therefore highly energetic, active 3. Acetylene by partial combustion of hydro-
radicals (such as H , OH , CH3 ) can occur in carbons (! Acetylene, Section 4.2).
the gas phase only if a third collision partner 4. CO2 by complete combustion of natural gas.
absorbs the energy of recombination (bond
energy) liberated. Apart from the very rare The degradation of hydrocarbons and chlor-
three-body collisions, this occurs mostly ohydrocarbons in the atmosphere takes place by
through collisions with surfaces. Thus gas- radical chain reactions.
phase oxidations, like all radical reactions
occurring in the gas phase (e.g., decomposition
of acetylene or ethylene oxide), are sensitive 5.6. Gas Explosions and Safety Data
towards an increase in surface area. This is the
mechanism of action of packings as flame Modern civilization depends to a great extent
arrestors, powder fire extinguishers, and dusts on the use of hydrocarbons. However, great
to control firedamp in mining. Degenerate rad- dangers can arise from these hydrocarbons in
ical chain explosions that proceed via hydro- the presence of O2 (see Fig. 11). Consequently,
peroxides (e.g., in hydrocarbonoxygen an extensive body of safety data has been
mixtures) can be stopped if fire-extinguishing generated to keep these dangers within accept-
powder or other radical scavengers are added able limits and make the handling of hydro-
early enough. This is because that due to carbons less hazardous. Extensive literature,
indirect chain branching, the pressure rise dur- standards and regulations exist in all industrial
ing the initiation period is so slow, that suffi- countries [358367]. The flammability of gas
cient time remains for releasing the fire-
extinguishing device. But after the initiation
period temperature and pressure can rise very
sharply, changing the slow oxidation in a ther-
mal explosion. These types of thermal explo-
sion can rapidly become detonations, especially
in enclosed spaces such as pipelines.
Nondegenerate branched radical chain
reactions (such as the H2/O2 reaction), on the
other hand, accelerate so rapidly due to direct
chain-branching that no time remains for extin-
guishing measures once the reaction has started
(see Fig. 3). They can only be hindered by
preventive measures such as filling spaces
with packings or capillary bundles.

Syntheses of Intermediates by Homolytic Gas-

Phase Oxidation. Because of the extreme con-
ditions, only a few simple products are pro-
duced by oxidation in the homogeneous gas
phase. These include:

1. Synthesis gas (or hydrogen) by combustion

of hydrocarbons or coal with a substoichio-
metric amount of oxygen and in the Figure 11. Characteristic damage caused by an atmo-
presence of water (! Gas Production, Sec- spheric shock wave reflected from an object as a function
tion 3.2; ! Gas Production, Section 4.1). of the peak pressure [359, p. 60]

mixtures [383] and the effect of inert gases
[384] have been reviewed.
The various safety terms are explained in
[359], which also gives the corresponding stan-
dards for France, Germany, Russia, the United
Kingdom, and the United States.
Explosion Limits, Explosion Groups, Ignition
Temperatures, Temperature Classes, Flash
Points, and Hazard Classes. All hydrocarbon
vapors, and also many other substances, form
explosive gas mixtures with oxygen within
certain concentration limits, and these mixtures
can be made to ignite if a certain, usually quite
small amount of energy (electrical sparks, hot
surfaces, etc.) is supplied. The lower and upper
limiting concentrations of combustible gas at
which an explosion can no longer be set off are
called the lower and upper explosion limits.
In [359, p. 65] the opposite and therefore
incorrect definition of the explosion limits is
given.
Figure 12 shows the explosion limits of
propane in air as a function of the pressure
of the gas mixture before ignition and the
ignition energy. Whereas the upper explosion
Figure 12. Explosion limits of propane in air as a function
of the pressure p prior to ignition and the ignition energy E
in a 7-L vessel
Exl lower explosion limit; Exu upper explosion limit
Reproduced from [358] with permission of the publisher
Oxidation 79
limit is extended significantly by increasing
either the pressure or the ignition energy, the
lower explosion limit is lowered only to a small
extent.
Combustible dusts behave in a manner simi-
lar to vapors [360].
In enclosed spaces (tanks, silos) the O2
concentration can be lowered by dilution
with inert gases (e.g., N2, CO2) to such an
extent that an explosion can no longer be set
off (see Table 14).
Above a certain temperature, the mixture
ignites without an external ignition source due
to autoxidation. This ignition temperature
decreases with increasing chain length (see
Table 15). It also decreases, in particular in the
case of hydrocarbons, the longer the gas mix-
ture has been kept at an elevated temperature
below the ignition temperature (see Section 4.5).
In pure oxygen the ignition temperatures can be
up to 300 C lower than in air. Like the explosion
limits, the ignition temperatures are not sub-
stance-dependent constants but depend to a great
extent on the measuring conditions. Table 15
lists explosion limits and ignition temperatures
for some compounds in air at atmospheric pres-
sure and 20 C.
For safe handling of hydrocarbons being
processed or stored in a plant the surfaces of
hot apparatus, tubing, machines, etc. must be so
well insulated that no danger of ignition can
arise. For this reason combustible substances
are classified according to ignition temperature
into temperature classes T1 to T6 (see
Table 16).
Also, areas where there is a danger of explo-
sion are classified into areas according to the
probability of the occurrence of explosive gas
mixtures [359]:
Zone 0 Areas in which an explosive atmosphere is always
present or present for an extended period of time.
Zone 1 Areas in which an explosive atmosphere is
occasionally present.
Zone 2 Areas in which an explosive atmosphere is rarely
present or present for only a short time.
Whereas hydrogen is diluted very quickly in
air because of its low density and high rate of
diffusion, hydrocarbons from propane onwards
sink to the ground because of their relatively
80 Oxidation

Table 14. Limiting values for the inerting of flammable gases and vapors with N2 or CO2 at 20 C and 1 bar [359]

Compound Minimum volume ratio Maximum O2 concentration in the FAinert gas

mixture for inerting with N2 or CO2

of inert gas to fuel (F) for of inert gas to air (A) for N2 CO2
inerting towards addition of air inerting towards addition of fuel

N2 CO2 N2 CO2 O2 (max), vol% O2 (max), vol%

Hydrogen 17 10 3.00 1.56 5.0 5.1

Carbon monoxide 4 2.2 2.13 1.13 5.4 5.4
Methane 6 3.3 0.61 0.34 12.1 14.6
Ethane 13 7.5 0.82 0.49 11.0 13.3
Ethylene 16 9 1.00 0.67 10.0 11.7
   
Ethylene oxide 17.2 15.5
Propane 15 8 0.75 0.43 11.8 14.2
Propene 14.5 8 0.75 0.43 11.5 14.1
Cyclopropane 15.5 8 0.75 0.45 11.7 13.9
Butane 17 9.5 0.70 0.39 12.1 14.5
Butadiene 19.5 13 0.89 0.51 10.4 13.0
Hexane 25 14 0.72 0.41 12.1 14.5
Benzene 21 13 0.79 0.45 11.2 13.9

