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p-Xylene Oxidation to Terephthalic Acid: A Literature Review Oriented toward

Process Optimization and Development

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DOI: 10.1021/cr300298j · Source: PubMed

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p‑Xylene Oxidation to Terephthalic Acid: A Literature Review

Oriented toward Process Optimization and Development
Rogério A. F. Tomás,† Joaõ C. M. Bordado,‡ and Joaõ F. P. Gomes*,‡,§
†
ARTLANT, Zona Industrial e Logística de Sines, Zona 2, Lote 2E1, Monte Feio, 7520-064 Sines, Portugal
‡
Instituto de Biotecnologia e Bioengenharia/Instituto Superior Técnico (IBB), Universidade Técnica de Lisboa, Av. Rovisco Pais,
1049-001 Lisboa, Portugal
§
Instituto Superior de Engenharia de Lisboa (ISEL), Á rea Departamental de Engenharia Química, R. Conselheiro Emídio Navarro,
1959-007 Lisboa, Portugal

*
S Supporting Information

5.6.1. Acetic Acid Derivatives AE

5.6.2. Benzaldehyde and Benzoic Acid Deriv-
atives AF
5.6.3. Terephthalic Acid Derivatives AG
5.6.4. Phenol Derivatives AG
5.6.5. Biphenyl and Benzophenone Deriva-
tives AG
5.6.6. Anthraquinone and Fluorenone Deriva-
tives AH
5.6.7. Ester Derivatives AH
5.7. Catalyst Deactivation AH
5.7.1. Catalyst Regeneration AI
6. Operational Optimization Studies AI
CONTENTS 7. Recent Research Trends in Terephthalic Acid
Synthesis AL
1. Introduction A 7.1. Oxidation in Sub- and Supercritical Water AL
2. Polyester History B 7.2. Alternative Catalyst Systems and Cocatalysts AM
2.1. AMOCO Process B 7.2.1. Zirconium AN
3. Chemistry Behind the Process C 7.2.2. Carbon Dioxide Use as Co-oxidant AO
3.1. General Aspects of Hydrocarbon Oxidation C 7.2.3. N-Hydroxyimides AP
3.2. p-Xylene Autoxidation to Terephthalic Acid E 7.2.4. Guanidine AQ
3.3. Catalyst Influence in Autoxidation F 7.3. Oxidation in Ionic Liquids AR
3.3.1. Cobalt and Manganese Acetates As 7.4. Heterogeneous Systems AS
Oxidation Catalysts F 8. Conclusions AT
3.3.2. Cobalt/Manganese/Bromide Catalyst Associated Content AT
Systems I Supporting Information AT
4. Activity P Author Information AT
4.1. Temperature and Pressure Effect on Activity P Corresponding Author AT
4.2. Water Effect on Activity P Notes AT
4.3. Catalyst Concentration Effect on Activity R Biographies AU
4.4. Cobalt/Manganese and Bromine/Metals Ra- Acknowledgments AU
tios Effect on Activity R References AU
4.5. Agitation Effect on Activity S
4.6. Alkali Metal Effects on Activity S
5. Selectivity T
5.1. Carbon Oxides U
1. INTRODUCTION
5.1.1. Carbon Oxides: Solvent Burning U Terephthalic acid is an aromatic carboxylic acid core to
5.1.2. Carbon Oxides: Mechanism of Solvent polyester fibers production. A large majority of the production
Burning W of terephthalic acid is via aerobic catalytic oxidation of p-xylene
5.2. Methyl Bromide Y with air in acetic acid medium, catalyzed by cobalt, manganese,
5.3. Methane Y and bromide compounds, in a process commonly known as the
5.4. Methyl Acetate Z
5.5. Selectivity Assessment AA Received: July 25, 2012
5.6. Byproduct Chemistry AC

© XXXX American Chemical Society A dx.doi.org/10.1021/cr300298j | Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews
AMOCO process. This work aims to be a review of the
chemistry fundamentals and kinetics behind the process of
catalytic oxidation of p-xylene, providing insight into the most
important aspects relevant for industrial terephthalic acid
production operation and optimization and also on the most
recent research aiming at alternatives to the existing dominant
aerobic catalytic oxidation with the cobalt−manganese−
bromine catalyst in acetic acid medium.
In the first section, a brief evolution of the industrial process
of terephthalic acid is given, followed by general aspects of
hydrocarbon oxidation, relevant to the chemistry behind the p-
xylene oxidation process and the difficulties inherent to the
oxidation reaction that conditioned evolution of the catalysts
used until discovery of the cobalt/manganese/bromine
AMOCO catalyst, together with the respective kinetic
mechanism. In the second section, factors that have influence
the activity of the catalyst are discussed focusing on process
parameters that have more impact on industrial process yield
and their optimization. In the third section, selectivity aspects
are presented with particular emphasis on the byproducts and
the direct influence of the catalyst composition and their
formation. A brief review of available references on operational
optimization studies is made in the fourth section. Finally, in
the fifth section, recent research in p-xylene oxidation is
reviewed, presenting alternative catalysts, solvents, and
promoters and also heterogeneous catalysis studies, which all
aim to be alternatives to the presently used dominant
technology.
2. POLYESTER HISTORY
Terephthalic acid history is closely related to polyester history.
Since the pioneering research of Wallace Carothers on
condensation of aliphatic dicarboxylic acids with diols to yield
polyesters and the first granted patent in 1941 to J. R.
Whinfield and J. T. Dickson, PET manufacture acted as a
driving force to terephthalic acid industrial process develop-
ment.1 The resistance of the p-xylene molecule to conversion to
terephthalic acid constituted from the beginning, an intrinsic
barrier, around which the several technologies developed
themselves to bypass that difficulty. One of the earliest
commercially viable routes to terephthalic acid was through
the explosive hazardous liquid-phase nitric acid p-xylene
oxidation using 30−40% diluted nitric acid as oxidant at
temperatures between 160 and 200 °C and pressures from 8.5
to 13.5 bar. Terephthalic acid precipitates are separated and
purified in subsequent steps but contaminated with colored and
color-forming impurities.2 To overcome this a diversion tactic
was used consisting of esterification with methanol to dimethyl
terephthalate (DMT); successive crystallizations and distilla-
tions were required to yield a product with acceptable quality.
For the first few years of PET production, the polymer was all
made by a DMT ester interchange route.1 The Dynamit−
Nobel process quickly replaced the rather unsatisfactory and
hazardous nitric oxidation route to DMT. p-Xylene was
oxidized with air, in the absence of solvent in the temperature
range of 140−180 °C and pressure between 5−8 bar using a
cobalt catalyst, to p-toluic acid, which was esterified by
methanol to form methyl p-toluate, which was then oxidized
by air to monomethyl terephthalate in the same vessel, which in
turn was esterified with methanol to make DMT.
The success of this process was that even though p-toluic
acid is very resistant to oxidation with a cobalt catalyst, its
methyl ester is not; it is rapidly converted to monomethyl
B dx.doi.org/10.1021/cr300298j | Chem. Rev. XXXX, XXX, XXX−XXX
Review
terephthalate, which readily esterifies to dimethyl terephthalate.
The two oxidations could be combined so that p-xylene and
methyl p-toluate were oxidized in the same vessel and so could
be the two esterification reactions. Currently, direct liquid-
phase catalytic oxidation processes, consisting of homogeneous
liquid-phase oxidation of p-xylene in a solvent with air in the
presence of a transition-metal catalyst, is the dominant
industrial process for terephthalic acid manufacture. There are
variations of this process depending on the operating
conditions and catalysts used, but from these, the Mid-Century
process, also known as the AMOCO process, is the most
widespread used technology.3
2.1. AMOCO Process
The drive behind the research effort to direct oxidation has
been the relatively high resistance to oxidation of the p-toluic
acid which was first formed. This obstacle was overcome by the
discovery of bromide-controlled air oxidation in 1955 by the
Mid-Century Corp.4−7 and ICI, with the same patent
application date. The Mid-Century process was bought and
developed by Standard Oil of Indiana, later AMOCO, with
some input from ICI. The process uses acetic acid as solvent,
oxygen from compressed air as oxidant, a temperature of about
200 °C, and a combination of cobalt, manganese, and bromide
ions as catalyst. Various salts of cobalt and manganese can be
used, and the bromine source can be hydrobromic acid, sodium
bromide, or tetrabromoethane among others. The preferred
system is composed of cobalt and manganese acetates and
hydrobromic acid as bromine source. If a bromoalkane is used
such as tetrabromoethane, the molecule must solvolyze or be
oxidized readily to HBr. An ionic source of bromide is
necessary to achieve an active catalyst. A feed mixture of p-
xylene, acetic acid, and catalyst is continuously fed to the
oxidation reactor. The feed mixture also contains water, a
byproduct of the reaction. The reactor is operated at 175−225
°C and 15−30 bar. Compressed air is fed to the reactor in
excess to provide measurable oxygen partial pressure and
achieve high p-xylene conversion. The reaction is highly
exothermic, releasing 2 × 108 J/kg of reacted p-xylene. Most
of the terephthalic acid precipitates, as it is formed, due to its
low solubility in acetic acid. This yields a three-phase system:
solid terephthalic acid crystals, solvent with some dissolved
terephthalic acid, and vapor consisting mostly of nitrogen,
acetic acid, water, and smaller amounts of oxygen and carbon
oxides. The heat of reaction is removed by solvent evaporation.
Over 98% of the p-xylene is reacted, and the yield to
terephthalic acid is greater than 95 mol %. Small amounts of
p-xylene and acetic acid are lost, owing to complete oxidation
to carbon oxides, and impurities such as oxidation inter-
mediates are present in reactor effluent. The excellent yield and
low solvent loss in a single reactor pass account for the near
universal selection of this technology for new plants. Oxidation
of the methyl groups is approximately consecutive, with two
main intermediates p-toluic acid and 4-formylbenzoic acid or as
it is customarily referred to 4-carboxybenzaldehyde (4-CBA).
4-CBA acid is troublesome, owing to its structural similarity
to terephthalic acid. It cocrystallizes with terephthalic acid and
becomes trapped and inaccessible for completion of oxidation.
Chemical Reviews Review

to acetophenone and acetaldehyde to acetic acid with air in the

The slurry is passed from the reactor to one or more surge
vessels where the pressure is reduced. Solid terephthalic acid is
then recovered by centrifugation or filtration, and the cake is
dried and stored prior to purification. This is typically referred
to as crude terephthalic acid (CTA) but is more than 99% pure.
Crude terephthalic acid is unsuitable as a feedstock for
polyester, primarily owing to the 4-CBA impurity concen-
tration, which acts as chain termination agent in PET
manufacture, and so goes through a purification process. In
the purification process, crude terephthalic acid is dissolved in
hot water and 4-CBA is reduced and recovered to p-toluic acid
via catalytic hydrogenation over a palladium catalyst at about
250 °C and recycled to improve the process yield. There are
also other color-forming impurities and residual amounts of
catalyst metals and bromine. The AMOCO purification process
removes 4-CBA to less than 25 ppm and also gives a white
powder from the light yellow CTA feed, commonly referred to
as purified terephthalic acid (PTA). This process allowed
development of a route to polyester from PTA by direct
oxidation, which has since become more widely used than the
process using DMT. Several other processes for manufacturing
TA have been patented, and some of them have been used
commercially, but these two remain the most important.1,3
temperature range of 102−104 °C for periods of 24 h, catalyzed
by metals. Catalysts used were acetates of cobalt, nickel,
manganese, vanadium, cerium, iron, and chromium. In the
catalyzed oxidation of ethylbenzene yields of acetophenone
were higher than those Stephens11 obtained for the uncatalyzed
oxidation. The basis of catalytic oxidation−reduction action is
electron transfer from the reductant to the catalyst, followed by
electron transfer from the catalyst to the oxidant, which is faster
than direct electron transfer from the reductant to the oxidant.
A necessary, but not sufficient, requirement for such catalysis is
that the metal must possess two distinct oxidation states, none
of them too stable when compared to the other. Oxidation and
reduction of saturated molecules frequently results in
generation of free radicals. Transition metals, such as Cu, Co,
and Mn, have the ability to catalyze these oxidations. Among
such reactions are the autoxidations of hydrocarbons and other
organic molecules, initially to hydroperoxides, which proceed
by free-radical chain mechanisms in which the most important
propagation steps are
R• + O2 → RO2• (3)
RO2• + RH → ROOH + R• (4)
overall: RH + O2 → ROOH (5)
Metals catalyze the oxidation, generating free radicals in
chain decomposition of hydroperoxides according to the
following equations.
ROOH + Co2 + → RO• + OH− + Co3 + (6)