Values do not exist due to ready decomposition of ethylene oxide.

high density and low rate of diffusion. It has
been shown experimentally that 10 m3 of liquid
propane evaporated within 10 min and distrib-
uted itself in a layer of 0.7 m thickness over an
area of 700 m diameter. In addition the lower
explosion limit of hydrogen is 4 vol%, while
that of hydrocarbons lies between 1 and 2 vol%.
Hydrocarbons are at least as dangerous as
hydrogen.
Explosions cannot occur in spaces occu-
pied by packing material. Explosions which
have already started are quenched in vessels or
pipes filled with Raschig rings, tube bundles,
or similar packing materials (explosion barri-
ers). The critical diameter of the capillary
tubes at which no flame can be propagated
is defined as the quenching distance. The
quenching distance depends above all on the
combustible gas, but also on the material,
temperature, and mass of the explosion bar-
rier. Capillaries and bead fillings are more
effective flame barriers than parallel plates
(see Table 17).
Closely associated with the quenching dis-
tance is the maximum experimental safe gap
(MESG), which principally applies to electrical
equipment in surroundings where there is a
danger of explosions. The safe gap is defined
as that through which an ignition occurring
inside the equipment is just unable to penetrate
to the outside.
Substances are divided into three explosion
groups corresponding to their hazard and
assigned particular MESG values (see
Table 18). The MESG is smaller than the
quenching distance because, unlike the explo-
sion barrier, the gap has a depth of only 25 mm.
The vapor pressure of liquids increases
with temperature. The temperature at which
the vapor pressure of organic liquids
exceeds the lower explosion limit so that
the vapor/air mixture above the liquid can
be ignited, is defined as the flash point.
Because dangers can arise, particularly from
low-boiling substances, they have been
divided into hazard classes according to flash
point (Table 19). Because of the complexity
and great number of regulations, the hazard
classes according to the UN Recommendation
which have arisen from the IATA and
RID regulations are becoming increasingly
important.
Self-Ignition of Solids, Fires from Liquids.
Similar to gases, heat removal from solids is
poor. In particular, with solids having large
surface areas (coal dust, flour, hay, straw, paper
waste, wood shavings etc.) oxidation can result
 Oxidation 81

Table 15. Explosion limits and ignition temperatures of some compounds (reproduced from [362] by kind permission of Deutscher
Eichverlag)

Compound Explosion limits in air (20 C, 103.3 kPa) Self-ignition

temperature,  C
Lower, vol% Upper, vol% Lower, g/m3 Upper, g/m3

H2 4.0 75.6 3.3 64 560

CO 12.5 74 145 870 605
NH3 15 28 105 200 630
H2N-NH2 4.7 100 60 1265 (270)
CH4 5.0 15 33 100 595
C2H6 3.0 12.5 37 155 515
C2H4 2.7 28.5 31 330 425
C2H2 1.5 100 16 1080 305
C3H8 2.1 9.5 39 180 470
C3H6 2.0 11.7 35 210 455
n-C4H10 1.52.0 8.5 3749 210 365
C(CH3)4 1.3 7.5 40 230 (450)
n-C5H12 1.4 7.8 41 240 285
n-C10H22 0.7 5.4 41 320 205
C6H5-C6H5 0.7 3.4 45 220 570
C6H6 1.2 8.0 39 270 555
C6H5CH3 1.2 7.0 46 270 535
CH3C6H4CH3 1.1 7.0 48 310 525
CH3OH 5.5 3144 73 410590 455
(CH3)2CHOH 2.0 12 50 300 425
n-C3H7OH 2.1 13.5 50 340 405
(C2H5)2CHOH 1.2 8 53 300 360
n-C5H11OH 1.3 10.5 47 380 300
CH2O 7.0 73 87 910 (420)
CH3CHO 4.0 57 73 1040 140
CH2CHCHO 2.8 31 65 380
(CH3)2CHCHO 1.6 11 47 320 165
CH3Cl 7.1 18.5 150 400 625
CH3Br 8.6 20 335 790 535
CH2CHCH2Cl 3.2 11.2 105 360 390
CH2CHCH2Br 4.3 7.3 215 370 (295)
n-C5H11Cl 1.41.6 8.6 6070 380 255

in a significant temperature rise, whereby igni-
tion occurs (see Table 20). The ignited solid
only glows (reaction between O2 and solids).
Flames are formed by gas-phase oxidation of
the gases and vapors formed by cracking and
evaporation of the volatile compounds.
In the case of liquids it is also only the vapors
formed which burn. For this the liquids must be
heated to temperatures above the combustion
point. At the flash point only the gas mixture
above the liquid burns and the flame is then
extinguished; however, when the combustion

Table 16. Criteria for temperature classes [363] Table 17. Quenching distances of various flame barriers [358, p.
58]
Ignition temperature Temperature Maximum Former
of flammable class surface ignition Fuel Parallel plate Flame barrier
material,  C temperature,  C class wmax, mm
Capillary, Bead filling
>450 T1 450 G1
dmax, mm d max, mm
>300 T2 300 G2
>200 T3 200 G3 H2 0.3 1 2
>135 T4 135 G4 CH4 1.3 4 7
>100 T5 100 G5 C3H8 0.9 3 6
>85 T6 85

Bead diameter.
82 Oxidation

Table 18. Classification of explosion groups according to extinguishers are due to the same cause: These
maximum experimental safe gap (MESG) and minimum ignition hydrocarbons form too many radicals. There-
current ratio (MIC) [363]
fore, at low temperatures, the proportion of
Classification Condition Example chain termination reactions is too high.
II A 0.9 mm < MESG propane
Particularly critical situations can arise from
0.8 < MIC fires involving containers of low-boiling
II B 0.5 mm  MESG  0.9 mm ethylene liquids, if the container is heated. This can
0.45  MIC  0.8 lead to sudden evaporation of a large quantity
II C MESG  0.5 mm H2, C2H2,
MIC  0.45
point is reached so much liquid evaporates that
the gas mixture continues to burn. The com-
bustion point is usually a few degrees above the
flash point. Halogenated hydrocarbons, for
which the combustion point can be up to
100 C above the flash point, are an exception.
This striking behavior and the suitability of
halogenated hydrocarbons to be used as fire
CS2
of liquid and a subsequent explosion. This
process is known as BLEVE (burning liquid
evaporating vapor explosion). A decision on the
particular procedure can only be taken on the
spot. But in all cases where the liquid can
neither be pumped off nor quenched by dilution
with water, a BLEVE should be hindered by
intensive cooling of the container. The liquid
which could otherwise not be disposed of
should, however, be allowed to burn away, since
clouds of gas forming after complete quenching
by subsequently evaporating liquid could ignite
at places which were still hot.