3. CHEMISTRY BEHIND THE PROCESS ROOH + Co3 + → RO2• + H+ + Co2 + (7)

3.1. General Aspects of Hydrocarbon Oxidation overall: 2ROOH → RO• + RO2• + H 2O (8)
Oxidation is a widely used synthetic route to a large range of followed by
chemicals. Published reports of oxidation studies of alkyl
aromatics with molecular oxygen are from as early as 1912, RO• + RH → ROH + R• (9)
when Ciamician and Silber8 studied the light effect on oxidation The chain reaction is continued by the newly formed
of toluene, o-xylene, m-xylene, p-xylene, and p-cymene. These radical.16 Indeed, there is in the literature accumulated evidence
hydrocarbons were lit by sunlight for a year in contact with that hydrocarbon oxidation follows a free-radical chain
oxygen, obtaining the corresponding carboxylic acids as main mechanism.17 Autoxidation is any oxidation that occurs in the
products. Isophthalic and terephthalic acids were formed presence of air or oxygen forming peroxides and hydro-
besides m- and p-toluic acids from m-xylene and p-xylene, peroxides. A generic commonly accepted mechanism for
respectively. Stephens (1926)9,10 carried out oxidation of hydrocarbon autoxidation found in literature reviews is as
several aromatic hydrocarbons with oxygen at temperatures follows18−21
around 100 °C in the presence of dimmed light. Hydrocarbons
such as xylenes and ethylbenzene were allowed to be in contact initiation step
with oxygen for periods from 24 up to 60 days obtaining for RH + initiator → R• + H ‐ initiator (10)
xylenes monoaldehydes as the major oxidation product and
only a fraction of the corresponding monocarboxylic acids. propagation steps
Stephens also accounted for a mechanism in which hydro- R• + O2 → ROO• (11)
carbon undergoes stepwise oxidation with aldehydes and
ketones as intermediates, excluding alcohols,11and also the ROO• + RH → ROOH + R• (12)
inhibiting effect of water in oxidation.11,12 Evidence for
formation of hydroperoxides as intermediates was found only termination steps
in cyclohexene oxidation.13 Hartman and Seibert succeeded in R• + R′• → R−R′ (13)
peroxide isolation in tetralin oxidation in 1932.14 Oxidation of
hydrocarbon induced by light is not practical for industrial ROO• + R′OO• → ROOOOR′ (14)
purposes due to the long induction times usually involved.
Action of catalysts is therefore necessary. The combined action ROO• + R′• → ROOR′ (15)
of molecular oxygen and metal catalysts is more suitable for RH represents a hydrocarbon from which a hydrogen atom can
industrial use, since the oxidation reaction happens much faster. be abstracted, yielding the free radical R•. ROO• and R′OO•
King et al.15 studied the liquid-phase oxidation of ethylbenzene are peroxide radicals and ROOH a hydroperoxide.
C dx.doi.org/10.1021/cr300298j | Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews
In the initiation step, the initiator attacks the substrate
molecule to generate the chain carrier free radical. At lower
temperatures, a long induction period precedes chain initiation
if the hydrocarbon is very pure or contains any molecules that
act as antioxidants that trap or decompose peroxide radicals,
inhibiting chain reaction. This is observed, for example, in the
oxidation of impure benzaldehyde with oxygen.22 When impure
benzaldehyde is allowed to react with oxygen, an induction
period is observed before any oxygen absorption occurs. After a
single distillation procedure, both the induction period and the
maximum rate were reduced considerably. Further distillations
eliminate the induction period, and the maximum reaction rate
is achieved immediately at the beginning of the reaction. In
addition, impure benzaldehyde oxidation shows both an
induction period and a maximum rate greater than that
observed for the pure substance, which is an indication of the
presence of both inhibitors and catalysts, the latter suggested to
be metallic ions.
In propagation steps, after the highly reactive free radical is
formed it reacts with an oxygen molecule to form a peroxy
radical (eq 11) which, by abstracting a hydrogen atom from
some other molecule, yields a hydroperoxide (eq 12). The
hydroperoxide will decompose in a sequence of further
oxidations to yield molecules with carbonyl and carboxyl
groups. Propagation steps are the product-controlling steps in
the autoxidation sequence. It is suggested in the literature19 that
radicals of intermediate stability can enter in equilibrium with
oxygen
R• + O2 ⇄ ROO• (16)
The equilibrium constant Keq is given by
[ROO•]
Keq =
[R•][O2 ] (17)
This equilibrium is important whenever radicals react with
oxygen in the presence of the parent hydrocarbon to yield the
dialkyl peroxide in preference to the hydroperoxide
ROO• + R• → ROOR (18)
The equilibrium between the radical, oxygen, and peroxy
radical may give only a low concentration of the peroxy radical
in the presence of alkyl radical, favoring formation of the dialkyl
peroxide and not the hydroperoxide. Assuming sequential
unimolecular kinetics for propagation steps, the propagation
rate, vP, is given by
vP = kP[ROO•][RH] (19)
The terms in right brackets represent the species concentration,
and kP is the propagation rate constant. If vP is fast enough, i.e.,
vP ≫ vT, where vT is the rate of termination, the chain reaction
is viable and products drop out of each cycle via the
hydroperoxide molecule ROOH. It is easily understood that a
critical issue is then how fast that peroxy radical is formed and
reacts with other molecules, as per reaction steps given by eqs
11 and 12, to form the hydroperoxide molecule: if the peroxy
radical stability is low, [ROO•] will be low and hydroperoxide
product formation will be low. The rate of propagation steps
controls the outcome of the autoxidation sequence, with radical
stability playing a major role. Factors governing radical
stabilization are the ability of delocalizing electrons through
resonance stabilization and electron availability of the carbon−
hydrogen bond being ruptured. The rate of interaction between
D dx.doi.org/10.1021/cr300298j | Chem. Rev. XXXX, XXX, XXX−XXX
Review
R• and O2 decreases with increasing resonance stabilization
energy of the radicals.23 Considering the equilibrium given by
eq 16, for free radicals with a higher resonance stabilization
than the peroxy radical, the left-hand side of the equation has
increased stability compared to the right-hand side. This means
that the energy difference between R• and O2 reactants and the
peroxide radical product RO2• is small. The energy barrier that
the peroxide radical has to overcome to decompose back to R•
and O2 is small. In a temperatures range from 300 to 700 K, Keq
decreases from the nonresonance-stabilized methyl radical to
the resonance-stabilized benzyl radical. Thus, according to the
equilibrium expression of eq 17 for Keq, [ROO•] will be smaller
than [R•].24 Consequently, hydroperoxide formation rates, as
per eq 12 will be low. Uncatalyzed oxidation will not be feasible
for practical purposes. In the case of olefins oxidation,
considering eq 12, the dissociation energy of the α C−H
bond decreases with increasing substitutions at the double
bond, i.e., olefins with higher substitution are more reactive
Similarly, α-hydrogen atom reactivity in toluene, ethyl-
benzene, and cumene toward a peroxy radical is 0.08, 0.5, and
1.0, which is in accordance with the increasing degree of
substitution at the α-carbon atom.19 In benzene derivatives, the
nature and position of a substituting group in the ring also plays
a role in the molecule’s reactivity toward a peroxy radical. A
series of changes in reaction conditions will cause changes in
the rate of a chemical reaction or in the position of its chemical
equilibrium. If the series of changes affects rates or equilibrium
of another chemical reaction in the same way minus the effect
of a given substrate, there will be a Gibbs free energy
relationship, ΔG, between the two sets of effects. This
relationship between free energy and equilibrium constants or
reaction rates was first established for the ionization reaction of
benzoic acid derivatives with meta and para substituents to each
other25
A ⎛⎜ B1 ⎞
−RT ln K + RT ln K 0 = ΔG = 2⎝
+ B2 ⎟
d D ⎠ (21)
K is a rate or equilibrium constant for a substituted reactant, K0
is the corresponding quantity for the unsubstituted reactants,
ΔG is the Gibbs free energy or its kinetic analogue, d is the
distance from the substituent to the reacting group, D is the
dielectric constant of the medium, and A, B1, and B2 are
constants independent of the temperature and solvent.
Equation 21 can be rearranged to eqs 22 and 23
log K = log K 0 + σρ (22)
or
log k = log k 0 + σρ (23)
Equations 22 and 23 are two simplified forms of what is known
by the Hammett equation, where
A
σ=−
2.303R (24)
and
Chemical Reviews
1 ⎛⎜ B1 ⎞ the polar effect is that p-xylene is much more reactive than p-
ρ= + B2 ⎟
d T⎝ D
2 ⎠ (25)
σ is a substituent constant dependent upon the substituent, and
ρ is a reaction constant dependent on the reaction medium and
temperature. With ρ values greater than 1, the reaction rate is
more sensitive to electronic effects than is the ionization of
benzoic acids. If 0 < ρ < 1, electron-withdrawing groups still
increase the rate constant but to a lesser extent than for benzoic
acids. If ρ is negative, electron-donating groups increase the
rate. Small ρ values, 0 < ρ < 1, often mean that the mechanism
involves intermediates with little charge separation, such as
radicals. High ρ values, both positive and negative, are
consistent with a mechanism in which charged intermediates
are present.26,27 The Hammett equation is also applicable to
oxidation of alkylaryl hydrocarbons, where polar effects in free-
radical reactions are present.28 Considering the reaction given
in eq 12 in the propagation step of the autoxidation, the
reactivity of a benzene derivative toward a peroxy radical can be
explained taking into account polar effects and the stability of
the radical formed. Considering cumene, the rate of reaction of
its para-substituted derivatives shows a pronounced polar effect,
as can be seen in Figure 1.
Figure 1. ρσ plot for the peroxy radical attack on substituted cumenes.
kx and kH are the rates of reaction of the peroxy radicals with a
substituted cumene and cumene, respectively. σ constants from ref 29.
Adapted from ref 28.
From Figure 1, it can be seen that electron-withdrawing
substituents, like nitro or cyano, decrease the rate when
compared with nonsubstituted cumene and an electron-
donating substituent, like tert-butyl, has the opposite effect on
rate. Oxidation is favored by increasing electron density at the
reaction site. This has been interpreted in terms of resonance
stabilization in the transition state for the reaction between the
peroxy radical and the hydrocarbon carbon−hydrogen bond.19
Polar effects have their influence in resonance structure I,
which is stabilized by electron-donating substituents and
destabilized by electron-withdrawing substituents in R′.
Resonance structure II explains the effects of the stability of
the ROO• radical upon the reactivity of a carbon−hydrogen
bond. Therefore, if both polar and radical stability effects are
present, the reactivity of a carbon−hydrogen bond toward a
peroxy radical can be very high. One practical consequence of
E dx.doi.org/10.1021/cr300298j | Chem. Rev. XXXX, XXX, XXX−XXX
Review
toluic acid toward a peroxy radical.
Exceptions to these findings exist. When electron-with-
drawing substituents increase the rate or when electron-
donating substituents decrease the rate, when compared with
the nonsubstituted molecule, a higher resonance effect can
explain an enhanced net aralkyl radical stabilization. Any
reactions in which free radicals are consumed, resulting in
molecules that are not free radicals, are the chain termination
steps (reactions steps given by eqs 13−15). These will stop the
chain and cause the chemistry to stop or be slow. Products
formed through termination reactions may not be necessarily
the same or similar to hydrocarbon being oxidized or its
hydroxyl, carbonyl, or carboxylic derivatives. Alcohols, ethers,
or peroxides may be obtained and even hydrocarbons resulting
from condensation of several hydrocarbon radicals. For
instance, as mentioned above, when the peroxy radicals are
resonance stabilized, reaction with the parent hydrocarbon may
yield peroxides as per eq 18 as well as dimer through
condensation in eq 13. Ketones may also be obtained through
interaction between two primary or secondary peroxide radicals
via a cyclic transition state.19
The effect of inhibitors (antioxidants) on hydrocarbon
oxidation, with influence also in initiation steps as mentioned
above, also is a factor in reaction termination. This effect will
depend upon whether a steady supply of free radicals (chain
initiators) is being generated in sufficient number to overcome
the chain-breaking action of the inhibitor. The view that the
action of inhibitors is a relative rather than an absolute effect is
substantiated by experimental evidence. For example, com-
pounds, such as phenols or alcohols, which also extend the
initiation inhibition period may have little effect on a reaction
which has reached a steady state.18
3.2. p-Xylene Autoxidation to Terephthalic Acid
In p-xylene oxidation, disregarding any byproducts formed in
secondary reactions, methyl groups are oxidized as per the
sequence of eq 2.3 The mechanism of oxidation is also through
free radicals as presented in eqs 11−15, and it is in that
mechanism where the limitations lie. Considering attack of an
initiator on a p-xylene molecule, the p-methyl benzyl radical
would be obtained as per eq 10.
This radical has the ability to become stabilized through
resonance.
Chemical Reviews
However, the product of radical interaction with O2, as per eq
11, the peroxy p-methyl benzyl radical, is not able to achieve
such kind of stabilization. The carbon atom to which the
oxygen atom is bonded has all four possible valences occupied,
and so the free electron in the peroxy oxygen atom is isolated
from the ring double-bond-conjugated system, and thus, the
radical cannot form any resonance hybrid, achieving a lower
stabilization. The equilibrium is therefore more favorable
toward the reactants in eq 11 and the peroxy radical
concentration is low, which according to eqs 17 and 19 causes
the propagation rate to be low. As mentioned above, in the
oxidation sequence in eq 2, an even slower step is oxidation of
p-toluic acid (eq 27). Consider the mechanism given by eqs
10−15: in the oxidation of the first methyl group of the p-
xylene molecule, the p-methyl benzyl radical is resonance
stabilized; in the oxidation of the second methyl group, in the
p-carboxyl benzyl radical, the COOH group is an electron-
withdrawing group, in opposition to the electron-donating
methyl group in the first oxidation. This will cause the electrons
of the ring to be attracted toward the COOH group, making
them less available to stabilize the CH2• group through
resonance structures.
The carboxyl group makes p-carboxyl benzyl radical
stabilization difficult. The methyl group carbon−hydrogen
bond of p-toluic acid is then strengthened. This is true also in
catalyzed oxidations. Oxidation of a methyl group to a
carboxylic group causes the σpara substituent constant to
increase from −0.1 to 0.42, making oxidation of the second
methyl group 4.9 times slower. Because p-xylene has the double
of oxidizable hydrogen atoms of p-toluic acid, p-xylene is 2 ×
4.9 = 9.8 times more reactive.21 The deactivating effect of the
carboxylic group is bypassed by converting the acid to a methyl
ester as is done in the Dynamit−Nobel process. Ester groups
are electron donating and do not deactivate the ring as
carboxylic groups do. As a consequence, methyl p-toluate
oxidizes to monomethyl terephthalate up to terephthalic acid.
Autoxidation of p-xylene to terephthalic has thus two great
major constrains: greater stability of the p-methyl benzyl radical
toward the p-methyl peroxybenzyl radical and p-toluic acid
resistance to oxidation due to the instability of the p-carboxyl
benzyl radical. These constrains make autoxidation a process
too slow for commercial processes. Air oxidation in commercial
processes requires the use of catalysts to achieve higher rates
and yields.
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Review
3.3. Catalyst Influence in Autoxidation
In the presence of small amounts of transition metals the
mechanism given by eqs 11−15 of oxidation is strongly
modified. The metal performs four important functions.16−21
• First, some transition metals participate in the initiation
steps, abstracting hydrogen atoms from hydrocarbons,
forming free-radical species, and enhancing the rate.
• Second, metals react quickly with the primary formed
peroxides via the Haber−Weiss cycle.30,31,18,21
The last step of this scheme, given by eq 37, shows reduction
of the metal catalyst to its initial oxidation state, showing that
decomposition is self-sustained with only small amounts of
metal.
• Third, metals also react very rapidly and selectively with
peracids, formed from benzaldehydes, and also with
higher yields.21
• Fourth, transition-metal complexes have the ability to
coordinate to radicals, such as the peroxy p-methyl
benzyl, trapping them, preventing them from reacting in
termination steps that decompose the radical and
decrease the rate, and driving them forward to
products.16
3.3.1. Cobalt and Manganese Acetates As Oxidation
Catalysts. Homogeneous transition-metal-catalyzed reactions
are widely used in Industrial Chemistry. Hydrogenation,
isomerization, polymerization, carbonylation, epoxydation, and
oxidation are some examples of industrial reactions catalyzed by
transition metals.32,33 Cobalt and manganese are metals used in
some homogeneous-catalyzed processes. Manganese acetyla-
cetonate and manganese acetate as well as cobalt bromide,
cobalt oleate, cobalt naphthenoate, and cobalt acetate are some
examples of the catalysts used. In oxidation, in particular,
manganese and cobalt acetates are very important cata-
lysts.2,34,35 Morimoto and Ogata proposed the following
mechanism for substituted toluene oxidation catalyzed by
cobalt acetate in acetic acid.36
PhCH3 + Co3 + → PhCH 2• + Co2 + + H+ (38)
PhCH 2• + O2 → PhCH 2O2• (39)
Chemical Reviews Review

Figure 2. Product concentration variation over reaction time: symbols, observed; line, calculated. Adapted from ref 43.

PhCH 2O2• + Co2 + → PhCHO + Co3 + + OH− (40)

PhCHO + Co3 + → PhCO• + Co2 + + H+
•
PhCO + O2 → PhCO3•
PhCO3• + PhCH3 → PhCO3H + PhCH 2•
PhCO3• •
+ PhCHO → PhCO + PhCO3H
PhCO3H + Co2 + → PhCO2• + OH− + Co3 +
PhCO2• + PhCH3 → PhCO2 H + PhCH 2•
PhCO2• + PhCHO → PhCO• + PhCO2 H
PhCHO, PhCO2H, and PhCO3H represent benzaldehyde,
benzoic acid, and perbenzoic acid, respectively, and PhCO•,
PhCO2•, and PhCO3• represent their respective radicals.
PhCH2• and PhCH2O2• represent the benzyl radical and
peroxy benzyl radicals, respectively. Generation of free radicals
can occur either by an electron-transfer mechanism in which an
electron is transferred from the aromatic hydrocarbon to the
metal catalyst with proton loss or hydrogen atom abstraction
from peroxy radicals, which is a propagation step. An induction
period may be observed or not depending on the amount of
cobaltic species (Co3+) present in the catalyst. It is observed
that it is suppressed by addition of benzaldehyde, which has the
effect of inducing oxidation of part of the catalyst from the
cobaltous (Co2+) to the cobaltic state (Co3+).36,37 Evidence of
the absence of an induction period for aromatic hydrocarbons
can be found in the literature.38−40 The induction period is due
to the low concentration of cobaltic ion and can be understood
as the time required for the inhibiting cobaltous ion to be
oxidized to cobaltic ion until its concentration is high enough to
initiate hydrogen abstraction from the hydrocarbon as per eq
38.41 This is confirmed by some experimentally established
hydrocarbon oxidation rate laws which are directly proportional
to [Co 3+ ] and [RH] and inversely proportional to
[Co2+].37−40,42
d[O2 ] [RH][Co3 +]2
− ∝k
dt [Co2 +]
The rate law, second order dependent on [Co3+],38−40,42
accounts for the postulated pre-equilibrium where a cobaltic
dimer, (Co(III)−Co(III)), is formed, with this dimer being the
active species for hydrocarbon hydrogen abstraction in the early
stage of the reaction
K′
2Co(III) ⇄ Co(III)2 (49)
(41) K″
Co(III)2 + RH ⇄ {RH+AcO− Co(III)} + Co(II) (50)
(42)
{RH+AcO− Co(III)} → R• + Co(III) + AcOH (51)
(43)
where AcO− and AcOH represent the acetate anion and acetic
(44) acid, respectively. During hydrocarbon oxidations in the
presence of oxygen the ratio of cobaltic ion to total cobalt
(45) tends to reach a steady state value close to 50%. When
cobaltous ion is added, cobaltic ion is regenerated to reach 50%
(46) again. This has been an argument to suggest that a dimer
comprising both cobaltic and cobaltous ions may also be an
(47) active catalytic species. As mentioned above, cobaltous ion has
been found to have an inhibiting effect; thus, the oxidation rate
is expected to decrease unless catalyst regeneration occurs. A
possible concerted mechanism for consumption and regener-
ation for Co(III) is given by37
The same type of concerted mechanism may account for the
activity of manganese as cocatalyst for cobalt
RH + O2 + Mn(III)− Co(II)
→ ROO− + Mn(II)− Co(III) + H+ (53)
Mn(II)− Co(III) ⇄ Mn(III)− Co(II) (54)
Ichikawa et al.43 proposed a similar mechanism to the one
given by eqs 38−46, excluding the reactions given by eqs 44
and 46, hydrogen abstraction from the aldehyde. The assumed
reaction steps are the same as those in eq 2. Their comparison
of the obtained results with the calculations made from the
assumed kinetic mechanism shows good results, as shown in
Figure 2.
In terms of catalyst structure, mixtures of several similar
(48)
multinuclear complexes have been proposed,44 the most
common being the proposed catalyst structure of a binuclear
μ-dihydroxy complex for both cobaltic and cobaltous acetates,
Figure 3.43
Hendriks et al.45 proposed a mechanism where the species
abstracting a hydrogen atom from the hydrocarbon molecule
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Chemical Reviews
Figure 3. Proposed structure for the catalyst in Teijin process.
Adapted from ref 43.
does not involve formation of a dimer, but initiation made by
Co3+ involves formation of an intermediate radical−cation.
k1(CH3CO2 H)
•
Co3 + + PhCH3 XoooooooooooooooY {(PhCH3+ )(CH3CO2−)}
k −1(CH3CO2 H)
+ Co2 + + H+
Co3 + + {(PhCH3+•)(CH3CO2−)}
⇄ Co3 +{(PhCH3+•)(CH3CO2−)}
Co3 +{(PhCH3+•)(CH3CO2−)}
→ Co3 + + PhCH 2• + CH3CO2 H
CH3CO2 H/H 2O
Co3 + + PhCH 2• ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Co2 + + PhCH 2OCOCH3
/PhCH 2OH + H+
PhCH 2• + O2 → PhCH 2O2•
Co3 + + PhCH 2O2• → Co2 + + PhCHO + 0.5O2
Co3 + + PhCHO → Co2 + + PhCO• + H+
H 2O
Co3 + + PhCO• ⎯⎯⎯→ Co2 + + PhCO2 H + H+
PhCO• + O2 → PhCO3•
H+
Co2 + + PhCO3• ⎯→
⎯ Co3 + + PhCO3H
PhCO3• + PhCHO → PhCO3H + PhCO •
+
2H
2Co2 + + PhCO3H ⎯⎯⎯→ 2Co3 + + PhCO2 H + H 2O
Some of the main differences between the two proposed
mechanisms are as follows.
• The Morimoto and Ogata mechanism explains benzylic
radical formation by direct hydrogen abstraction by the
cobaltic ion, and in the mechanism proposed by
Hendriks et al. a radical−cation is formed. The
Morimoto and Ogata mechanism explains aldehyde
formation from Co2+ oxidation and peroxide radical
reduction, whereas Hendriks et al. explains aldehyde
formation through Co3+ reduction and peroxide radical
oxidation.
• Acids in the Morimoto and Ogata mechanism are formed
from hydrogen atom abstraction from a hydrocarbon
molecule by the PhCO2• radical, and the Hendriks et al.
mechanism explains it by PhCO• oxidation in the
presence of water by reduction of a Co3+ ion and
hydroperacid decomposition with Co2+ ions.
• Peracids in the Morimoto and Ogata mechanism are
formed exclusively from PhCO3• hydrogen abstraction
from a hydrocarbon molecule, and in the Hendriks et al.
mechanism it is from PhCO3• hydrogen abstraction from
Review
an aldehyde and from acid-catalyzed reduction with Co2+
ions.
• In the Hendriks et al. mechanism Co2+ ion appears to be
more active in generating more nonradical products,
especially in peracid decomposition, and the Co3+ ion
also appears to be more active, generating both
nonradicals and radicals from aldehydes.
Hendriks et al.45 found that the oxidation rate of toluene by
Co(III) in anaerobic and aerobic conditions follows the same
rate equations, and the rate constants under different
conditions differ slightly. The product distribution, on the
other hand, was found to be considerably different: in anaerobic
conditions products were mainly benzyl acetates and
(55) benzaldehydes derived from the several toluene derivatives; in
aerobic conditions products were mainly benzaldehydes and
benzoic acid. The finding that hydrocarbon oxidation by
benzylperoxy radicals is not a reaction of any significance led to
(56) the conclusion that aerobic oxidation is not a radical chain
reaction, in opposition to the typical free-radical chain
mechanism proposed by Morimoto and Ogata. A similar
(57) conclusion was obtained by Heiba et al.,46 who found that the
cobaltic-catalyzed tertiary alkyl benzene oxidation rate was
slower than that of primary alkyl benzene. This is in opposition
with what was mentioned above for the α-hydrogen atom
(58) relative reactivity of 0.08, 0.5, and 1.0 for toluene, ethylbenzene,
and cumene in free-radical autoxidations.19 The σ plot data
(59) from Hendriks et al.45for the relation between the hydrogen
abstraction rate from a substituted toluene by Co3+ and the
(60) Hammett substituent constants are shown in Figure 4.
(61)
(62)
(63)
(64)
(65)
(66)
Figure 4. ρσ plot for hydrogen abstraction by Co3+ on substituted
toluenes. kx1 and kH are the reaction rates for substituted toluene and
toluene, respectively. σ+ constants from ref 47 Adapted from ref 45.
The ρ value found for this series plot is −1.97, a large
negative ρ. Like in the case of autoxidation of cumene
derivatives previously mentioned, a ρ negative value means that
electron-donating groups, like the methyl group, increase the
rate constant and electron-withdrawing groups, like the carboxy
group, decrease the rate constant. However, unlike the case of
autoxidation, ρ has a large value, meaning that the in the
transition state positively charged intermediates develop, which
is inconsistent with a free-radical mechanism26,46,49,52. In
addition, from Figure 4 it can be seen that p-toluic acid (p-
carboxy toluene) is less reactive toward oxidation than toluene,
even in the presence of a catalyst. Kashima and Kamiya40 also
observed that the apparent chain length of p-toluic acid
oxidation by cobaltic acetate in acetic acid is much shorter
compared to that of p-xylene. This is related with the increased
oxidation potential arising from the carboxylic group presence,
causing electron transfer from the molecule to the catalyst
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Chemical Reviews Review

Figure 5. Data fitting for product concentration variation over reaction time according to the Hendriks et al. mechanism: symbols, observed; line,
calculated. Adapted from ref 45.

complex to be harder. This feature has been of great as a solvent that no terephthalic acid yield was observed. They
importance in the industrial oxidation of p-xylene to also concluded that Co and Mn action in the Co/Mn/Br
terephthalic acid. The resistance of p-toluic acid toward catalyst was synergistic, other halide salts of Co and Mn gave
oxidation accounts for some reported need for use of larger low terephthalic acid yields, and finally acetic acid was the most
amounts of catalyst in industrial processes, compared with what stable solvent. The main discovery was the ability of bromine to
is usually employed in other autoxidations.48,43 Despite the increase the rate of oxidation.7 Bromine and bromine and
differences in the mechanisms, the oxidation rate in the cobalt show activity toward hydrocarbon oxidation, but the
Hendriks et al. mechanism, Figure 5, follows the same most successful combination has proved to be combination of
proportionality as the one found in the Morimoto and Ogata bromine, cobalt, and manganese, the core catalyst of the
mechanism, given by eq 48, and the fit for periodical variation AMOCO MC method.
of each compound, like the one obtained by Ichikawa et al.43 3.3.2.1. Catalysis by Bromine. Bromine compounds, in
also shows good results. Both mechanisms therefore explain the particular, hydrogen bromide, are known hydrocarbon oxidants,
product formation sequence given by eq 2. according to the mechanism54−56
The catalyst structure, as proposed by Hendriks et al., in
acetic medium is a six-ligand mononuclear complex, rather than HBr + O2 → Br • + HO2• (68)
a dimer structure, based on magnetic susceptibility measure-
RCH3 + Br• → RCH 2• + HBr (69)
ments. 49 Cobaltous acetate can be represented as
CoII(OAc−)2(AcOH)4 and cobaltic acetate by RCH 2• + O2 → RCH 2OO• (70)
CoIII(OAc−)3(AcOH)3. In solution the acetic acid ligands can
be progressively exchanged by water, aldehydes, phenol, and k
carboxylic acids. Octahedral geometry is the usual geometry for RCH 2OO• + HBr → RCH 2OOH + Br • (71)
d-block six-coordinated metal complexes, such as cobalt The peroxide, on loss of a water molecule, yields an aldehyde
complexes, Figure 6.50 (or ketone). Further oxidation yields a carboxylic acid.
Recent research has shown that in acetic acid solution two
forms of mononuclear catalytically active cobaltic complexes
may coexist in equilibrium. Reduction of cobaltic species is
accompanied by oxidation of the solvent and is given by the
following mechanism51
Coα 3 + ⇄ Coβ 3 + → Co2 + (67)
3.3.2. Cobalt/Manganese/Bromide Catalyst Systems.
The resistance of p-toluic acid toward oxidation was overcome
with a successful catalyst breakthrough obtained by Saffer and
Barker 4−6 almost simultaneously with McIntyre and
O’Neill.52,53 The first attempts to increase rates in aromatic
hydrocarbon oxidation were made with manganese bromide
playing the role of catalyst in p-cumene oxidation in acetic acid
medium. The overall oxidation yield was found to be no better
than that obtained using other manganese salts, but practically
no intermediates were found. They also tried all the elements in
the periodic table and found Co and Mn to give the highest
terephthalic acid yields. They then varied the anion of Mn and 3.3.2.2. Catalysis by Cobalt and Bromine. Ravens57 studied
discovered that bromide increased both the yield and the rate the oxidation of p-toluic acid by cobalt and manganese
of oxidation. They then switched to p-xylene as the reagent and bromides in acetic acid. They found a rate law given by
found that Mn/Br gave a 77% terephthalic acid yield while
d[O2 ]
Mn(II) acetate gave a very low yield. Then they established that − ∝ k[Co2 +][NaBr]1/2 [O2 ]1/2
Co/Br gave a 79% yield and that if benzene replaced acetic acid dt (77)

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Chemical Reviews
The reaction rate has a linear dependence on cobalt acetate
concentration at constant sodium bromide concentration and a
square root dependence on sodium bromide concentration
with constant cobalt concentration dependence. The rate
dependence on [NaBr]1/2 holds only up to a bromide:cobalt
ratio smaller than 2, where an inflection point occurs, and
beyond it, large deviations occur due to structural changes in
the cobaltous ion complex. The small initial rate in the absence
of one or the other ion shows that the combined action of both
catalysts has a beneficial effect on the reaction rate. The
Figure 6. Octahedral representations of CoII(OAc−)2(H2O)4 (1) and
CoIII(OAc−)3(H2O)3 (2).
dependence of the reaction rate on [Co2+] and [NaBr] found
by independent variation of the catalyst component concen-
trations is further substantiated by the rate dependence on
[CoBr2]3/2, which may also be expressed as [Co2+][NaBr]1/2.
The dependence of the reaction rate on [NaBr]1/2 and [O2]1/2
indicates that both oxygen and sodium bromide are involved in
the initiation step and that chain termination is by a
bimolecular radical−radical reaction. The initiation step by
reaction between HBr and O2, as per reaction in eq 68, arises
from pre-establishment of the equilibrium
NaBr + CH3CO2 H ⇄ HBr + CH3CO2 Na (78)
The proposed mechanism for p-toluic acid oxidation is given
by
PhCH3 + Br • → PhCH 2• + HBr (79)
• •
PhCH 2 + O2 → PhCH 2OO (80)
PhCH 2OO• + Co2 + → PhCHO + OH− + Co3 + (81)
Co3 + + HBr → Co2 + + H+ + Br • (82)
2PhCH 2OO• → PhCH 2CH 2Ph + 2O2 (83)
PhCH 2OO• + PhCH 2• → PhCH 2OOCH 2Ph (84)
2PhCH 2• → PhCH 2CH 2Ph (85)
where Ph stands for
An important aspect of this mechanism is that p-toluic acid
does not enter in its propagation, reaction propagation being
through the electron-transfer reaction between a cobaltous ion
and peroxide radical, as given by eq 81. This absence of p-toluic
acid is accounted for in agreement with the rate law equation
given by eq 77. The role of cobalt is that of decomposing
peroxide radical and regenerating the mechanism initiating
species, Br•, through eq 82. Bawn and Wright58 also studied p-
toluic acid oxidation by cobalt bromide in acetic acid medium
and divided the oxidation in two stages. The first stage involved
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Review
catalysis in solvent media by either cobaltous bromide or a
mixture of a cobaltous salt and inorganic bromide as catalyst. At
the end of the first stage, all ionic bromide disappeared from
solution and the bromine is present in the form of p-
bromomethyl benzoic acid. The second stage is catalyzed by a
cobalt salt and p-bromomethyl benzoic acid with no bromide
ions in solution. The role of bromine in the catalytic oxidation
of hydrocarbons is explained as to be other than that of reaction
initiation by hydrogen abstraction as postulated by Ravens,
Bawn, and Wright, since formation of hydrobromic acid from
bromide salts as per eq 78 proceeds to a very low extent due to
the low equilibrium constant. In fact, the long induction periods
observed in cobalt-bromide-catalyzed oxidations lead to the
hypothesis that its role is to catalyze propagation steps.59−63
Figure 7 shows the oxygen absorption rate for p-xylene
oxidation catalyzed by cobalt dibromide, CoBr2, and cobalt
decanoate, CoDe2, and sodium bromide.
Figure 7. Oxygen absorption curves in the autoxidation of p-xylene in
acetic acid catalyzed with 10−2 M CoBr2 and with a mixture of 10−2 M
CoDe2 and 2 × 10−2 M NaBr at 80 °C. Adapted from ref 62.
Cobalt dibromide shows an initial higher rate, but it
decreases after approximately 30 min, showing that catalyst is
becoming deactivated. The rate of the mixture containing
CoDe2 and NaBr is kept constant over a large period. Higher
cobalt dibromide concentrations show pronounced induction
periods, which, on addition of sodium bromide, are eliminated.
This shows that cobalt dibromide is not the active catalyst, but
cobalt acetate bromide, formed by eq 86, is
CoBr2 + NaCH3COO → CoBrCH3COO + NaBr (86)
In addition, increasing the ratio between sodium bromide and
cobalt increases the rate from a ratio of 0.5 to 1.0 from which
the rate is kept constant, as Figure 8 shows. At a ratio of 1.0, the
concentration of free HBr is very low and most of the bromide
is complexed with cobalt. This confirms that the oxidation rate
increase is due to catalysis by cobalt acetate bromide and not by
HBr.62
The catalytic mechanism in the propagation step is given
by62
RH
⎯ R•
ROOH + (Co)2 → radical ⎯→ (87)
• •
R + O2 → RO2 (88)
• •
RO2 + RH → ROOH + R (89)
RO2• + Co2 +BrH → products + (Co2 + + Br•) (90)
(Co2 + + Br•) + RH → (Co2 +BrH) + R• (91)
Chemical Reviews
Figure 8. Steady state rate of oxidation of p-xylene in acetic acid as a
function of the NaBr/Co molar ratio. Adapted from ref 62.
RO2• + RO2• → products + O2
(Co)2 represents a dimer cobalt species as postulated above for
cobalt acetate catalysis,38−40,42 and Co2+BrH represents the
cobalt acetate bromide, the active species in this catalytic
scheme
Replacement of approximately 20% of cobalt by manganese
increases by a factor of 5 the rate of oxidation, showing that a
strong catalytic synergy exists, due to the ability of manganese
to react with peroxy radicals. This synergy exists up to a liming
extent, from where manganese deactivation starts to occur,
Figure 9.
3.3.2.3. Catalyst Breakthrough: AMOCO MC Method. The
corollary of the experiments with inclusion of bromine was the
conclusion that the critical combination of components
required to achieve high efficiency in the oxidation of p-xylene
to terephthalic acid was a source of bromine and a mixture of
cobalt and manganese salts.7 This is the basis of the AMOCO
Mid-Century (MC) method
Figure 9. Mixing effect of cobalt with manganese in the rate of oxidation of p-xylene in acetic acid. Adapted from ref 62.
Review
hydrocarbon + dioxygen
catalyst = metal(s)/bromide
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ oxygenate + water
solvent (94)
More than 251 alkylaromatic compounds have been oxidized
using the method described in eq 94.21 The most common
example is oxidation of alkylbenzenes to aromatic carboxylic
acids
When bromine and manganese compounds are added to a
reaction catalyzed by cobalt compounds, creating a Co/Mn/Br
(92)
catalysts system, five important changes result, indicating that
new catalytic pathways are available.21
• Catalyst becomes 16 times more active.
• Formation of CO2 and CO from secondary reactions
decreases by a factor of 10, indicating a more selective
reaction, accompanied also by a higher activity.
• The steady state concentration of cobaltic ion is reduced
to only 0.6%.
• The maximum temperature of oxidation achievable is
higher than the 150 °C usual for cobalt-catalyzed
oxidations with comparable yields.
• Long induction times are absent, except for highly
purified hydrocarbons.
Although Co/Mn/Br catalyst type is most common in the
AMOCO MC method, there are other catalyst systems with
bromide and with one, two, or three metals, Table 1.
The most common catalyst is Co/Mn/Br followed by Co/Br
and Mn/Br. Cobalt is present in the majority of the catalysts
due to its known ability to rapidly decompose hydroperoxides
via the Haber−Weiss cycle,30,31 the primary products of the
oxidation process. The new available kinetic pathways for a Co/
Mn/Br MC catalyst type in an aromatic hydrocarbon oxidation
can be depicted as shown in Figure 10.
In simple terms, bromine acts as promoter, initiating
hydrogen abstraction from the hydrocarbon and generating
bromide. Bromide ion is oxidized by Mn3+, yielding Mn2+. Mn2+
is oxidized back to Mn3+ by Co3+, yielding Co2+, which, by
peroxide decomposition, will be oxidized back to Co3+.
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Chemical Reviews Review