Table 19. Flash point limits of various transportation and storage regulations [359]

Regulation Applies to Class Flash point limit,  C Notes

VbF storage AI < 21 incompletely miscible

A II 2155 with water
A III 55100
B < 21 completely miscible with water
IATA (RAR) air transport < 37.8 measured in closed cup
37.893.3
IMDG Code sea transport 3.1 < 18
3.2 18 to 23
3.3 23 to 69
RID, EVO, ADR, transport by rail, road, Materials of UN 21
ADNR, etc. and canal class 3 55
100

Table 20. Smoldering temperature of deposited dust (5 mm thick layer) [359]

Material Particle size Bulk density, kg/L Smoldering temperature,  C

Majority, mm Max., mm

Coal dust 510 50 0.41 225

Charcoal 12 20 0.36 340
Flour 3050 200 0.31 325
Phosphorus, red 3050 150 0.99 305
Polystyrene 4060 150 0.23 melts
Poly(vinyl chloride) 45 10 0.55 chars
Zinc 1015 90 4.9 430

Temperature of the surface on which the dust lies. It decreases with increasing thickness of the dust layer. The maximum permissible surface
temperature must be ca. 100 C lower than the smoldering temperature.
 Oxidation 83

6. Heterolytic Oxidation 6.1. Heterolytic Oxidation in the Liquid

Both liquid- and gas-phase heterolytic oxida-
tions have long been known and are used both
in the laboratory and in industry.
For example, the oxidation of naphthalene to
phthalic anhydride was carried out by BASF
with sulfuric acid and K2Cr2O7 since 1872, and
since 1896 by the Sapper process with sulfuric
acid and mercury as the catalyst. From 1916
this process was replaced by air oxidation on
V2O5 catalysts.
Oxidations with HNO3, SO3/H2SO4, perox-
omonosulfuric acid, MnO2, KIO4, etc., still
play a role in industry today [344347],
although, with the exception of HNO3, this is
limited to products with a very small volume.
A more systematic investigation and deter-
mination of these reactions began in the 1960s,
principally as a result of two developments:
Phase
In heterolytic oxidations in the liquid phase
other oxygen donors are frequently used instead
of molecular oxygen. Some of these are listed in
Table 21, together with the byproducts formed
from them.
Example 1: Uncatalyzed Epoxidation of Ole-
fins by Peroxy Acids (Prilezhaev Reaction).
Due to the polarization of the neighboring CO
bond, the hydroperoxy group of peroxyacids can
epoxidize CC double bonds (Eq. 218). Alkyl
hydroperoxides are less electrophilic and require
a catalyst (see Example 3 b).

1. The oxidation of ethylene to acetaldehyde

with PdCl2, developed by Wacker [386] and
Hoechst.
2. Molybdenum-catalyzed epoxidation of pro- 218

pene with tert-butyl hydroperoxide, intro-

duced by Halcon and Arco, and their joint
venture, Oxirane.
Example 2: Stoichiometric Oxidation with
Oxidation in the presence of heterogeneous Metal Oxides. Oxides such as SeO2, CrO2Cl2,
catalysts is still based almost entirely on empir- MnO 4 , OsO4, etc. have long been used as
ical principles (both in the liquid and gas oxidizing agents for organic substrates. The
phases). It profits considerably from develop- following mechanism is assumed for the oxi-
ments in homogeneous liquid-phase oxidation dation of propene by SeO2 (Eqs. 219221):
since the course of reactions on solid surfaces
cannot yet be directly investigated. It may be
assumed, however, that many reactions on het- 219
erogeneous catalysts proceed in the same or at
least similar ways with corresponding catalysts
in the homogeneous liquid phase.
Depending on the substrate, oxidizing agent,
Table 21. Oxygen donors [342, p. 5]
type of catalyst, participating complexing
agents, reaction medium, temperature, and Donor Active oxygen, % Byproduct
the other reaction conditions, heterolytic oxi- H2O2 47.0 H2O
dations proceed by various mechanisms. From tert-BuO2H 17.8 tert-BuOH
the combination of different substrates with the NaClO 21.6 NaCl
NaClO2 35.6 NaCl
different catalysts, oxygen donors, and reaction
NaBrO 13.4 NaBr
media, there is an extraordinarily large number C5H11NO2 a 13.7 C5H11NO
of possible reactions. For this reason only a KHSO5 10.5 KHSO4
short overview can be given here, based on NaIO4 29.9b NaI
[342]. Further reviews can be found in [339, a
N-Methylmorpholine-N-oxide.
343, 345348]. b
Assuming all four O atoms are utilized.
84 Oxidation
220
221
In the presence of tert-butyl hydroperoxide
(TBHP) and small quantities of SeO2 the
reaction proceeds catalytically (see also Exam-
ple 3).
The active oxidizing agent is an oxometal
species in the case of metal ions that are strong
oxidizing agents in their highest oxidation state
(e.g., Se4, Cr6, V5, Ce4, Ru8), while
weakly oxidizing metal ions (e.g., Mo6,
Zr4, Ti4) react as peroxometal species.
V5 can react by both mechanisms.
It should be noticed that metal ions reacting
via oxometal mechanism are reduced by the
substrate and reoxidized by the active oxidizing
agent during one cycle, whereas the metal ions
in the peroxometal complexes do not change
their oxidation state but add the active oxygen
donor to their complex sphere. In this way,
primary alcohols can be oxidized (with Zr
complexes) to aldehydes, secondary alcohols
to ketones, and olefins to epoxides or glycols
(see Example 3).
Example 3: Transition Metal Catalyzed Oxi-
dation of Olefins.
a. Some transition metal oxides form
inorganic peroxo acids with H2O2, analo-
gous to the reactions shown in the above
scheme. These inorganic peroxoacids,
known as Milas reagents, oxidize olefins
to epoxides. The epoxide formed is hydro-
lyzed in water (H2O2 is usually added as a
30% aqueous solution) (Eqs. 222 and 223):
222
223
The best known Milas reagent is OsO4.
However, it does not oxidize the olefins via
the epoxides but via the osmates (Eq. 224):
224
b. HalconOxirane Process (! Milas
reagentsPropylene Oxide). If olefins are
treated with organic hydroperoxides in
nonaqueous solvents in the presence of
Milas reagents as catalysts, epoxides are
formed in high yields (Eq. 225):
225
Homogeneous catalysis: Mo6, W6, V5,
Ti4 (Arco)
Heterogeneous catalysis: Ti4/SiO2 (Shell)