Table 1. Examples of Catalyst Systems Using Bromine and with n = 1 and 2, denoting monomer or dimer, and the square
One, Two, or Three Metalsa brackets denote the ligands in the inner coordination sphere of
the metal, M. Figure 11a and 11b shows suggested structures
one metal Co/Br Mn/Br Co/Br/ Co/Br/Cl
acetate for the left-hand side structures with n = 1 and 2, respectively.
V/Br Cu/Br Ce/Br
two metals Co/Mn/Br Co/Ce/Br Co/Cu/Br Co/Mn/Br/
acetate
Co/Mn/Br/ Mn/Si/Br Mn/Cu/Br Ni/Mn/Br
Cl
Co/Ca/Br Mn/Fe/Br Co/Te/Br Co/Ni/Br
Co/U/Br
three Co/Mn/Zr/ Co/Mn/Ce/ Co/Ce/Zn/ Co/Ce/Zr/Br;
metals Br Br Br
Ni/Mn/Zr/ Co/Mn/Hf/ Co/Mn/Ru/ Co/Mn/Cr/Br Figure 11. Suggested structures for Co/Mn acetate catalyst in
Br Br Br;
anhydrous acetic acid mixtures. M = Co(II), Co(III), Mn(II), Mn(III).
Co/Mn/Fe/ Co/Mn/Mo/
Br Br Adapted from ref 65.
a
Adapted from ref 21.
Addition of water to acetic acid results in acetic acid ligands
The nature of the Co/Mn/Br catalyst in the oxidation of p- being exchanged with aqua ligands
xylene can be very diverse and complex.64 The reaction mixture
[M(HOAc)m (H 2O)m − 4 (OAc)2 ]n
may contain, in addition to Co(OAc)2·4H2O and Mn-
(OAc)2·4H2O other mononuclear species like Co(OAc)Br ⇄ {[M(HOAc)m (H 2O)m − 5 (OAc)]n (OAc)} (97)
and Co(OAc)3, multinuclear species like Co3(O)(OAc)x and
Mn3(O)(OAc)x, and heteromultinuclear complexes like with m ranging from 1 to 4 and decreasing with increasing
Co2Mn(O)(OAc)x or CoMn2(O)(OAc)x. Mononuclear com- water concentration. Figure 12a and 12b shows the ligand
plexes are the predominant species in the initial stages of distribution around the metal in acetic acid/water mixtures.
oxidation: they show the ability to abstract a hydrogen atom At water concentration close to 10%, which is common in
from p-xylene. Some of these species like cobalt acetate industrial processes, the predominant structure has four aqua
bromide, Co(OAc)Br, are very short lived due to their high and two acetate ligands. The proposed structure is shown in
reactivity toward p-xylene, arising from their very high redox Figure 13.
activities. Cluster heteromultinuclear complexes, found in the Addition of hydrobromic acid in anhydrous acetic acid results
later stages, probably play an important role in the oxidations of in acid−base neutralization between HBr and acetate ions,
both p-toluic and 4-carboxybenzaldehyde. Cobalt acetate leading, predominately, to bromine inner-sphere coordination
bromide, Co(OAc)Br, which as previously mentioned is [M(HOAc)4 (OAc)2 ]n + {[M(HOAc)5 (OAc)](OAc)}n
described to be a powerful and active species in aromatic
hydrocarbon oxidation, is often studied in anhydrous acetic + HBr ⇄ [M(HOAc)4 (OAc)(Br)]n
acid.65 In industrial oxidation of p-xylene, the reaction medium
contains 5−15% of water to make the solvent less aggressive + {[M(HOAc)4 (OAc)](Br)}n + HOAc
toward the materials used in the equipment and associated (98)
pipework. In anhydrous acetic acid the predominant species can Most of the bromide is coordinated in anhydrous acetic but
be described through the right-shifted equilibrium rapidly decreases as water concentration increases. If HBr is
+HOAc added with more than 5% water, as is the case for most
[M(HOAc)4 (OAc)2 ]n XoooooooY {[M(HOAc)5 (OAc)](OAc)}n industrial processes, little bromide is coordinated and the
(96) predominant species is the ion-paired bromide salt

Figure 10. Catalytic pathway for MC oxidation of p-toluic acid. Adapted from ref 21.

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Chemical Reviews Review

Figure 12. Distribution of ligands around cobalt(II) (a) and manganese(II) (b) as a function of water concentration in acetic acid. Adapted from ref
65.

RO2 + [Co(II)− Mn(II)]

Figure 13. Suggested structures for Co/Mn acetate catalyst in an
acetic acid solution with water concentration of 10%. M = Co(II),
Co(III), Mn(II), Mn(III). Adapted from.65.
{[M(HOAc)m (H 2O)m − 5 (OAc)n ]n (OAc)} + HBr
⇄ {[M(HOAc)m (H 2O)m − 5 (OAc)]n (Br)} + HOAc
(99)
The proposed structure for a Co/Mn/Br catalyst in acetic acid
solution in the presence of water is shown in Figure 14.
H+
XooY ROOH + [Co(III)− Mn(II)] (102)
Peracids react preferentially with metal dimers
RO2 H + [Co(II)− Co(II)]
H+
XooY ROH + [Co(III)− Co(III)] (103)
RO2 H + [Co(II)− Mn(II)]
H+
XooY ROH + [Co(III)− Mn(III)] (104)
Ligands were not represented for simplicity.
3.3.2.3.1. Kinetic Mechanism of the AMOCO MC Method.
In the literature there are several studies describing p-xylene
oxidation, but these were performed at conditions different
from those adopted in industrial processes or the models were
based on empirical data and not a kinetic mecha-
nism.43,45,61,66−68 Recently, Wang et al.69 proposed a stepwise
mechanism through intermediates formed as per eq 105 to
explain the oxidation of p-xylene catalyzed by cobalt and
manganese acetates and hydrobromic acid in acetic acid at
conditions close to those used in an industrial process.

Figure 14. Suggested structures for Co/Mn/Br catalyst in an acetic

acid mixture solution. M = Co(II), Co(III), Mn(II), Mn(III). Adapted
from ref 65.

Bromide is hydrogen bonded to one of the coordinated aqua

ligands.
The homogeneous Co/Mn/Br catalyst is thus not a single
catalyst but a mixture in which several catalytically active
species can coexist. In this sense a catalyst is any structure made The combined effect of Co and Mn is to decompose
when its metals are oxidized by oxidants like peroxy radicals or peroxides to yield the oxygenate product. Mechanism initiation
peracids. In such a mixture the oxidants may react with either a is done by hydrogen abstraction from the hydrocarbon by
monomer or a dimer bromine radicals generated through bromide ion oxidation by
H+ the metals
RO2• + [Co(II)] XooY ROOH + [Co(III)] (100)
Mn 2 + + Co3 + → Co2 + + Mn 3 + (106)
•
RO2 + [Co(II)− Co(II)] Co3 + + Br − → Co2 + + Br • (107)
H+
XooY ROOH + [Co(III)− Co(II)] (101) Mn 3 + + Br − → Mn 2 + + Br • (108)

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Chemical Reviews Review

3.3.2.3.1.1. Oxidation of p-Xylene to p-Tolualdehyde (PX Br• + HOOCPhCH 2O2• → HOOCPhCH 2O2 Br (127)
to TALD).
3.3.2.3.1.4. Oxidation of 4-Carboxybenzaldehyde to
Br• + CH3PhCH3 → Br − + CH3PhCH 2• + H+ (109) Terephthalic Acid (4-CBA to TA).
CH3PhCH 2• + O2 → CH3PhCH 2O2• (110) Br• + HOOCPhCHO → Br − + HOOCPhCO• + H+
(128)
CH3PhCH 2O2• + Co2 + + H+ HOOCPhCO + O2 →•
HOOCPhCO3• (129)
3+
→ CH3PhCHO + Co + H 2O (111)
HOOCPhCO3• + Co2 + + H+
CH3PhCH 2O2• + Mn 2 + + H+ → HOOCPhCOOOH + Co3 + (130)
3+
→ CH3PhCHO + Mn + H 2O (112) HOOCPhCO3• + Mn 2 + + H+
Br• + CH3PhCH 2• → CH3PhCH 2Br (113) → HOOCPhCOOOH + Mn 3 + (131)

Br• + CH3PhCH 2O2• → CH3PhCH 2O2 Br (114) HOOCPhCOOOH + HOOCPhCHO

Electron-transfer mechanism initiation between metal and → 2HOOCPhCOOH (132)
hydrocarbon producing a radical cation by reactions given in
eqs 55−57, more common in the absence of bromine, was not Br• + HOOCPhCO• → HOOCPhCOBr (133)
considered. Attack of peroxide radical on hydrocarbon and •
Br + HOOCPhCO3• → HOOCPhCO3Br (134)
solvent molecules was neglected. Also, hydroperoxide for-
mation and decomposition reactions by Co2+ and Mn2+ via the The reaction rates for the most important intermediates, PX,
Haber−Weiss cycle were not considered. The only termination TALD, PT, and 4-CBA, are given by
reactions considered were those between the bromine radical
d[PX]
and the free radicals (eqs 113, 114, 120, 121, 126, 127, 133, and = −r1 = ke.99[PX][Br •]
134). dt (135)
3.3.2.3.1.2. Oxidation of p-Tolualdehyde to p-Toluic Acid d[TALD]
(TALD to PT). = r1 − r2 = r1 − [TALD](ke.105[Br •]
dt
Br• + CH3PhCHO → Br − + CH3PhCO• + H+ (115) + ke.109[CH3PhCOOOH]) (136)
•
CH3PhCO + O2 → CH3PhCO3• (116) d[PT]
= r2 − r3 = r2 − ke112[PT][Br •]
CH3PhCO3• + Co 2+ +
+ H → CH3PhCOOOH + Co 3+ dt (137)
(117) d[4‐CBA]
• 2+ + 3+
= r3 − r4 = r3 − [4‐CBA](ke.118[Br•]
CH3PhCO2 + Mn + H → CH3PhCOOOH + Mn dt
(118) + ke.122[CH3PhCOOOH]) (138)
CH3PhCOOOH + CH3PhCHO → 2CH3PhCOOH Applying the steady state approximation to all radical and
(119) peracids and considering that the total concentration of
Br• + CH3PhCO• → CH3PhCOBr (120)
radicals, [I•], is approximately equal to a constant, ε, i.e.
4
Br• + CH3PhCO3• → CH3PhCO3Br (121) [I•] = ∑ ki[I•] = ∑ fi ci[Br•] = ε
Product p-toluic acid is yielded through reaction between j=1 (139)
aldehyde and peracid by the Baeyer−Villiger70 oxidation (eq then the general rate law is given by
119).
3.3.2.3.1.3. Oxidation of p-Toluic Acid to 4-Carboxyben- kici
ri = kici[Br •] =
zaldehyde (PT to 4-CBA). λ1c1 + λ 2c 2 + λ3c3 + λ4c4 + ε (140)
Br• + HOOCPhCH3 → Br − + HOOCPhCH 2• + H+ λi are rate constants from the reaction mechanism, and c1, c2, c3,
(122) and c4 are PX, TALD, PT, and 4-CBA concentrations,
respectively. Equation 140 shows that the rate follows a direct
HOOCPhCH 2• + O2 → HOOCPhCH 2O2• (123) proportionality to [Br•], a critical factor to initiate the oxidation
reaction. Bromine radical concentration depends on inter-
HOOCPhCH 2O2• + Co2 + + H+ mediate product concentrations. As these decrease, [Br•]
→ HOOCPhCHO + Co3 + + H 2O (124) increases, increasing the reaction rate. When the intermediate
concentration is very low when compared with ε, ∑j4= 1 λjcj ≪
HOOCPhCH 2O2• + Mn 2 + + H+ ε, the rate is first order to the intermediate, which is found in
several other kinetic mechanisms.37−40,42 The rate law is also
→ HOOCPhCHO + Mn 3 + + H 2O (125) independent of oxygen concentration, which in industrial
processes is fed to the oxidation reactor in excess to achieve
Br• + HOOCPhCH 2• → HOOCPhCH 2Br (126) high conversion of the limiting reactant p-xylene and also of the
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Chemical Reviews Review

Figure 15. Evolution of reactants concentration as a function of time: (a) batch experiment at 160 °C and 14 atm; (b) semicontinuous experiment at
160 °C and 18 atm. Adapted from ref 69.