The following mechanism is assumed
(Eqs. 226228):
226
227
228
Whereas the alcohols formed from the
hydroperoxides have a strongly inhibiting
effect on the activity of vanadium, they inhibit
the action of molybdenum only in high con-
centrations (e.g., when used as the solvent).
For homogeneous catalysis the metals are
added in the form of complexes that are readily
soluble in organic materials in concentrations
of 1500 ppm. The reaction temperatures are
between 80 and 120 C. The problem of catalyst
recycling was solved by Shell by rendering the
catalyst heterogeneous.
The major problem of this process is that
ca. 2 t tert-butanol (TBA) are formed per tonne
of propylene oxide. Up to the 1980s Arco
recycled the TBA by dehydration to isobutene
and subsequent hydrogenation to isobutane.
Today, isobutene is converted to methyl-tert-
butyl ether (MTBE) for which a large market as
gasoline additive has developed (! Methyl-
Tert-Butyl Ether).
Example 4: Palladium-Catalyzed Oxidation of
Olefins. Wacker/Hoechst process (! Acetal-
dehyde). SMIDT et al. [386] attempted to oxidize
ethylene to ethylene oxide in the gas phase over
Pd/C. In contrast to their expectations acetal-
dehyde was formed. In this way a reaction
was rediscovered, which was known since
1894 and used analytically for a long time
Oxidation 85
for determination of palladium. Since the cata-
lysts rapidly became inactive in the gas phase
because of formation of palladium aggregates,
it was decided to carry out the reaction in the
liquid phase (water). By combination with a
redox system (CuCl/CuCl2), a catalytic process
for acetaldehyde synthesis was developed. Con-
siderable corrosion problems arose due to the
use of chloride ions in an acidic medium (pH
0.83) at 100130 C.
The reaction scheme is as follows
(Eqs. 229231):
C2H4 PdCl2 H2O ! CH3CHO Pd0 2 HCl (229)
Pd0 2 CuCl2 ! PdCl2 Cu2Cl2 (230)
Cu2Cl2 2 HCl 1/2 O2 ! 2 CuCl2 H2O (231)
From experiments with C2D4 (very small
isotope effect), D2O (kH/kD 4.5, no deuterium
in the acetaldehyde), with varying H and Cl
concentrations (both ions inhibit the reaction),
with various nucleophiles (acetic acid or etha-
nol instead of water as the solvent), and from
the finding that trans OX substitution occurs in
ethylene (OX thus comes directly from the
solvent and not from the ligand sphere of the
complex) it was concluded that the mechanism
is as follows:
1. Substitution of a chloride ligand by ethyl-
ene, with formation of a p-complex, which
is in equilibrium with the corresponding
solvent complex by rapid ligand exchange
(Eqs. 232 and 233):
232
233
2. Formation of the p-complex lowers the
electron density on the ethylene ligand,
86 Oxidation

rendering it susceptible to nucleophilic CuCl2) is not required, unlike with Pd2.

attack. The p-complex is in equilibrium With water as solvent acrylic acid is formed
with the s-complex. The latter loses a Cl (Reaction 241).
ion in a slow reaction and decomposes after Vinyl mechanism
hydride migration from C1 to C2 via the Pd,
and two-electron transfer from C1 to Pd, to
give the final products. The Pd0 is then
reoxidized (Eqs. 234236). Alternatives to
this mechanism are discussed in [387, 388].
238

Allyl mechanism

234

239

240

236

241

Palladium(0) on activated carbon also cata-

lyzes the oxidation of the methyl group of
237
toluene under mild conditions (Reactions
242, 243):

The two major drawbacks of the Wacker

processchlorinated byproducts and severe
corrosioncan be overcome by using hetero-
polyacids (HPA) as the reoxidizing agents [389]
instead of the CuCl/CuCl2 system.
Higher olefins are oxidized to ketones.
Yields of over 95% are only obtained with
HPA as the reoxidizing agent for palladium.
242; 243
As shown above, vinyl acetate is formed in
acetic acid (and in the presence of Na acetate). Further examples of the heterolytic oxida-
Isopropenyl acetate is formed from propene tion of olefins are:
since Pd2 is electrophilic and therefore reacts
with the double bond in the manner shown in
Reactions (232237) and (238). In contrast, Pd0
244
abstracts the allylic H atom and gives a p-allyl
complex. Thus propene is oxidized to allyl
compounds on Pd0 (on activated carbon or
another carrier), whereby a cocatalyst (e.g., TBHP tert-butyl hydroperoxide
 Oxidation 87

Oxidative CC cleavage:
252

245

cat. : Pb2.63Ru1.37O6.5 or Bi2.39Ru1.61O7y

Heteropolyacids (HPA) are gaining increas-
246 ing importance because of their unique combi-
nation of properties:

Alcohols can be oxidized in a similar manner, 1. Strong Brnsted acids

as the following examples (Eqs. 247252) show: 2. Multi-electron oxidizing agents
3. Solubility in water and oxygenated organic
solvents (soluble oxides)
247 4. HPA anions are stable to oxidation and
function as multi-electron ligands that can
stabilize reactive, higher-valent oxometal
species

248 For example, the oxidative cleavage of

diols was achieved with H2O2 in tert-butanol
in the presence of the cetylpyridinium salt of
the heteropolyacid H3PW12O40 as catalyst
(Eq. 253).
249

253

acac acetylacetonate
NAFK Nafion R 511 perfluorinated ion-
cat.: (cetylpyridinium)3 PW12O40
exchange resin
To avoid the problems associated with cat-
alyst recycling, Anic/Enichem has incorpo-
rated Ti4 into a zeolite lattice and obtained
titanium-silicalite (TS-1). TS-1 has the same
elemental composition as the Shell TiSiO2
catalyst, but a considerably wider range of
applications. It is assumed that active, isolated
titanyl species are responsible for the catalytic
activity (Eq. 254):

250
254

TS-1

With TS-1 as catalyst, the following

reactions have, among others, been carried
251 out with 30% H2O2 (Eqs. 254259):
88 Oxidation
255
256
257
258
259
For hydrogen peroxide and the inorganic
water-soluble oxygen donors, there is often a
miscibility problem with the organic com-
pound. This problem can be solved in many
cases by using a two-phase aqueousorganic
solvent system in conjunction with a phase
transfer catalyst.
Process Technology of Heterolytic Liquid-
Phase Oxidation. Because of the great number
of possible reactions, general rules cannot be
drawn up. In the cases where only liquids are
reacted with each other, stirred tanks are suit-
able reactors for small batches. For continuous
production, reactors with turbulent plug flow
are generally the most suitable.
If a catalyst precursor is used a formation
phase is necessary for initiation. After this
formation phase or when using preformed cat-
alysts, the reaction proceeds immediately with
its maximum possible rate.
The reactions are generally very selective. If
the catalyst permits, they can be run until
complete conversion of the starting material
is reached.
6.2. Heterogeneously Catalyzed Gas-
Phase Oxidation
The area of heterogeneously catalyzed gas
phase oxidations is still largely empirical,
with regard to the composition and preparation
of the catalysts, and the control and influencing
of the processes occurring on the catalyst sur-
face during the reaction.
Considerable progress has been made in the
investigation and characterization of surfaces.
Surface analysis methods, such as Auger elec-
tron spectroscopy (AES), secondary ion mass
spectroscopy (SIMS), and low energy electron
diffraction (LEED), have been applied to cata-
lysts. By using such techniques, considerable
advances in the characterization of and the
differentiation between good and poor catalysts
have been made. This is important both for
reproducible catalyst production and for the
explanation of poisoning and aging processes.
Most of these spectroscopic methods can,
however, only be performed under high vac-
uum. Thus for all industrially interesting cata-
lysts one is still far away from investigating the
processes occurring on the catalyst surface
during the reaction. Nevertheless, a large num-
ber of observations and indirect methods of
investigation (e.g., sorption measurements,
use of isotopically labeled compounds, alter-
nating oxidation and reduction) in combination
with the above-mentioned methods of physical
analysis allows a rough picture to be built up of
what happens on the surface of the catalyst.
As long as the processes on the surface of the
catalyst are practically inaccessible to direct
investigation, all proposed mechanisms can
only be speculative.
For a summary of the literature up to 1972,
see [390]; up to 1979, [343, 391, 392]; (see also
! Heterogeneous Catalysis and Solid
Catalysts).
6.2.1. Oxidation Catalysts
Table 22 lists the most important oxidation
catalysts and the reactions catalyzed by them
[393]. The catalysts are divided into three
groups:
1. The noble metals Pt and Ag are the longest
known catalysts. Their large-scale use as

Table 22. Types of catalyst for heterogeneous gas-phase oxidation
Catalyst
Noble metals(Pt, Pd, Ag)
Pt( Rh,Au) gauze
Pt( Rh)/TiO2/carrier
Pt( Bi,Au)/carrier
Ag(Cs)/carrier
Ag (pure)
Cu - Fe catalysts
CuCl2 (Alkali chloride)/carrier
Cu - Mn-Cr oxide
Mg - Cr ferrite
CuO - ZnO
Cu2O/carrier
Catalysts based on V2O5 MoO3
V2O5( K2S2O7)/carrier
V2O5( P2O5)/carrier
V2O5( P2O5 TiO2)/carrier
V2O5( MoO3 additives)/carrier
V2O5( SnO2 additives)/carrier
MoO3 - Bi2O3 ( various additives)
MoO3 - V2O5 ( various additives)
MoO3 - Fe2O3
Of minor industrial importance.
oxidation catalysts was limited for a long
time to the combustion of ammonia (Pt/Rh,
Ostwald process) and the synthesis of form-
aldehyde (Ag; BASF process). After World
War II, the direct oxidation of ethylene to
ethylene oxide on Ag, the oxydehydrogena-
tion of ethanol on Ag to give acetaldehyde,
and the Andrussow process for the synthesis
of HCN on Pt catalysts became important. In
the late 1960s, the combustion of off-gases
on Pt/Rh and the acetoxylation of olefins on
Pd were introduced.
2. In the 1940s copper-based catalysts became
important for the oxidation of propene to
acrolein. In the 1950s various mixed-oxide
catalysts based on Fe/Cr oxide were devel-
oped for the oxidative dehydrogenation of
butenes to give butadiene. In the 1960s the
CuCl2/carrier catalysts, known since 1868,
achieved renewed industrial importance for
Oxidation 89
Reactions and examples
NH3 oxidation to NO/NO2
Andrussow process: CH4 NH3 32 O2 ! HCN 3 H2O
off-gas combustion/purification
oxyacetylation, e.g.:
ethylene ! vinyl acetate
propene ! allyl acetate
ethylene oxide direct synthesis
oxidative alcohol dehydrogenation:
methanol ! formaldehyde
ethanol ! acetaldehyde
Deacon process: 2 HCl 1/2 O2 ! Cl2 H2O
oxychlorination: C2H4 2 HCl 1/2 O2 ! ClCH2CH2Cl H2O
off-gas combustion/purification
oxidative dehydrogenation:
butene ! butadiene
oxidative decarbonylation:
a-branched aldehydes ! ketones
(e.g., isobutyraldehyde ! acetone)
propene ! acrolein
contact process: SO2 1/2 O2 ! SO3
o-xylene ! phthalic anhydride (! phthalic acid)
butane/butene ! maleic anhydride (! maleic acid)
benzene ! maleic anhydride (! maleic acid)
ammonoxidation: alkyl aromatics ! aromatic nitriles
oxidative dehydrogenation: butene ! butadiene
ammonoxidation: propene ! acrylonitrile
propene ! acrolein
acrolein ! acrylic acid
Formox process: methanol ! formaldehyde
the oxyhydrochlorination of ethylene/HCl
mixtures to give dichloroethane (precursor
for vinyl chloride).
3. After Pt and Ag, the vanadium oxide catalysts
are the longest used industrial catalysts for
oxidation processes; V2O5 was first used in
the oxidation of SO2 to SO3, and later in the
oxidation of naphthalene to phthalic anhy-
dride, and benzene to maleic anhydride.
The discovery of the Bi2O3MoO3 catalysts
by Sohio had a similarly revolutionary effect on
the development of mixed-oxide catalysts for
gas-phase oxidation, as the discovery of the
palladium catalysts for ethylene oxidation on
the development of the heterolytic liquid-phase
oxidation.
Properties and Mechanism of Action of Het-
erogeneous Oxidation Catalysts. Most heter-
ogeneously catalyzed oxidations probably
90 Oxidation
proceed by heterolytic mechanisms. As shown
in Section 5.1 these mechanisms differ, depend-
ing on the catalyst used.
Noble Metal Catalysts. A characteristic of
noble metal catalysts is that reducing condi-
tions must generally be used for selective oxi-
dations; i.e., the hydrocarbon must be in excess
and oxygen in deficiency. With excess oxygen
the pure platinum metals in particular catalyze
only complete combustion, which begins at
200250 C on active catalysts.
The most active catalysts for total combus-
tion (off-gas purification) are based on Pt/Rh;
they catalyze the complete oxidation of hydro-
carbon compounds to CO2 and H2O at a stoi-
chiometric O2 availability.
For the acetoxylation of olefins over a Pd0
catalyst, a mechanism was proposed in
Reaction (97). It is assumed that this mecha-
nism is also valid for the corresponding
reactions in the gas phase. The palladium
must be modified with Bi and Au, and sodium
acetate must be continuously added to the
starting material as a moderator, so that the
reaction proceeds with the desired selectivity.
Oxidation of Ethylene to Ethylene Oxide on
Silver Catalysts (see also ! Ethylene Oxide,
Chap. 4.1., ! Ethylene Oxide, Chap. 4.2.). Up
to now ethylene is the only olefin which can be
selectively oxidized to the epoxide in the gas
phase, and silver is the only catalyst on which
the reaction proceeds with high selectivity.
Ethylene can be oxidized to ethylene oxide
with an excess of oxygen on silver catalysts.
Because the selectivity decreases with increas-
ing conversion, small ethylene conversions are
used industrially. Because of the need to recycle
the ethylene, pure oxygen is generally used.
The oxygen concentration is determined by the
lower explosion limit with respect to oxygen.
Figure 13 shows the development of the
ethylene oxide selectivity. The first catalysts
gave selectivities of ca. 50%, which were grad-
ually increased to 6570% by addition of a few
ppm of a chlorohydrocarbon to the make-up gas
to lower the activity, and by improvements in
catalyst preparation. In the 1970s Shell raised
the ethylene oxide selectivity from below 70%
to ca. 75% by doping the catalyst with 100500
mg/kg cesium [394]. Later, ethylene oxide
Figure 13. Development of the selectivity in the oxidation
of ethylene oxide since 1950
The selectivities attained in industrial plants lie in the
shaded region
selectivities of over 86% were achieved by
additional doping of the Ag/Cs/carrier catalysts
with rhenium and sulfate ions.
Although the oxidation of ethylene on silver
has been known for 70 years and has been
investigated intensively, there is no clarity
over the mechanism either with regard to the
activation of the oxygen or the ethylene. Two
mechanisms are principally discussed for the
oxygen activation (see also ! Ethylene Oxide,
Section 4.2):
According to mechanism 1 oxygen mole-
cules adsorbed end-on on the silver surface at
certain interstitial sites are believed to oxidize
the ethylene diffusing to the site from the gas
phase to give ethylene oxide selectively. The
oxygen atom bound to the silver remains on the
surface.
Ethylene oxide and carbon dioxide forma-
tion proceed in parallel in the industrially used
temperature range and also over wide ranges of
ethylene and oxygen concentration, and appear
to be coupled with one another. Moreover,
several studies showed that chemisorbed oxy-
gen atoms only totally oxidize ethylene. It was
therefore assumed that the chemisorbed oxygen
atom remaining after transfer of one oxygen
atom to ethylene, is subsequently removed by
the other ethylene molecule with total oxida-
tion. Subsequently, the cycle can start again.
 Oxidation 91