intermediates. Figure 15 shows intermediate concentration d[TALD]

evolution as a function of time. = k1[PX] − k 2[TALD]
dt (142)
The results show good agreement between the data from the
batch and semicontinuous experiment and the concentration d[PT]
= k 2[TALD] − k 3[PT]
predicted from eq 140. Figure 15a shows the typical behavior of dt (143)
consecutive reactions and that the methyl groups are oxidized
consecutively, in agreement with the sequence given by eq 105. d[4‐CBA]
= k 3[PT] − k4[4‐CBA]
The concentration of p-toluic acid tends to build-up in the dt (144)
experiments, showing the typical difficulty in oxidizing the On integration with the initial conditions, t = 0, [PX] = [PX]0,
second methyl group of p-xylene, as confirmed by Figure 15b. [TALD] = [TALD]0, [PT] = [PT]0, and [4-CBA] = [4-CBA]0,
The above mechanism and rate law proposed by Wang requires rate laws are given by
regression from experimental data of 9 parameters. The number
of these parameters increases as the number of elementary [PX]
= e−k1t
reactions considered in the mechanism increase. This inevitably [PX]0 (145)
increases the complexity of the mathematical model as it
requires more and more kinetic parameters determined from [TALD] k1
= (e−k1t − e−k 2t )
experimental data fitting regression. Several authors have [PX]0 k 2 − k1 (146)
adopted simplifications.67,68 Sun et al.71 established a radical
chain mechanism that assumes that all participating peroxide [PT] k1k 2e−k1t k1k 2e−k 2t
free radicals have the same reactivity for removing an α- = −
[PX]0 (k 3 − k1)(k 2 − k1) (k 3 − k 2)(k 2 − k1)
hydrogen from any hydrocarbon intermediate substrate shown
in eq 105. It is also assumed that all substrates have the same k1k 2e−k3t
+
initiation rate constants. This assumption in particular is (k 3 − k 2)(k 3 − k1) (147)
cumbersome: historically, development of chemical process
technology in the process of terephthalic acid from p-xylene [4‐CBA] k1k 2k 2(e−k1t − e−k4t )
oxidation encountered resistance in the oxidation of p-toluic =
[PX]0 (k 3 − k1)(k 2 − k1)(k4 − k1)
acid and differences in reactivity have been largely accounted
for, as easily seen from a σ-constant plot. Finally, in Sun’s k1k 2k 2(e−k 2t − e−k4t )
mechanism, differences in the termination rate constants are −
(k 3 − k 2)(k 2 − k1)(k4 − k 2)
small and, therefore, negligible. Nevertheless, the first-order
kinetic model only relies on six rate constants, and the data fit k1k 2k 2(e−k3t − e−k4t )
+
of concentration changes of reactants for different catalyst (k 3 − k 2)(k 3 − k1)(k4 − k 3) (148)
concentrations shows, like in the case of Wang’s mechanism,
good agreement. The ultimate simplification of the kinetics of [TA] = [PX]0 − [PX] − [TALD] − [PT] − [4‐CBA]
p-xylene oxidation is to consider a lumped scheme, as per eq (149)
105, with no initiation, propagation, and termination 72
Li and Li adopted a lumped scheme for characterization of
elementary reactions as in a “classical” reaction chain p-xylene oxidation catalyzed by Co(OAc)2/Mn(OAc)2 in the
mechanism, considering only the most relevant intermediates presence of CoBr2 and MnBr2 at temperatures of 100, 110, and
in the overall reaction pathway. The kinetics can be explained 120 °C and oxygen pressures of 2 and 10 atm. They obtained a
in terms of classical kinetics of a consecutive reaction involving good fit of eqs 145−149 to their experimental results, showing
four steps. Considering the simplified eq 105 scheme, reaction that assuming pseudo-first-order reaction rates for each step of
rates are given by p-xylene oxidation is a reasonable simplification of the reaction
mechanism. Wang et al.73 adopted the same lumped kinetic
d[PX] scheme for the oxidation catalyzed with Co(OAc)2/Mn(OAc)2
= −k1[PX]
dt (141) and HBr in acetic acid in the temperature range from 188 to
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Chemical Reviews
197 °C and oxygen partial pressures from 12 to 40 KPa. The
rate law is given by
Cj
ri = kj
4
(∑i = 1 diCi + θ )βj
with β and θ being kinetic parameters. The agreement between
experimental data and model prediction based on the lumped
scheme is satisfactory, being detailed enough to characterize the
distribution of the most important species concentration with
different reaction conditions. Lumped kinetic schemes show
enough detail to give time function concentrations of the main
intermediate species; more detailed mechanisms account for
other issues of great importance in industrial processes like
formation of byproduct and solvent burning into carbon oxides.
4. ACTIVITY
In the AMOCO process, oxidation of p-xylene progresses
nearly to completion: over 98% of the p-xylene is reacted and
the yield to terephthalic acid is greater than 95 mol %. This
presents a problem when monitoring reaction activity in a
continuous reactor. A major change in activity does not result
in an easily measured decrease in the level of reactant, as p-
xylene is only present in the reactor contents in small amounts
as it quickly reacts with oxygen. Monitoring an intermediate
concentration can be a useful method to monitor the activity.
Among the several intermediates, considering only those given
by eq 105, p-toluic acid and 4-carboxybenzaldehyde can both
be, in a first approach, chosen to monitor activity. As expected,
p-toluic acid is present at the highest concentration among
intermediates in the reaction medium due to its known
resistance in oxidizing the second methyl group of p-xylene.
Because it is very soluble in the acetic acid solvent, very little
precipitates with terephthalic acid. In the purification process, it
is removed from terephthalic acid, because of its solubility in
water. Historically, p-toluic acid has not been the major concern
when assessing the AMOCO process terephthalic acid quality.
Because 4-carboxybenzaldehyde is less soluble in acetic acid
than p-toluic acid and it has a structure similar to terephthalic
acid, part of it coprecipitates with terephthalic acid and is
present as an impurity in the CTA. Therefore, it presents itself
as the preferred intermediate to monitor the activity, even
though p-toluic acid can also be used to assess it.
4.1. Temperature and Pressure Effect on Activity
An Arrhenius plot of the rate constant for the oxidation
reaction of 4-carboxybenzaldehyde to terephthalic acid is shown
in Figure 16.
Figure 16. Temperature dependence of the rate constant for the
oxidation reaction of 4-carboxybenzaldehyde to terephthalic acid. Data
from ref 69.
Review
It can be seen that as temperature increases, the conversion
rate of 4-carboxybenzaldehyde to terephthalic acid also
increases. Figure 17 shows the trend of 4-carboxybenzaldehyde
concentration.
(150)
Figure 17. Concentration of 4-carboxybenzaldehyde vs time at
different reaction temperatures. Adapted from ref 69.
At all times, the concentration of 4-carboxybenzaldehyde is
smaller at greater temperatures. Temperature has the effect of
decreasing the amount of 4-carboxybenzaldehyde as it
increases. In an industrial reactor, temperature is indirectly
controlled by pressure, showing a direct proportionality
between both physical properties.
4.2. Water Effect on Activity
The stoichiometric reaction of p-xylene oxidation with oxygen
yields two water molecules. Water is produced mainly as a
byproduct in the main reaction but also in other chemical
reactions such as oxidation to carbon oxides of both p-xylene
and acetic acid. Water is separated from acetic acid by means of
fractional or azeotropic distillation. In addition, the water
present in the reaction medium may also come as part of the
feed streams to the reactor, as an impurity or contamination.
Concerning the reaction rate, water has a net decreasing
effect,21,48,66 as seen from Figure 18b.
From Figure 18a, as water concentration increases, relative
rate decreases, showing that water concentration has a
decreasing effect on activity. The decreasing effect is due to a
progressive substitution of acetate ligands coordinated to
cobalt,48 which occurs as water in the medium increases,65 as
seen from Figure 19a and 19b. However, the effect of water on
activity may not be so direct and is, and it has, in fact, a subtle
effect, which needs to be balanced and accounted for. Water
may have a positive effect on activity, as74 found for peroxide
initiation of hydrocarbons like tetralin, cumene, cyclohexene,
and methylcyclohexane. The protons of the water molecule
interact with hydroperoxide molecules, favoring splitting of the
O−O bond, yielding more radicals. This effect is only visible at
small quantities of water, water having an inhibiting effect at
higher quantities. Partenheimer75 compared the effect of water
in the oxidation of 4-chlorotoluene in anhydrous acetic acid and
acetic acid containing 5% water. The initial rate of oxidation is
higher in anhydrous acetic acid than the rate with 5% water, but
at longer reaction times, the effect is the opposite.
Water may have an oxidation-promoting effect due mainly to
the interaction with catalyst. During oxidation, benzylic
bromides are formed, which are known to be catalytically
inactive forms of bromine. In fact, in anhydrous acetic acid the
initial rates are high, but as benzylic bromides are formed, the
catalyst loses bromine, becoming deactivated, which explains
the decreasing rates of oxidation at longer reaction times. In
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Chemical Reviews Review

Figure 18. Decreasing effect of water in p-xylene oxidation catalyzed by cobalt acetate: (a) data from ref 48; (b) reaction temperature 120 °C and air
pressure of 10.3 bar. Adapted from ref 21.

Figure 19. Effect of water on (a) Co/Mn/Br-catalyzed oxidation of 4-chlorotoluene and p-toluic acid; (b) molecular oxygen uptake during Co/Mn/
Br-catalyzed oxidation of 4-chlorotoluene. Adapted from ref 75.

acetic acid with 5% water, the initial rates are lower, due to
water inhibition, but at higher reaction times, water hydrolyzes
the benzylic bromide, releasing it to regenerate the catalyst,
increasing the rate.
The balanced effect of water may be summarized as follows:
reactivity of peroxy radicals of aldehydes and alcohols, catalyst
inhibitor conversion, and less oxidation of Mn(II) to Mn(IV),
leading to less MnO2 formation and faster Br− oxidation, are
favored at lower water concentrations; hydrolysis of benzylic
bromide, less formation of aryl formate and inhibiting phenol,
less carboxylic acid metal precipitation, and higher reactivity of
peroxy radicals due to acetic acid H bonding are favored at
higher water concentrations.75 Wang et al.76 found that water
has the effect of decreasing the rates of the oxidation reactions
in the first methyl group and increasing the rates of the
oxidation reactions of the second methyl group. Overall, there
is an optimum water content in the reaction media above which

Figure 20. Reaction rate constant kj as a function of water content and batch reaction time as a function of initial water. Data from ref 76.

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Chemical Reviews
Figure 21. Experimental and simulated 4-carboxybenzaldehyde concentration at different catalyst concentrations at 191 °C and 40 bar oxygen partial
pressure: scatter, experimental; line, data fitting. Br/metals ratio = 0.7. Adapted from ref 73.
the global reaction rate is decreased, hence activity, and below
which the rate is increased.
The reason can be explained in terms of changes in the
catalyst structure. In anhydrous acetic acid most of the bromide
ions are coordinated to the metal, but this rapidly decreases as
water increases. When bromide is coordinated directly to the
metal, electron transfer from the Br− ligand to the Mn3+
metallic complex center occurs easily. At higher water
concentrations, as aqua ligands progressively substitute bromide
ligands, the latter are in the outer coordination sphere of the
complex, coordinated through hydrogen bonds to aqua ligands
(see Figure 14). This increases the resistance of electron
transfer from Br− to the metal cation, as per eqs 107 and 108,
decreasing the reaction rate. Also, with increasing number of
aqua ligands approach of the organic intermediates and
transient species from entering them metallic inner coordina-
tion sphere of the catalyst is prevented.77 On the other hand,
the oxidation potential of metals is also changed. For the redox
pair Co3+/Co2+, the reduction potential decreases from 1.9 V in
acetic acid to 1.84 V in water, making reduction of the cobaltic
ion to cobaltous ion easier, thus enhancing the reaction rate as
water increases. For oxidation of p-xylene and p-tolualdehyde,
the control steps are Mn3+ reduction by Br− as per eq 108 and
hydrogen abstraction by eqs 109 and 115, respectively.
Addition of water increases the resistance of electron transfer
from bromide ion to the metal cation, slowing down the
oxidation rate. However, for oxidation of p-toluic acid and 4-
carboxybenzaldehyde oxidation, for the abstraction step, the
first methyl has been oxidized to the electron-withdrawing
carboxy group. The electron-withdrawing effect decreases the
reaction rates of the step given by eq 108 and hydrogen
abstraction steps given by eqs 122 and 128, respectively. The
carboxyl group makes radical stabilization difficult to occur (see
eq 32), and the control step of both p-toluic acid and 4-
carboxybenzaldehyde oxidation processes shifts to generation
of Co3+, controlled by the reaction given by eq 109 and
propagation steps given by eqs 123−125 and eqs 129−131,
respectively. Addition of water decreases the redox potential of
Co2+/Co3+ and Mn2+/Mn3+ and makes the oxidation of Co2+
by Mn3+ as per eq 106 and reactions in the propagation steps
easier, resulting in oxidation rate enhancement. When water
content exceeds the optimal value wH2O, the resistance of
electron transfer becomes the control step once again. Overall,
the effect of water on rate is a competition between an
inhibiting coordination effect and an electrochemical promot-
ing effect.
4.3. Catalyst Concentration Effect on Activity
Activity normally increases with catalyst concentration up to a
maximum value and then decreases.21 This observation is
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consistent with the rate law given by eq 48. Figure 21 shows the
time evolution of 4-carboxybenzaldehyde concentration in p-
xylene air oxidation in acetic acid with different concentrations
of Co/Mn/Br catalyst.
Similar observations resulted for p-xylene, p-tolualdehyde,
and p-toluic acid. In all experiments, the total amount of
catalyst varied but the Co/Mn/Br ratio was kept constant,
keeping the catalyst composition identical. Drawing a vertical
line intercepting the 4 curves at a given time, it is easily seen
that 4-carboxybenzaldehyde and the other main intermediates
concentration decrease as catalyst concentration increases,
showing that the activity of the catalyst has increased, Figure
22.
Figure 22. Intermediate product concentration variation with total
catalyst concentration. Catalyst composition kept constant. Adapted
from ref 73.
4.4. Cobalt/Manganese and Bromine/Metals Ratios Effect
on Activity
The cobalt/manganese ratio has an overall strong effect on the
rate of each main step in the oxidation of p-xylene, but the
different steps of eq 105 show different sensitivities.78 The two
last steps, oxidation of p-toluic acid and 4-carboxybenzaldehyde,
show a higher rate of sensitivity toward the [Co]/[Co + Mn]
ratio when compared with the rather insensitive two first steps.
The rate constant shows an increasing trend with increasing
ratio, up to an inflection maximum, from where it starts to
decrease, showing that a minor quantity of manganese metal is
required. Because the electron-transfer rate between catalyst
and electron depends on the catalyst cluster structure, catalysis
activation of the cluster is different at different [Co]/[Co +
Mn] ratios. The optimum ratio, the highest achieved rate at a
given ratio, shows a decreasing trend with increasing temper-
ature, as shown by Figure 23.
At lower temperatures, the optimum ratio is nearly close to 1,
meaning that cobalt is the dominant metal species is the
catalyst, which accounts for its well-known higher catalytic
activity when compared with manganese. As temperature rises,
its effect on promoting activity compensates for the lower
Chemical Reviews
Figure 23. Temperature dependence trend of the optimum [Co]/[Co
+ Mn] ratio. Adapted from ref 78.
manganese catalytic activity, allowing its content in the catalyst
to increase. This trend is consistent with the observation made
by Cheng and co-workers, that the [Co]/[Co + Mn] ratio
effect on the variation is much more remarkable at lower
temperatures. Figure 2479 shows a plot of the variation of the
Figure 24. Catalyst concentration as a function of the bromine/metals
at constant activity. Adapted from ref 79.
total catalyst concentration as a function of the bromine/metals
ratio to keep activity constant, in this case, the same 4-
carboxybenzaldehyde in product. It can be seen catalyst
function decreases with decreasing bromine/metals over a
ratio of 0.3; increasing the ratio has little effect on activity.
However, below 0.3, the amount of catalyst required to hold
the activity constant increases sharply. This observation is
consistent with the known Br role in the mechanism: bromine
Figure 25. Difference in oxygen uptake variation with addition of alkali metals throughout the oxidation reaction of p-xylene. Adapted from ref 81.
S dx.doi.org/10.1021/cr300298j | Chem. Rev. XXXX, XXX, XXX−XXX
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is required even at low amounts to catalyze the reaction
properly, and its absence has to be compensated with larger
amounts of catalyst. Similar trends on both ratios were found
by Kamiya and co-workers,62 as shown in Figures 8 and 9.
4.5. Agitation Effect on Activity
Brill48 reported that the oxidation reaction of p-xylene appears
to be independent of rapid stirring, although with very slow
agitation both the rate and the yields are strongly affected. As
one may expect, a regime of poor mixing will lead to a decrease
in the contact between the oxygen molecule and the
hydrocarbon radicals.
4.6. Alkali Metal Effects on Activity
Apart from hydrogen bromide, other sources of active bromine
possible in the AMOCO MC include sodium bromide and
potassium bromate.21 Use of sodium bromide as a substitute for
hydrogen bromide is desirable in order to minimize corrosion
of equipment and pipework. When hydrogen bromide is used
as the source of active bromine, sodium hydroxide is added to
control corrosion in several points of the plant and necessarily
ends in the recycled solvent to the reactor feed lines. Line
flushing between vessels is also made with sodium hydroxide
whenever a line choke occurs. It is therefore important to assess
sodium influence in the p-xylene oxidation chemistry. Jhung
and co-workers,80−82 studied the effect of alkali metal addition
to p-xylene oxidation media by establishing a comparison of the
acceleration and deceleration of oxygen uptake relative to a
baseline with no alkali metal addition.
As Figure 25 shows, deceleration occurs in the early stage of
the reaction and acceleration occurs in the later stage and both
increase with the alkali metal concentration, in the studied case,
potassium. In addition, the deceleration in the beginning of the
reaction is of the same magnitude as the acceleration in the
later phase of it. Also, Jhung and co-workers found that the
effect of potassium addition is higher when the manganese and
bromine contents in the catalyst are low. In fact, the Co/Mn/Br
catalyst system is activated the most when alkali metal addition
equalizes the atomic concentration of bromine, which,
according to Jhung, means the existence of an optimum for
its concentration. The acceleration and deceleration effect is
due to the alkali metal and not to the basicity of the
companying anion and explained by the influence in the
coordination of bromine to the catalyst metals throughout the
Co−Mn−Br oxidation−reduction catalytic cycle shown in
Figure 10. The alkali metal influence on the catalytic cycle
Chemical Reviews
Figure 26. Influence of the alkali metal in the Co−Mn−Br catalytic cycle. Adapted from ref 80.
appears to be independent of the functional groups of the
molecule being oxidized, which suggest that the interaction is
with the catalyst and not with the organic substrate. Figure 26
shows the influence of the alkali metal in the Co−Mn−Br
catalytic cycle.
In the early stage of the reaction, rate deceleration is caused
by interaction of the alkali metal with the bromine ion, binding
it and diverting it from the reduction of Mn3+ ion in the
catalytic cycle. With the progress of the reaction are formed
other substances; catalyst poisoning species that also interact
with bromine, slowing the reaction. In a later stage of the
reaction, as the alkali metal progressively interacts with bromine
and the poisonous species, the interaction between bromine
and the poisonous species will decrease and rate will increase
again.
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5. SELECTIVITY
The selectivity of a reaction may be defined as the fraction of
the starting material that is converted to the desired product. In
a broader view, selectivity can be defined between the desired
chemistry and the undesired chemistry. Within the scope of p-
xylene catalytic oxidation in acetic acid media, one can consider
not only the main and parallel reactions in which p-xylene is
consumed yielding other products than terephthalic acid but
also reactions that consume acetic acid. Degradation of p-xylene
to carbon oxides and to aromatic byproducts and acetic acid
degradation also to carbon oxides, methyl bromide, methane,
and methyl acetate are reactions that contribute to an overall
economic yield decrease of a the process. Like in activity
monitoring, for selectivity evaluation, 4-carboxybenzaldehyde
can be used to establish a baseline to assess the competitive
chemistry in p-xylene oxidation. In the AMOCO process,
Chemical Reviews
conversion of p-xylene to terephthalic acid is nearly 100%
complete, so 4-carboxybenzaldehyde as a percentage of
terephthalic acid product is normalized against the p-xylene
feed rate, thus being a good selectivity indication. This allows
byproduct formation also to be normalized against the feed rate
of p-xylene and be used as a comparative measure against 4-
carboxybenzaldehyde as a percentage of terephthalic acid
product in selectivity assessment.
5.1. Carbon Oxides
Complete oxidation of a hydrocarbon yields water and carbon
dioxide. As seen from eq 105, progressive and partial oxidation
of a methyl group in organic molecules yields a carboxylic acid
group. If further oxidation is occurs then decarboxylation of the
molecule occurs, yielding carbon monoxide and carbon dioxide
as products, COx. Decarboxylation occurs not only in the
aromatic acids, either intermediate or product, but also in the
acetic acid solvent. In acidic medium, acid-catalyzed decarbox-
ylation reactions are dependent on factors such as the ionic
strength and substituents on the aromatic ring.83 The
mechanism is given by
In dilute acid solution, ipso protonation is the rate-
determining step, whereas in highly acidic solutions, the rate-
determining step is aromatic carbocation decarboxylation.
Aromatic acid decarboxylation can also occur by a free-radical
pathway, catalyzed by metals and radicals, though hydrogen
abstraction from the carboxylic group of the molecule.
The benzoyloxyl radicals formed rapidly decarboxylate to
yield aryl radicals. The aryl radicals can then react with several
other molecules to yield other undesired byproducts,
decreasing the overall selectivity. Regarding decarbonylation,
very little carbon monoxide, generally less than 0.01%, is
formed during the reaction of benzaldehydes described, which
is indicative that decarbonylation is not important in aromatic
aldehyde autoxidations.77 It may then be expected that most of
the CO comes from decarbonylation of acetic acid and not the
benzaldehydes. As may be expected, the effect of catalyst
increase in the oxidation is to increase COx formation, as shown
by Figure 27.
The effect of catalyst composition in terms of bromine/
metals ratio is shown in Figure 28.
The total amount of carbon oxides moles per feed mole of p-
xylene shows a minimum for a molar bromine/metals ratio
close to 0.3. As the ratio falls below the 0.3 minimum
production of carbon oxides increases rapidly. Above the
minimum formation of COx shows a less steep trend. This
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Review
Figure 27. Carbon oxides formation trend with increasing catalyst
concentration during p-xylene oxidation catalyzed by a Co/Mn/Br
catalyst at 197 °C. Adapted from ref 79.
observation is consistent with a need for a balance between
bromine and metals: metals in their trivalent oxidation state
react with bromide ions to form bromide atoms, which will
abstract hydrogen atoms from methyl groups to yield radicals;
however, competitive degradation of carboxylic groups of both
product and solvent molecules to carbon oxides is favored by a
high concentration of metals, in particular cobalt, which has a
well-known ability to decarboxylate acids.49,84
Co3 + + CH3CO2 H ⇄ Co2 + + CH3CO2• + H+ (154)
Co3 + + CH3CO2•
CH3CO2 H
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Co2 + + CO2 + CH3CO2 CH3 + H+ (155)
Thus, as a result of these two competitive reactions, one can
expect an optimum Br/metals ratio to achieve greater catalyst
selectivity with respect to carbon oxides formation.
5.1.1. Carbon Oxides: Solvent Burning. Of particular
importance in industrial manufacture of terephthalic acid is
acetic acid solvent degradation to carbon oxides, as this is one
of the greatest parcels of operational costs. Not only does
addition of manganese into the catalyst feed promote oxidation
of the hydrocarbon due to the synergistic effect with cobalt, as
shown in Figure 10, but also it has been found that it decreases
the content of carbon oxides in the oxidation off-gas. 14C
isotopic experiments performed by Kenigsberg et al.85 lead to
the conclusion that acetic acid degradation into carbon oxides,
i.e., solvent burning, has a dependence on the manganese to
cobalt ratio. In addition, they also found the following.
• Carbon dioxides are formed from both the methyl and
the carboxylic groups of the acetic acid molecule.
• CO2 is formed in quantities higher than CO: from 3 to
26 times more.
• Cobalt has a stronger ability to form COx from the
carboxylic group.
• Manganese has a stronger ability to form COx from the
methyl group.
• Radicals from the main reaction also decompose acetic
acid, yielding methyl radicals and CO, CO2, formic acid,
and formaldehyde, Figure 29.
There is a minimum, located toward low [Mn]/[Mn + Co]
ratios, where COx formation can be optimized: low cobalt
content in the catalyst caused carbon oxides formation to
increase, but the same will be expected to happen if the cobalt
content becomes too high, Figure 30.
In Figure 30, the minimum COx formation corresponds to a
high cobalt content, with a general trend of COx formation
increasing with increasing manganese. However, Cheng78 and
Chemical Reviews Review