In this mechanism one ethylene molecule Copper Catalysts. Whereas the oxidation of
can remove a maximum of six oxygen atoms HCl and the oxychlorination of ethane require
from the interstitial sites at which ethylene temperatures over 400 C, the oxychlorination
oxide has previously been formed. Therefore, of ethylene proceeds at ca. 230 C. An electro-
the ethylene oxide selectivity should not exceed philic attack of the ethylene double bond on a
the limit of 100
6/7 85.7%. copper hydroxy chloro complex with formation
In mechanism 2 oxygen atoms adsorbed on of an ethylene-chloronium complex and reduc-
the silver surface bring about both selective and tion of Cu2 to Cu with subsequent trans
total oxidation of ethylene. It is assumed that addition of a second chloride ion to this chloro-
promoter and moderator ions in the neighbor- nium complex is assumed. This is followed by
hood of the active oxygen atom (e.g., Cs, Cl, reoxidation of the copper (Reaction 260 and
and also O2) influence its electronegativity 261).
and thus determine whether it acts as a selective
or total oxidant (lowering the electronegativity
favors selective oxidation).
Given the available experimental evidence,
arguments can be made in support of either
mechanism [395].
If the ethylene oxide selectivity of more than
86% reported in [396] is confirmed, the second
part of mechanism 1 would be refuted. 260
There have been practically no investiga-
tions of the nature of the ethylene activation.
It only seems certain that it does not react
directly from the gas phaseas postulated in
mechanism 1but is first adsorbed on the
catalyst surface.
The reaction is zero, first, or fractional order,
depending on the ethylene/oxygen ratio in the
gas phase. Under industrial conditions (concen-
tration < 9% O2, 3040% ethylene; per pass,
40% of the O2 and only ca. 10% of the ethylene
are converted), the reaction is zero order with
respect to ethylene and first order with respect
to oxygen.
The oxidative dehydrogenation of ethanol to
give acetaldehyde (see ! Acetaldehyde, Chap.
4.1.) on silver or copper catalysts has long been
known and was formerly the method of choice
in the laboratory. Formaldehyde was also pre-
viously produced by this method, but is now
mainly produced in the Formox process by
oxidative dehydrogenation of methanol on
iron molybdate catalysts (! Formaldehyde,
Chap. 4.2.).
In the Huls process (originally developed by
BASF), ethanol is mixed with air and passed
over coarse-grained crystals of pure silver at
500650 C. There is only 5070% conversion
of ethanol, but complete consumption of oxy-
gen. The off-gas contains up to 11% unoxidized
261
hydrogen.
92 Oxidation
Mixed Oxide Catalysts. There are essentially
two groups of mixed oxide catalysts:
1. Molybdenum-based catalysts that contain
bismuth or vanadium and/or tungsten as
the second main component and which are
used, for instance for the oxidation of pro-
pene to acrolein and acrylic acid or to acry-
lonitrile, and for oxidative dehydrogenation
of butene to give butadiene.
2. Catalysts based onvanadium, with, e.g., phos-
phate, sulfate, TiO2, or MoO3 as the second
main component, are principally used for the
oxidation of aromatics and butane/butene to
give acid anhydrides (benzene or butane/
butene to maleic anhydride, naphthalene or
o-xylene to phthalic anhydride).
While V2O5 and MoO3 belong to the oxides
which are themselves catalytically active,
oxides such as Bi2O3, Sb2O3, SnO2, and TiO2
possess virtually no catalytic activity of their
own. However, in combination with V2O5 and
MoO3 the catalytic activity and selectivity of
the latter are greatly increased.
Hydrocarbon Activation on Mixed-Oxide Cat-
alysts. Experiments with 14C-labeled propene
indicate that it is chemisorbed as a p-allyl
complex on the Mo/Bi catalysts with hydrogen
abstraction (Eq. 262). It is assumed that this
p-complex reacts further with the metal oxo
complex in a manner analogous to the reaction
with SeO2 with oxygen transfer and metal
reduction (see Reactions 219 to 221).
262
On a catalyst with the composition Mo10Bi-
FeCo4W2K0.06Si1.35 a selectivity for acrolein
of 90% was achieved at a propene conversion
of 98%. Only ca. 6% of the acrolein was
further oxidized to acrylic acid on this catalyst
[total selectivity (acrolein acrylic acid):
96%].
The selective further oxidation of acrolein
can be achieved on MoV catalysts (see !
Acrylic Acid and Derivatives). Obviously the
addition of vanadium leads to stronger adsorp-
tion and activation of the acrolein than on the
MoBi catalyst.
The oxidative dehydrogenation of butene to
give butadiene proceeds similarly. On MoBi
catalysts the first step of the oxidation proceeds
as with propene. Like acrolein, the butadiene
formed is practically completely desorbed from
the catalyst (selectivity > 90%) and is not
further oxidized. Two mechanisms can be dis-
cussed (Eqs. 263 and 264):
263
264
On vanadium-containing catalysts (see
Table 22), however, the butadiene is rapidly
oxidized further to maleic anhydride.
At the high temperatures necessary for the
oxidation of butane (400450 C), vanadyl
phosphate catalysts, (VO)2P2O7, have proven
particularly selective. The P : V ratio in the bulk
catalyst particle is 1 : 1, corresponding to
the stoichiometry, but on the catalyst surface
it is 2 : 1. The phosphate apparently has two
functions: it stabilizes the vanadium in high
valence states by complexation and it inhibits
homogeneous gas-phase oxidation of butane
and its intermediates.
Methyl aromatics (toluene, xylene) and
naphthalene are oxidized with the greatest
selectivity on vanadium catalysts via the

aldehydes to the acids or acid anhydrides. High
yields are obtained only with those hydrocar-
bons that form moderately polar, readily
desorbable, volatile products, such as o-xylene,
from which phthalic anhydride is formed. p-
Xylene initially affords terephthalic acid, which
is too polar and is therefore hardly desorbed.
The anhydride of terephthalic acid is oligo-
meric and therefore insufficiently volatile.
For this reason p-xylene can be oxidized selec-
tively in the gas phase only by ammoxidation to
give terephthalonitrile. Normal air oxidation, in
contrast, results predominantly in total
oxidation.
Mixed oxide catalysts are only catalytically
active and selective in their higher oxidation
states. Unlike the noble metal catalysts they
must be used in an excess of oxygen, i.e., in an
oxidizing atmosphere.
It is generally assumed that the oxygen
originates from the oxide lattice in selective
oxidations on mixed oxide catalysts and that the
metal ions are reduced and oxidized again
alternately (redox mechanism of MARS and
VAN KREVELEN). Up to now there are only vague
ideas about the way in which atmospheric
oxygen is activated and incorporated into the
lattice.
Whereas reoxidation proceeds very rapidly
on vanadium catalysts (the reaction temperature
is mainly determined by the temperature nec-
essary to activate the hydrocarbon), the reox-
idation of the catalyst is the activity-
determining process for molybdenum-based
catalysts, which also determines the reaction
temperature. This is demonstrated, for example,
by the fact that for catalysts based on V2O5 the
active mass can be applied as a thin layer on a
carrier (egg-shell catalyst), while catalysts
based on MoO3 only exhibit sufficient activity
as bulk catalysts.
The importance of the reoxidation rate in
mixed oxide catalysts, is exemplified by the
development of the BiMo catalysts. When
they were introduced by Sohio in the early
1960s, the temperature required for oxidation
of propene was 400450 C, and the selectivity
for acrolein, between 60 and 70%. By the
addition of metal ions such as FeII/III, CuII,
CoII and NiII, which only catalyze one-electron
transfers, the reaction temperature could be
lowered to 300330 C and the selectivity
Oxidation 93
increased to 9095%. It is assumed that the
very high activation energy of the oxygen dis-
sociation necessary for the reoxidation of molyb-
denum is strongly lowered by these additives.
Today the reduction/oxidation-mechanism
developed by MARS and VAN KREVELEN in the
1960sis generally accepted as the only valid
one. However, taking the later developed
oxometalperoxometal scheme (see Section
5.1) into account, with oxidation catalysts con-
taining Mo and even V, a peroxometal mecha-
nism without reduction and reoxidation of the
central metal ion should be considered too.
The oxidation of hydrocarbons on mixed
oxide catalysts generally follows Langmuir
Hinshelwood kinetics, i.e., the reaction rate
depends on both the concentration of the hydro-
carbon and the concentration of oxygen in the
gas phase.
Because of the large number of parallel and
consecutive processes occurring simulta-
neously on the catalyst surface (adsorption,
chemical reactions, and desorption) kinetic
measurements only give apparent values for
heterogeneously catalyzed oxidations. CREMER
was the first to point out the compensation
effect occurring in these types of kinetic mea-
surements [397]. In the Arrhenius equation
(265)
k Ao  eEa =RT 265
the collision factor A decreases with decreasing
activation energy and vice versa.
6.2.2. Process Technology of Heteroge-
neously Catalyzed Oxidations
Here only the oxidation processes on carrier or
mixed oxide full-contact catalysts are
described, whereas processes involving gauzes
or thin layers of noble metals and waste gas
combustion are not considered.
Catalyst Preparation and Characterization
[349] (see also ! Heterogeneous Catalysis
and Solid Catalysts). The surface area of oxi-
dation catalysts should be relatively small
(0.110 m2/g), i.e., the catalyst should have
no pores smaller than 50 nm, since these favor
total combustion due to the poor material
transport.
94 Oxidation
Reactors. Because of the large quantities of
heat liberated in oxidation reactions and the
poor heat transport through the gas, either
multitube reactors (with up to 40 000 tubes
of 1040 mm diameter and 112 m length) or
fluidized-bed reactors are used.
In multitube reactors the heat is removed
either by boiling liquids (water or organic heat
transfer media) or by salt melts (e.g., 53 wt%
KNO3, 40 wt% NaNO2, 7 wt% NaNO3, mp
150 C, usable up to 550 C; reactor material
preferably untempered mild steel). In fluidized-
bed reactors the heat is removed by cooling
tubes containing water (high-pressure steam
production).
Because of the unavoidable back-mixing in
fluidized-bed reactors the selectivity is always
lower than in multitube reactors with their plug
flow. For this reason fluidized-bed reactors are
only used for catalysts with particularly short
lifetimes (< 1 year). In multitube reactors, cat-
alyst exchange always means a shutdown of
several weeks. In particular, the pressure loss
compensation of the freshly filled tubes is still a
tedious manual process. In fluidized-bed
reactors the catalyst can be continuously
exchanged, even during operation. Typical
examples for the use of fluidized beds are in
the older acrylonitrile plants, and the oxidation
of butane to maleic anhydride.
Temperature Profiles. In fluidized-bed
reactors, heat transport by the turbulent mixed
solid catalyst is very good. Therefore, uniform
temperature is established throughout the entire
bed.
In fixed-bed reactors, heat transport by the
gas is poor and characteristic temperature pro-
files develop along the axis of each tube.
Because the temperature differences between
catalyst bed and bath in each spot along the
tubes are proportional to the heat evolved in the
catalyst bed at this spot, these temperature
profiles give a fairly accurate indication of
the overall reaction taking place at each spot
along the catalyst bed. If capillaries (thermo-
wells) are mounted in the axis of some tubes,
these temperature profiles can be measured by
moveable thermocouples. Figure 14 shows
three typical temperature profiles.
With highly active catalysts (Fig. 14 A) the
main reaction occurs in a very limited region
with a sharp temperature peak (hot spot), whose
height is generally proportional to the hydro-
carbon loading (large reserve of catalytically
active centers in the region of the main reaction
zone). Because of the large temperature differ-
ence between the cooling medium and the
catalyst in the region of the temperature maxi-
mum (high temperature in the main reaction
zone and relatively low temperature in the post-
reaction zone), the hydrocarbon is generally not
completely converted, but often only to the
extent of 80 or 90%. The reaction is first order
with respect to the hydrocarbon.
With a moderately active catalyst (Fig. 14 B),
there is only a small temperature rise with
increasing hydrocarbon load, and the tempera-
ture maximum is broadened (most active centers
of the catalyst in the region of the temperature
maximum participate in the reaction). The
reaction is first order with respect to the hydro-
carbon provided that sufficient catalytically
active sites are free in the contact bed region
below the reaction zone, which is indicated by
the decrease of the reaction temperature below
the temperature maximum to the level of the
cooling medium. The hydrocarbon conversion is
more complete the smaller the difference
between the temperature maximum and the cool-
ing medium (mode of operation typical of an
integral reactor).
With a low-activity catalyst (Fig. 14 C) the
reaction is zero order with respect to the hydro-
carbon because all active centers are occupied.
Because of the hydrocarbon excess which is
usually necessary, the reaction is run according
to the permitted oxygen conversion (mode of
operation typical of a differential reactor with
hydrocarbon recirculation).
Regular measurements of the temperature
profile reveal changes in catalyst behavior (e.g.,
due to aging or poisoning). In addition, the true
catalyst performance (kilogram product per
kilogram catalyst per second) in sections of
the bed can be evaluated from the temperature
profile.
Addition of Steam. Water is adsorbed more
strongly on the catalyst surface than most
organic products because of its high polarity.
By addition of steam to the make-up gas, polar
substances can thus be desorbed from the cata-
lyst surface by competing adsorption and their
 Oxidation 95