Figure 28. Carbon oxides formation trend with increasing bromine/metals molar ratio during p-xylene oxidation catalyzed by a Co/Mn/Br catalyst
at 197 °C. Adapted from ref 79.

Figure 29. Carbon oxides degree of decomposition trend dependence with [Mn]/[Mn + Co] ratio for 14CH3COOH and CH314COOH. Adapted
from ref 85.

Figure 30. Total COx formation trend dependence with [Mn]/[Mn + Figure 31. Carbon oxides generation trend dependence with [Co]/
Co] ratio for 14CH3COOH and CH314COOH. Adapted from ref 85. [Co + Mn]. Adapted from ref 78.

Li et al. showed that the formation rate constants of CO2 and

co-workers found the opposite trend at similar catalyst CO vary with process conditions that normally also affect p-
concentration magnitudes and temperature ranges, as seen xylene oxidation. CO2 and CO formation rate constants
from Figure 31. The main difference in the catalyst feed was the increase with increasing [Co]/[Mn] ratio and decrease with
source of bromine. Kenigsberg used NaBr, whereas Cheng used [Br]/[Co] ratio and decreasing temperature. Water concen-
HBr as the bromine source. Yet, the bromine to metals ratio tration has a promoting effect on COx formation rate constants
used by Kenigsberg was almost three times higher, which up to 10−15%, from which it begins to have an inhibiting effect.
suggests that bromine is the differentiating factor, most likely Increasing temperature, air flow rate, and total metals
due to changes in catalyst structure. concentration also increases COx formation rates.86 In later
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Chemical Reviews Review

Figure 32. Formation rates of (a) CO2 in batch oxidation experiment, (b) CO in batch oxidation experiment, (c) CO2 in semicontinuous oxidation
experiment, and (d) CO in semicontinuous oxidation experiment. Acetic acid/p-xylene weight ratios: (□) 20/1, (○) 10/1, (△) 5/1, (▽) 3/1; ()
model fitting. Adapted from ref 87.

work, Cheng et al. suggested that rates of solvent burning and 1

rCO2 = rCO
the main reaction are related and have a competitive 1−η x (158)
relationship between them.87 The observed rates of COx
formation during p-xylene oxidation in batch and semi- η
rCO = rCO
continuous experiments are shown in Figure 32a and 32b. 1−η x (159)
Data fitting is given by
and η being within the 0.244−0.252 range.
0.791NyCO 5.1.2. Carbon Oxides: Mechanism of Solvent Burning.
rCO2 = 2
Like the main reaction, solvent burning follows a free-radical
Vr{1 − (yO + yCO + yCO )} (156) oxidation mechanism. Throughout the p-xylene oxidation
2 2
several radicals are formed which can abstract hydrogen
atoms from other reactant, intermediate, product, or solvent
0.791NyCO molecules. Among these radicals, RCO• and RCOO• radicals
rCO =
Vr{1 − (yO + yCO + yCO )} will undergo decarbonylation and decarboxylation yielding CO
2 2 (157)
and CO2, respectively
where rCO2 and rCO are the CO2 and CO formation rates, RCO• + R′H → RCHO + R′• (160)
respectively, N is the air flow rate, Vr is the reaction volume,
and yO2, yCO2, and yCO are, respectively, the oxygen, carbon RCO• + O2 → RCOOO• (161)
dioxide, and carbon oxide molar fractions in the reactor off-gas. RCOO• + R′H → RCOOH + R′• (162)
The behavior of the batch experimental curves shows a camel
back like shape: an initial sharp increase of COx to a first peak, RCO• → R• + CO (163)
from which it decreases to a minimum; from this minimum the
rate increases again to a new peak, from which it drops at the RCOO• → R• + CO2 (164)
end of the reaction. In the semicontinuous curves the COx where R represents any hydrocarbon radical and R′H
generation rate increases sharply at the beginning of the represents any molecule with an abstractable hydrogen atom
reaction, after which it shows a relatively stable decreasing including acetic acid
plateau throughout most of the reaction time. At the end of the
reaction the COx formation rate drops sharply when the p- I• + CH3COOH → HI + CH3COO• (165)
xylene feed stops. The fact that CO and CO2 formation rates
show the same behavior either in batch or in semicontinuous I• + CH3COOH → HI + •CH 2COOH (166)
experiments leads to the conclusion that the two rates are •
proportional, i.e., rCO2 = ηrCO, with CH 2COOH + O2 → CO2 , CO, H 2O (167)

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Chemical Reviews Review

Figure 33. Comparison between solvent burning and the main reaction on (a) batch experiment and (b) semicontinuous experiment. Adapted from
ref 87.

87
Figure 34. Relation of terephthalic acid selectivity and rC̅ Ox in (a) batch experiment and (b) semicontinuous experiment. Adapted from ref .

CH3COO• → CH3• + CO2 (168)
I• represents any radical, like the very strong oxidizing radical
OH• or PhCH2OO• but also cobalt or manganese in their
trivalent oxidation state, originating from the thermal
decomposition of the respective acetates, which is found to
be the most important.88 Consumption of I in the burning
reaction thus shows a competition relationship between the
main reaction and the solvent burning reaction. In the latter,
the methyl radical is of particular importance as it yields some
the most important byproducts in the MC-AMOCO industrial
process, such as methyl bromide, methane, and methyl acetate
CH3• + Br• → CH3Br (169)
CH3• + RH → CH4 + R• (170)
reaction and the main reaction is shown in Figure 33 for both
batch and semicontinuous experiments.
The results suggest an interstimulative relationship between
both reactions. Considering the scheme in eq 105, the rate of
CO2 formation shows an accompanying behavior to both the
rates of formation of all intermediates, rall, and formation rates
of p-toluic acid and terephthalic acid, r2 + r4, suggesting a
proportionality relation. While Call increases, the opportunity
that the reactant and intermediates are attacked by the active
free radicals and metal ions increases too and the opportunity
for solvent being attacked decreases reversely. Therefore, the
rate of the burning side reaction, rCO2, will decrease faintly with
increasing concentrations of reactant and intermediates, Call.
For batch and semicontinuous oxidations, the rate of CO2
formation is, according to Cheng, given by

CH3• + CH3COO− → CH3COOCH3 (171) α1(r1 + r2)

rCO2 = 4
+ α2(r1 + r2)
(∑i = 1 Ci + ε) (173)
CH3• + O2 → CO2 , CO, H 2O (172)

Comparison between the CO2 generation rate and rates of with α1 and α2 being empirical model parameters and rCO2 =
intermediate reaction as per eq 105 for the solvent burning ηrCO.
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Chemical Reviews Review

Figure 35. Methyl bromide formation trend at a constant 4-carboxybenzaldehyde with increasing bromine/metals molar ratio during p-xylene
oxidation catalyzed by a Co/Mn/Br catalyst at 197 °C. Adapted from ref 79.

Figure 36. Comparison of methane formation with CO2 and CO formation with increasing metal concentration at constant air flow. Adapted from
ref 84.

From the relationship between the main reaction and solvent
burning, the following COx formation−terephthalic acid
selectivity relation arises as depicted in Figure 34.
In batch oxidation, the burning side reaction rC̅ Ox decreased
with the increase of p-xylene/acetic acid mass ratio but
terephthalic acid selectivity increased. In semicontinuous
oxidation, the burning side reaction rate rC̅ Ox increased with
the increase of p-xylene feed rate but terephthalic acid
selectivity remained relatively constant. In semicontinuous
oxidation, rC̅ Ox is lower than that in batch oxidation and
terephthalic acid selectivity is slightly higher. One conclusion is
that the operation mode affects the p-xylene oxidation process,
and therefore, in an industrial continuous reactor there is an
optimal operation mode in which low burning side reaction and
high terephthalic acid selectivity can be achieved.87
5.2. Methyl Bromide
As mentioned above, methyl bromide is formed in side
reactions during oxidation of p-xylene. Its formation is the
result of a combination of methyl radicals with bromine, as per
the reaction in eq 169. Methyl radicals come from degradation
of solvent or other aromatic molecules and bromine from
catalyst: therefore, methyl radical formation decreases the
overall yield and is an example of both catalyst selectivity
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decrease, as it formed one undesired product, and of activity
decrease. Methyl bromide, a gas in industrial process operating
conditions, is partially lost in the off-gas process and treated as
an effluent. The higher the formation of methyl bromide, the
lower the amount of bromine present in the catalyst, which has
the effect of decreasing its activity and selectivity.
Figure 35 indicates that there is an optimum Br/metals ratio
which yields a minimum of methyl bromide at a constant 4-
carboxybenzaldehyde in the product. At low Br/metals ratios,
the catalyst is not active enough and so a higher catalyst
concentration is required to keep 4-carboxybenzaldehyde
constant. However, high absolute catalyst concentrations lead
to decarboxylation of solvent and other carboxylic acids present
in the reactor. This yields more methyl radicals, which will yield
methyl bromide. At high Br/metals ratios, the high
concentration of bromine favors formation of methyl bromide
as it reacts competitively with the methyl radical, diverting it
from other reactions. Optimal conditions for low methyl
bromide formation and high catalyst selectivity are a balance
between other factors, which includes catalyst concentration
and composition.
5.3. Methane
As one of the byproducts formed from decarboxylation
degradation, methane is formed in eq 170. Methane is insoluble
Chemical Reviews
Figure 37. Comparison of methane formation with carbon dioxide formation with increasing air flow/metal ratio. Adapted from ref 84.
in the reaction media and present in the reaction off-gas. As
expected, increasing catalyst concentration causes more
decarboxylation to occur and more methyl radicals will be
formed, Figure 36. These will abstract hydrogen atoms from
other molecules yielding methane. Abstraction of hydrogen
from methyl groups of p-xylene is favored by the resonance
stabilization of the radical, as per eq 30.
Less methane, relative to carbon oxide, is seen as the air
flow/metals ratio increases, as shown in Figure 37, and the ratio
of carbon dioxide/methane increases. As the air flow/metals
ratio decreases, the oxidation media becomes increasingly
starved of oxygen and methyl radicals tend to preferentially
abstract hydrogen atoms from other molecules to form
methane as per eq 170 rather than forming carbon oxide as
per eq 172. A competitive behavior appears to exist. In addition,
one may expect that increasing the degree of agitation within an
industrial reactor would also contribute to formation of
methane the same way increasing the air flow/metals ratio.
5.4. Methyl Acetate
Methyl acetate is one of the main byproducts in the
terephthalic acid process.66 Its formation can be described as
oxidative decarboxylation of acetic acid89
2CH3COOH + 0.5O2 → CH3COOCH3 + H 2O + CO2
(174)
Methyl acetate formation in industrial production of
terephthalic acid is of great importance as it is formed mainly
by acetic acid degradation, causing solvent loss, which is
controlled to a certain extent by recovering it in the process and
recycling it to the oxidation reactor, where it is reconverted to
acetic acid by hydrolysis.66,90,91 Decarboxylation is initiated by
peroxide interaction with the carboxylic or methyl groups of
acetic acid, followed by degradation of the resulting radicals,
yielding carbon monoxide, carbon dioxide, methanol, form-
aldehyde, and formic acid.85,88,89 Methanol results from
reaction between a methyl radical and water. Oxidation of
methanol initially yields formaldehyde, which upon further
oxidation yields formic acid. Formic acid can esterify with
methanol to yield methyl formate.88
CH3CO2 H + ROO• → ROOH + CH3• + CO2 (175)
CH3CO2 H + ROO• → ROOH + •CH 2CO2 H (176)
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•
CH 2CO2 H + O2
→ CO, CO2 , CH3OH, CH 2O, HCOOH (177)
Both methyl radical and methanol can react with acetic acid
to yield methyl acetate
CH3• + Mn + 1 + CH3COOH
→ CH3COOCH3 + Mn + + H+ (178)
CH3OH + CH3COOH → CH3COOCH3 + H 2O (179)
When the metal catalyst is in the form of acetates, the metal
in its higher oxidation state can oxidize the acetate ligand to
carbon dioxide and methyl acetate49
2Co(CH3COO)3 → 2Co(CH3COO)2 + CO2
+ CH3COOCH3 (180)
Methyl acetate formation depends on the process conditions
that lead to acetic acid degradation like water concentration,
temperature, p-xylene oxidation rate, catalyst concentration,
and composition, as shown in Figures 38 and 39.
The role of water in decreasing methyl acetate formation is
due to ligand substitution in the catalyst, decreasing its
activity49,77 by destabilizing the highest oxidation states of the
metals responsible for the decarboxylation reaction and also
due to its role as reactant in methyl acetate hydrolysis to acetic
acid and methanol, the latter undergoing oxidation to carbon
oxides.
CH3COOCH3 + H 2O → CH3COOH + CH3OH (181)
Just like the activity behavior of catalyst with water
concentration, methyl acetate formation does not always
decrease with increasing water. Roffia found the water
concentration optimum to be within the range 12−16%. At
lower water concentrations, methyl acetate formation is high
mainly due to increased catalyst activity, decomposing solvent
molecules. The increase of p-xylene rate in an oxidation reactor
is proportional to its feed rate. Increasing the amount of p-
xylene comparatively increases its competition with acetic acid
solvent molecules for reacting with catalyst and peroxides,
decreasing methyl acetate formation. An optimized p-xylene/
solvent ratio will contribute to less methyl acetate formation.
Like in formation of carbon oxides, increasing the total catalyst
Chemical Reviews
Figure 38. Methyl acetate formation trends with variation of water
concentration. (a) Three levels of p-xylene oxidation rate (mol kg−1
h−1); Co2+, 0.022%; 220 °C; stirring speed, 500 rpm. (b) Three levels
of Co2+ concentration (% wt); 220 °C; p-xylene oxidation rate, 3.8
stirring speed, 500 rpm. (c) Three levels of temperature; Co2+,
0.022%; p-xylene oxidation rate, 3.8; stirring speed, 500 rpm. Adapted
from ref 89.
concentration also leads to increased methyl acetate formation.
Association of these two trends is explained easily by the
mechanism of methyl acetate formation which requires methyl
radicals, as per eq 178, which in turn are formed during solvent
decomposition through eq 175. The effect of increasing
temperature increases methyl acetate formation, especially at
low water concentrations. This is explained by the higher
catalyst activity at higher temperatures, leading to more methyl
acetate formation. Methyl acetate formation also depends on
the catalyst composition. As shown in Figure 39, methyl acetate
formation tends to decrease with increasing bromine/metals
ratio. As seen previously, to a certain extent decreasing the
AA
Review
Figure 39. Methyl acetate formation trend with varying bromine to
metals ratio. Adapted from ref 89.
bromine/metals ratio decreases COx formation, meaning less
methyl radicals and hence less methyl acetate. Also, bromide
ions, by coordinating to the catalyst metals, replace acetate ions
in the electron-transfer process between ligand and metal in its
high oxidation state, hindering RCOO• acyloxy radicals
formation and promoting formation of bromine radicals,
which are promoters of the main reaction synergistic cycle in
detriment of the methyl acetate byproduct formation secondary
reaction.89
Increasing the relative amount of acetate ion in catalyst
composition also has the effect of increasing methyl acetate
formation.92 As seen above,65 as the catalyst is more acetate
ligand rich, i.e., less coordinated aqua ligands, its activity
increases, yielding more carbon oxides and methyl acetate.
5.5. Selectivity Assessment
As mentioned above, for selectivity evaluation during p-xylene
oxidation, monitoring 4-carboxybenzaldehyde in terephthalic
acid product is a valuable tool. The optimization goal is to have
a high yield of terephthalic acid with a low content of 4-
carboxybenzaldehyde and simultaneously low burning to
carbon oxides. Figure 41 shows CO2 formation vs 4-
carboxybenzaldehyde content in terephthalic acid product at
different temperatures.
The shape of the curves shows competition behavior
between 4-carboxybenzaldehyde content in terephthalic acid
product and unwanted degradation of p-xylene and acetic acid
to carbon dioxide. It can be seen that for all the curves carbon
dioxide formation increases as 4-carboxybenzaldehyde de-
creases. Driving 4-carboxybenzaldehyde to low levels requires
use of a higher catalyst concentration. This causes carbon
oxides formation to be higher, as shown in Figures 28 and 36,
in particular, if higher cobalt concentrations are used, as shown
in Figures 30 and 31. As an alternative, for achieving a lower 4-
carboxybenzaldehyde concentration, more severe oxidation
conditions, i.e., higher temperatures are required. This will
cause more carbon dioxide to be formed, as also confirmed
when looking at Figure 42, which shows the effect of
temperature on 4-carboxybenzaldehyde and carbon oxides at
constant catalyst composition.
Typically, for a constant level of burn, an optimal catalyst
composition to obtain a minimum 4-carboxybenzaldehyde
exists.97 The trade-off is to achieve terephthalic acid product
with low 4-carboxybenzaldehyde content suitable for PET
manufacture and simultaneously reduce solvent burning, which
has a detrimental effect on the manufacturing process
economical reliability. The cobalt to manganese ratio and the
bromine to metals ratio are essential 4-carboxybenzaldehyde
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Figure 40. Carbon oxides and methyl acetate formation trends with varying catalyst acetate to metals ratio during p-xylene and pseudocumene
oxidation. Adapted from ref 92.

Figure 41. Carbon dioxide formation vs 4-carboxybenzaldehyde present in terephthalic acid product at different temperatures. Black curves on the
left vertical axis, and gray curves on the right vertical axis. Adapted from refs 93−95.

Figure 42. Effect of temperature on 4-carboxybenzaldehyde and Figure 43. 4-Carboxybenzaldehyde in terephthalic acid product as a
carbon oxides at constant catalyst composition. Scatter: data points at function of the Co/(Co + Mn) ratio trends at different relative levels
190, 175, and 170 °C. Solid line: data trend. Adapted from ref 96. of burning. Adapted from ref 97.

optimization parameters. Figure 43 shows trends of 4-
carboxybenzaldehyde at different levels of burning with
changing metals ratio in the catalyst. The minimum of 4-
carboxybenzaldehyde occurs at higher cobalt concentrations,
showing its higher selectivity when compared with manganese.
However, a further increase causes a steep increase in 4-
carboxybenzaldehyde, which means that the catalyst is losing its
selectivity: the Br/Mn/Co synergy cycle (Figure 10) is being
broken. In addition, the loss of selectivity is also accompanied
AB
by an increase in carbon oxides formation, as cobalt is attacking
the molecules’ carboxylic group, in particular, that of acetic acid.
Figure 44 shows a similar behavior when varying the
bromine/metals ratio at different levels of burning. Decreasing
the bromine/metals ratio causes 4-carboxybenzaldehyde
concentration to increase, because the catalyst loses activity,
resembling a bromine-free metal catalyst. Increasing the ratio
too much causes the catalyst to be poor in metals and not to be
able to catalyze peroxide decomposition reactions properly.
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Chemical Reviews
Figure 44. 4-Carboxybenzaldehyde in terephthalic acid product as a
function of the Br/(Co + Mn) ratio trends at different relative levels of
burning. Adapted from ref 97.
Other substances formed in the oxidation process, such as
2,6-dicarboxyfluorenone or 2, 6-DCF, which have a detrimental
effect on terephthalic acid color and hence in its quality, may
also be used for selectivity monitoring.98 Figure 45 shows the
2,6-dicarboxyfluorenone concentration and carbon oxides
formation trends with changing catalyst composition.
Increasing COx formation with increasing the cobalt to
manganese ratio and with the relative increase of the bromine
to metals ratio is a consequence of greater catalyst activity,
leading to higher decomposition of carboxylic groups of the
molecules within the reaction media. Decreasing the 2,6-
dicarboxyfluorenone concentration requires both a more active
and a more concentrated catalyst, with progressively greater
cobalt/manganese ratios and bromine contents, either in a
smaller range as shown by Figure 45b or in a wider ratios range
as shown by Figure 46.
Like in the case of 4-carboxybenzaldehyde, 2,6-dicarboxy-
fluorenone and carbon oxides show an antagonistic competitive
behavior. Figure 47 shows that cobalt-rich catalyst composi-
tions, i.e., increasingly higher Co/Mn, lead to progressively less
2,6-dicarboxyfluorenone at the expense of more COx formation.
Figure 48 shows the effect of bromine to metals ratio on
selectivity at constant 2,6-dicarboxyfluorenone concentration.
The data shows that for a given catalyst composition,
allowing the Br/(Co + Mn) to vary to maintain a constant 2,6-
dicarboxyfluorenone concentration, carbon oxides formation
Figure 45. (a) 2,6-Dicarboxyfluorenone concentration trend in reaction effluent slurry, and (b) carbon oxides formation trend with simultaneously
changing Br/(Co + Mn) and Co/Mn ratios: cobalt held constant; bromine and manganese varying. Adapted from ref 98.
AC
Review
increases as Br/(Co + Mn) decreases. This shows that the
catalyst selectivity toward product terephthalic acid worsens as
the bromine to metals ratio decreases, forming more carbon
oxides. The reason behind this is that catalyst activity decreases
as bromine content decreases. To keep 2,6-dicarboxyfluorenone
concentration constant a catalyst compensation is necessary. In
proportion, cobalt content will necessarily increase, making the
catalyst more selective to decarboxylation reactions, thus
forming more carbon oxides.
Figure 49 shows the carbon oxides formation trend when the
inverse of 4-carboxybenzaldehyde concentration in product
terephthalic acid changes at different sodium concentrations
and constant catalyst feed.
As seen in Figures 41 and 48, the inverse relationship
between 4-carboxybenzaldehyde and carbon oxides is also
maintained in the presence of sodium. From Figure 49, despite
the scarcity of experimental data, a trend arises: for constant 4-
carboxybenzaldehyde concentration in product terephthalic
acid, as the sodium concentration increases, carbon oxides
formation tends also to increase, which means that higher
sodium concentrations tend to worsen the selectivity. This
selectivity decrease may be related with decreased activity in the
presence of alkali metals in the early stage of the reaction as
observed by Jhung and co-workers.80−82 Overall, 4-carbox-
ybenzaldehyde, 2,6-dicarboxyfluorenone, and carbon oxides all
have an unfavorable effect on terephthalic acid manufacture,
either by having a quality specification decrease effect as high 4-
carboxybenzaldehyde and 2,6-dicarboxyfluorenone do or by
accounting for process economic losses as the burning of
solvent does. Driving process conditions to less solvent burn
leads to undesired byproducts increase and vice versa. In
addition, carbon oxides formation is preceded by degradation
not only of solvent but also of carboxylic groups of other
molecules in the reaction media, which yields several free
radicals. This causes not only solvent and terephthalic acid loss,
but the combination of these radical also leads to formation of
other undesired byproducts, decreasing the overall selectivity
and efficiency of the process and product quality.
5.6. Byproduct Chemistry
The extent of selectivity of the oxidation of p-xylene to
terephthalic acid will determine the amounts of byproducts
formed during the reaction. Byproducts formation arises both
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Chemical Reviews Review

Figure 46. 2,6-Dicarboxyfluorenone concentration trend in reaction effluent slurry with changing Co/Mn and Br/(Co + Mn) ratios over a wide
range. Adapted from ref 98.

Figure 47. Carbon oxides vs 2,6-dicarboxyfluorenone concentration trend (black line read on left vertical and low horizontal axis), and 2,6-
dicarboxyfluorenone and carbon oxides formation trends with changing Co/Mn ratio (dark gray and light gray lines read on right vertical and upper
horizontal axis). Adapted from ref 98.

Figure 48. Carbon oxides vs 2,6-dicarboxyfluorenone concentration at different Br/(Co + Mn) ratios. Adapted from ref 98.

from degradation of the molecules and subsequent combina- As seen previously, acetic acid degradation leads to formation
tions among them to form several more products. of the methyl radical, which then leads to formation of carbon
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Chemical Reviews
Figure 49. Carbon oxides formation with changing 4-carboxybenzaldehyde concentration in product terephthalic acid at different sodium
concentrations. Dashed gray lines represent trend extrapolations. Adapted from ref 99.
oxides, methane, formic acid, formaldehyde, methanol, methyl
bromide, and methyl acetate. Decarboxylation of the carboxylic
group of any other molecule, including both terephthalic acid
and its preceding intermediates, also leads to formation of
methyl radical with subsequent formation of those products
and also to formation of other radicals, which upon further
recombination can yield more complex molecules. In addition,
the impurities present in p-xylene and in the solvent in
commercial manufacture of terephthalic acid are also a source
of molecules that can undergo several transformations like full
or partial oxidations and subsequent decarboxylation to yield
other byproducts. For instance, p-xylene may contain impurities
such as toluene, o-xylene, m-xylene, pseudocumene, 1,2,3-
trimethylbenzene, and 1,3,5-trimethylbenzene. The corre-
sponding carboxylic acids resulting from oxidation of these
impurities, i.e., benzoic acid, o-phthalic acid, isophthalic acid,
trimellitic acid, hemimellitic acid, and trimesic acid, are then
found in the oxidation mother liquor.100 Formation of alkyl
radicals throughout the oxidation reaction can also cause
catalyst decomposition and deactivation. Considering reaction
of the methyl radical with bromine to yield methyl bromide as
per eq 169 is the simpler form of bromoalkane formation. This
last secondary section is of particular importance as it consumes
bromine from the catalyst, deactivating it. Some of the several
byproduct pathways are shown in Figure 50.
Aside from yield decrease, byproducts represent a quality
issue for PET manufacture, as many of them decrease
polymerization rate and, being monofunctional, act as chain
termination agents, causing the polymer to have an undesired
molecular weight and improper color and optical properties.101
Because solvent is recycled, they are always present the
Figure 50. Byproduct chemistry pathways in the oxidation of p-xylene
in acetic acid by a Co/Mn/Br catalyst.
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oxidation media and their concentration tends to build up,
unless a process purge is made. It is therefore important to
know what the main byproducts formed are.102
5.6.1. Acetic Acid Derivatives. Decomposition of acetic
acid and acetate ligands by radicals or metals yields several
byproducts via the CH3• , •CH2COOH, and CH3COO•
radicals, as shown previously by eqs 160−167 and 175−181,
Figure 51.
Figure 51. Main byproducts formed from decomposition of acetic
acid.
Sun et al. attributes formation of the acetic acid hydro-
peroxide intermediate HOOCH2CO2H as the source of CO,
CO2, formaldehyde, and formic acid.103 As mentioned above,
acetic acid degradation together with aromatic acid decarbox-
ylation and decarboxylation are the main sources of CO and
CO2. Formation followed by coupling of two •CH2COOH
radicals is related also to formation of succinic acid102
2•CH 2COOH → HO2 CCH 2CH 2CO2 H (182)
Succinic acid can be brominated, yielding bromosuccinic
acid, which in turn can lose a HBr molecule to yield maleic acid
and fumaric acid isomers. When manganese in the trivalent
oxidation state attacks the methyl group of acetic acid
generating the carboxymethyl radical, glycolic acid can result
from reaction with methane in the presence of water. Glycolic
acid can then either react with acetic acid with loss of one water
molecule to yield acetoxyacetic acid or be oxidized to glyoxylic
acid. The latter can yield oxalic acid upon reaction with a water
molecule. All these substances upon decarboxylation and
decarbonylation will yield, respectively, CO2 and CO in the
off-gas.88
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This electrophilic radical can add to p-xylene and other
aromatic molecules
Methyl radicals formed from acetic acid decomposition can
also react with other aromatic molecules and radicals forming
more byproducts via methyl bromide. They can add to an
aromatic ring in Friedel−Crafts-type reactions,104,105 promoted
by excessive solvent degradation and poor gas−liquid oxygen
transfer and catalyzed by metals, such as iron, from corrosion of
equipment. An example of this reaction is formation of
trimellitic acid
byproduct chemistry as they yield considerably diverse radicals
which on combination with themselves, in nonmainstream
chemistry free-radical termination reactions, yield progressively
more complex products. Formation of benzoic acid derivatives
is preceded by decarbonylation and decarboxylation reactions
of carbonyl and carboxylic groups, respectively, and formation
of a phenyl radical. Phenyl radicals can abstract hydrogen from
other hydrocarbon and form benzoic acid, react with bromine
from the catalyst to form p-bromo benzoic acid, and be
oxidized to p-hydroxy benzoic acid.79,102

5.6.2. Benzaldehyde and Benzoic Acid Derivatives.

Considering p-tolualdehyde and p-toluic acid to be, respec-
tively, benzaldehyde and benzoic acid derivatives and 4-
carboxybenzaldehye a derivative of either one of them, their
reactions, other than those leading to terephthalic acid, also
account for formation of byproducts. Figure 52 shows some of Figure 53. Benzoic acid derivatives byproducts formed from
the byproducts formed from benzaldehyde reactions. decarbonylation and decarboxylation reactions. Adapted from ref 102.
Together with the common free-radical hydrogen abstraction
reaction, decarboxylation reactions play a major role in

Figure 52. Benzaldehyde byproduct chemistry; X = H, CH3. Adapted from ref 77.