Figure 14. Temperature profiles of various catalysts

A) Temperature profile of a highly active catalyst (V2O5 type) as a function of hydrocarbon loading (DT1, low loading; DT3,
high loading).
B) Temperature profile of a moderately active catalyst (BiO3MoO3 type) as a function of hydrocarbon loading (DT1, low
loading; DT3, high loading).
C) Temperature profile of a low-activity catalyst (Pd0/Al2O3 moderator). The activity can only be increased by raising the
temperature.

yields increased. This method is used above all
in the oxidation of propene to acrolein and
acrylic acid and in oxidative dehydrogenation.
For acid anhydrides the addition of steam
clearly leads to a lower yield, although the
dehydration equilibrium lies completely on
the side of the anhydride at the reaction
temperatures.
Addition of steam also improves heat
removal. Because the diffusion rate in gases
96 Oxidation
increases with decreasing molecular mass, the
heat conducting capacity of a gas mixture
increases with the number of small molecules.
Like methane and ammonia, water is one of the
smallest stable gas molecules.
Laboratory and Pilot Plant Experiments;
Applicability of the Results. The choice of
reactor is orientated according to the planned
investigations:
For kinetic measurements gradientless
reactors must be used; details of construction
are given in [349, 398, 399].
For the development of catalysts, reactors
similar to those used on industrial scale should
be used.
In tube reactors catalyst testing is straight-
forward. A suitable apparatus is described in
[400]. Smaller reactors (e.g., made of glass with
an inner diameter of 20 mm and a bed height of
100200 mm) gave identical results to pilot
plant reactors with bed heights of 13 m,
provided that the reactor diameter, catalyst
diameter and height, and the residence time
based on the free reactor volume were in agree-
ment with the pilot plant-reactor; that the resi-
dence time was not greater than 5 s (at longer
residence times it is not certain whether the
flow is still turbulent); and that the catalyst was
not too active.
With very active catalysts, whose tempera-
ture profiles are similar to Figure 14 A, scaling
up is often associated with loss in selectivity
due to the higher temperature in the hot spot or
a lower conversion as a result of the lower bath
temperature to compensate for the increasing
heat production with increasing starting mate-
rial load.
For catalysts with temperature profiles cor-
responding to those in Figures 14 B and 14 C,
laboratory and pilot plant results are largely
consistent, i.e., they are also valid for the
industrial multitube reactor, as the pilot plant
reactor behaves like a single tube from the
multitube reactor.
Fluidized beds behave similarly to liquid
bubble columns; i.e., results that are valid for
a large industrial scale are only obtained in beds
with a diameter exceeding 300 mm. The expen-
diture associated with this requirement in the
pilot plant is considerable. Due to lower back
mixing the selectivity data obtained in the
narrower laboratory fluidized beds are gener-
ally considerably higher than on the industrial
scale.
Influence of Homogeneous Gas-Phase Oxida-
tions. As a rule, homogeneous gas-phase oxi-
dations generally play only a minor role, if any,
in heterogeneously catalyzed gas-phase oxida-
tion, because for safety reasons the temperature
of the gas mixture above the catalyst bed must
be kept well below the (sometimes very low)
ignition temperature. Owing to the short resi-
dence times, a significant oxidation reaction
cannot normally occur in this region. In the
contact bed no significant oxidation reaction
should be able to take place in the homoge-
neous gas phase because of the very small free
gas space. Below the catalyst bed, the gas
mixture is normally cooled so rapidly that
hardly any oxidation in the homogeneous gas
phase can occur.
Safety. Although under normal operating con-
ditions homogeneous gas-phase oxidation does
not play an important role, critical states can
quickly arise during start-up and shutdown and
in the case of faults. Particular attention must be
paid to the make-up gas compressors, which
drive the make-up gas through the reactor. If the
compressor stops, the flow rate of the gas about
to enter the reactor decreases so much that the
gas mixture in the voluminous head of the
reactor, can be ignited by the hot catalyst.
Equally critical states can occur if the catalyst
falls out of one reactor tube during the reaction
or if the flow resistance in the reaction tubes
becomes very different. Particularly in pro-
cesses with high oxygen conversion, ignitable
gas mixtures can enter the space downstream
from the catalyst bed and can ignite either
spontaneously or through the action of catalyst
dust. Most plants should have been equipped in
the meantime with safety devices which render
the plant inert in critical areasindependent of
service personnelor bring it to a safe state in
another way.
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