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In the decarbonylation process, when a carboxy benzoyl
radical is formed it can react with methyl radicals to form p-
carboxy acetophenone
p-Xylene oxidation intermediates can undergo bromination
catalyzed by equipment corrosion metals
Another possible route for benzyl bromide formation is
through direct interaction of the alkyl aromatic molecule with
the bromide ion present in the coordination sphere of the
catalyst75
Phenol derivatives can react to form brominated compounds,
Figure 54.
Figure 54. Products resulting from bromination of phenol byproduct
derivative from benzoic acid. Adapted from ref 102.
Bromination reactions not only represent formation of
undesired products but also have the consequence of
deactivation of the catalyst. As benzylic bromides are formed,
byproduct cascades are started due to conversion of a much
more Co/Mn/Br active catalyst to a less active and less
selective Co/Mn catalyst, Br/(Co + Mn) decreases, which is
also responsible for coloration of the product.76 In addition, as
Figure 55. Some of the terephthalic acid derivatives formed in p-xylene oxidation. Adapted from ref 102.
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catalyst becomes progressively deactivated and the Br/(Co +
Mn) ratio decreases, formation of insoluble and product
blackening Mn(IV) compounds, like MnO2, also occurs.76,106
5.6.3. Terephthalic Acid Derivatives. Terephthalic acid
can also undergo decarboxylation and bromination reactions to
form some of the compounds shown in Figure 55. Evidence of
addition of a methyl radical to the benzene ring is given when
formation of 2-methyl terephthalic acid and trimellitic acid is
found in quantities larger than expected if all the
pseudocumene found as a p-xylene contaminant would have
its methyl groups oxidized partially or totally to carboxylic
groups.102
Trimellitic acid can react with manganese and form
manganese trimellitate, which is moderately insoluble in acetic
acid/water mixtures and contributes to depletion of manganese
from the liquid medium
5.6.4. Phenol Derivatives. The importance of phenols in
p-xylene oxidation is related to the fact that they are known to
be effective oxidation inhibitors.107,108 Decarbonylation or
decarboxylation followed by oxidation of phenyl radicals
represents the intermediate stage in byproduct phenol
synthesis. Bromination then yields substances like 2,4-
dibromophenol and 2,4,6-tribromophenol. 2-Hydroxy-4-meth-
ylbenzaldehyde can be either the result of solvolysis of a
brominated compound or a product of oxidation of
trialkylbenzene formed as a byproduct or present as an
impurity in p-xylene, Figure 56.102
Figure 56. Some of the phenol derivatives formed in p-xylene
oxidation. Adapted from ref 102.
5.6.5. Biphenyl and Benzophenone Derivatives.
Coupling of aryl radicals, a termination reaction, yields biphenyl
derivatives. The presence of these compounds in the mother
liquor is evidence of the occurrence of decarbonylation and
decarboxylation of aromatic acids and aldehydes. Coupling
between phenyl and an aroyl radical is also a termination
reaction that yields benzophenones. Formation of an aroyl
radical depends on the reaction conditions. If conditions are
such that the aroyl radical does not have enough oxygen to
form a peroxy radical, it will attack a substrate molecule to yield
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Figure 57. Formation routes of biphenyl and benzophenone derivatives during p-xylene oxidation: X, Y = H, CH3, CHO, COOH, OH; m, n = 0, 1,
2. Adapted from ref 102.
a benzophenone.101 Other route to benzophenones is through
alkylation of an aromatic with a benzyl bromide derivative via
Friedel−Crafts alkylation. This yields a biphenylmethane,
which upon oxidation yields a benzophenone compound,
Figure 57.102
5.6.6. Anthraquinone and Fluorenone Derivatives.
Cyclization of o-carboxy benzophenones is the most likely path
to yield anthraquinone derivatives. Oxidation of dihydroan-
thracene derivatives is also a plausible route. Note that the
dihydroanthracene may be the reduction product of an
anthraquinone recycled to the process. Fluorenones, in
particular, 2,6-dicarboxyfluorenone, have a detrimental effect
on terephthalic acid color.98 Fluorenone can be formed by two
distinct paths. One route may start with decarboxylation of an
o-carboxy benzophenone, yielding an o-benzoylphenyl radical,
which upon electron bonding completes the cyclization.102,109
The other route is via a biphenyl with a methyl group in the
ortho position. Oxidation of the methyl group yields a
carboxylic or a carbonyl group, which after formation of an
aroyl radical is converted to a ketone group via cyclization. This
later route has been employed successfully to synthesize 2,6-
dicarboxyfluorenone via oxidation of 2,4,5-trimethylbiphenyl to
2,4,5-tricarboxybiphenyl, Figure 58.110
5.6.7. Ester Derivatives. p-Toluic acid and terephthalic
acid esterification products are also byproducts found in p-
xylene oxidation mother liquor. The routes to esterification
may involve other byproducts as intermediates such as benzoyl
peroxides, phenols, and aroyloxy radicals. Esterification of p-
toluic acid and terephthalic acid with 4-(hydroxymethyl)-
benzoic acid, a minor intermediate found in terephthalic
acid,111 is also one possible route for ester formation. Benzyl
acetate esters formation is also important as the main reaction
is carried out in acetic acid media. Examples of esters formed in
p-xylene oxidation in acetic acid together with other byproducts
of the families mentioned above are given in Table 2.
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5.7. Catalyst Deactivation
A catalyst is usually defined as a substance which increases the
rate of a reaction without being consumed and with its
properties indefinitely unchanged. However, this is not an
absolutely true, as a catalyst undergoes chemical and physical
degrading modifications which alter its activity and selectivity.
This degradation of catalytic properties is often referred to as
catalyst deactivation and despite being more common in
heterogeneous catalysis also occurs in homogeneous catalysts,
mainly due to the high reactivity of the active species in the
metal complex.113 With a Co/Mn/Br catalyst, deactivation is
due mainly to reactions of bromine with organic substrate
molecules and precipitation of insoluble manganese com-
pounds. The bromination reaction as a form of catalyst
deactivation is closely related to formation of byproducts.
Coupling between a bromine atom and a methyl radical, as per
eq 169, yields methyl bromide which being volatile at normal
reaction conditions is removed together with the reaction off-
gas and is taken this way from the reaction media. Formation of
benzylic bromides also accounts for catalyst deactivation
despite remaining in the reaction media. Benzylic bromides,
as a source of bromine to the Co/Mn/Br catalyst, have little or
no catalytic activity in the oxidation of alkyl aromatics.75
Addition of a benzylic bromide to the oxidation media
comprising a Co/Mn catalyst and an alkyl aromatic has a
negligible effect on the rate of oxidation, Figure 59.
When bromine is lost from the catalyst one passes from a
high active Co/Mn/Br catalyst to a much less active Co/Mn
catalyst. Bromine losses, in particular, to methyl bromide, make
the Br/(Co + Mn) ratio decrease. This leads, according to
Figures 28 and 35, when at the optimum, to carbon oxides and
methyl bromide formation increases.
Considering the catalytic cycle given in Figure 10, the redox
reactions between manganese and bromine cease and the
concentration of Mn3+ ion tends to reach a steady state. The
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Figure 58. Formation routes of anthraquinone and fluorenone derivatives during p-xylene oxidation: X, Y = H, CH3, CHO, COOH, CH2OH; m, n =
0, 1, 2. Adapted from ref 102.
implication is that because water is present in the oxidation
media, disproportionation of Mn3+ can occur
2Mn 3 + → Mn 2 + + Mn 4 + (189)
Water is known to increase the proportion of Mn4+
formation in acetic acid/water solutions, and more Mn4+ is
formed as the water concentration increases, Table 3.114
From Mn4+, MnO2 is formed, a product coloring substance
and also insoluble, which by removing manganese from the
reaction media also contributes to catalyst deactivation.
Manganese trimellitate, as seen previously, has the same effect
on the catalyst system. Bromine loss to byproducts, together
with manganese precipitation of insoluble compounds, results
in a cyclic cascade of events that ends ultimately in a low
catalyst activity, Figure 60.
5.7.1. Catalyst Regeneration. The quickest way to
regenerate a bromine-depleted Co/Mn/Br catalyst is through
addition of hydrobromic acid, but other forms are possible.
Benzylic bromides can be reconverted, recovering bromine in
its ionic form, thus regenerating the catalyst. Addition of
sodium chloride leads to displacement of the covalent bonded
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organic bromide to the ionic bromide form, causing the
reaction rate to increase significantly.75
In addition, because in the oxidation media water is present,
hydrolysis of benzylic bromide can also occur.This reaction is
another possible route for formation of benzylic alcohols.
6. OPERATIONAL OPTIMIZATION STUDIES
Optimization of an operating plant deals with reducing costs
while maintaining product quality. In a commercial terephthalic
acid plant to achieve this objective the variables are many and
to better manipulate them understanding of the chemistry
behind the process is fundamental. The main goal is to
minimize 4-carboxybenzaldehyde in the final product, keeping
operational costs within controlled economical limits while
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Table 2. High Molecular Weight Byproducts Found in p-Xylene Oxidation Solvent101,102,112

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Table 2. continued

Table 3. Effect of Water in the Calculated Equilibrium

Values of Mn4+ from the Mn3+ Disproportionation in Acetic
Acid/Water Mixturesa
water (vol %) water (M) Kd (×106) Mn as Mn(IV) (%)
1 0.56 7.6 2.7
4.7 2.61 8 2.8
9.1 5.06 30 5.2
16 8.89 800 22
a
Data from ref 114.
Figure 59. Effect of different bromine sources on the O2 uptake rate
during Co/Mn/Br-catalyzed oxidation of pseudocumene. Adapted
from ref 75.
concentrations, water concentration in the mother liquor, rate,
impurities, etc.
maximizing production rate. In a simplified manner, this is 4‐CBA = ϕ([Mn], [Co], [Br], vent O2 %, H 2O%,
usually a trade-off between product quality, expressed in 4-CBA
content, and production cost, expressed in terms of solvent p‐xylene feed rate, total feed rate,
burning, i.e., COx in reactor off-gas, Figure 61. residence time, temperature, ...) (192)
In a more sophisticated model, solvent burning by itself is
not the only cost factor but parcels like catalyst concentration, Construction of models based on process variables allows us
power, utilities, etc., should also be taken into account and 4- to predict 4-CBA in the product and establish which process
CBA is dependent on many process variables, like catalyst variables have greater influence in its variation. Selection of
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7. RECENT RESEARCH TRENDS IN TEREPHTHALIC

Figure 60. Schematic cyclic cascade of events leading to catalyst
deactivation.
ACID SYNTHESIS
7.1. Oxidation in Sub- and Supercritical Water
Water is an excellent environmentally friendly solvent. Because
it is nontoxic, readily available, inexpensive, and benign to the
environment, it has been the subject of much research as
solvent media for oxidation of p-xylene.123 More recently,
research has turned to sub- and supercritical water as oxidation
media.124,125 Sub- and supercritical water (Tc = 647.3 K; Pc =
221.2 bar]126) are interesting reaction media because their
properties vary considerably as temperature increases. As the
temperatures rises up to the critical temperature, some of the
physical properties of water progressively approach those of
organic solvents. Figure 62 shows the dielectric constant,

Figure 61. Trade-off between product quality and production cost.

these variables allows their proper manipulation within a

product quality and cost policy.
Han et al.115,116 uses Multivariate Statistical Process Models
to build 4-CBA prediction models based on regression of
process variable data. Liu et al.117 use a Fuzzy Neural Network
with a reduced number of variables, and Zhang et al.118 use a
Fuzzy Support Vector Regression Model built from 10 process
variables of industrial data to predict 4-CBA concentration. Mu
et al.119,120 using a set of 10 process variables developed a
genetic algorithm which optimizes operation profit either by
manipulating product quality, i.e., 4-CBA and process
throughput, or by operating the process variables sequence in
the proper operating order. Hong et al.121 present a Fuzzy
Adaptive Immune Algorithm. Gujarathi and Babu122 present a
multiobjective optimization algorithm based on effect of six
decision variables identified, namely, catalyst concentration,
vent oxygen content, % water in solvent, feed xylene rate,
temperature of reactor, and total feed rate, also to achieve the
same effect of allowing the industrial operator to make the
desirable improvement in the process design decisions.
It is a difficult and time-consuming method to choose an
appropriate set of operation conditions for PTA production by
empirical means alone. These models, reflecting the same
individual trends observed individually from experimental
observations, provide a useful way to manipulate one variable
individually or several variables in a given sequence, within
preset limits, to aim for a desired 4-CBA concentration and
economical profit with a comfortable confidence margin to Figure 62. Properties of water as a function of temperature at 25 bar:
avoid unnecessary economical cost caused by poor trial and (a) dielectric constant; (b) terephthalic acid solubility; (c) ion product.
error industrial experiments. Adapted from ref 125.

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Table 4. Yields of p-Xylene Oxidation to Terephthalic Acid in Sub- and Supercritical Water
media T (°C) catalyst max yield (%) 4-CBA yield (%) oxidant ref
subcritical 300 MnBr2 49 ± 8 0.03 ± 0.04 H2O2 127
supercritical 380 MnBr2 57 ± 15 H2O2 128
supercritical 400 MnBr2 >90 ∼0 H2O2 129
supercritical 380 MnBr2 95 <0.1 H2O2 130,131
subcritical 300 MnBr2 80 0.6 O2 132
supercritical 380 HBr 19.1 0.06 O2 133
supercritical 380 CoBr2 6.3 5.13 O2 133
supercritical 380 MnBr2/HBr 22.7 4.66 O2 133
supercritical 380 MnBr2/benzoic acid 35.6 5.12 O2 133
supercritical 380 CuBr2 55.6 0.77 O2 124
supercritical 380 CuBr2/ NiBr2 59 ∼0 O2 124
supercritical 380 Cu/Co/Br 60 O2 124
supercritical 380 Cu/Co/NH4/Br 70.5 O2 124

Figure 63. (a) Rate of p-xylene consumption and (b) degree of a Co/Mn/Br catalyst activation as a function of the Zr/Co ratio with air oxidation at
atmospheric pressure at 95 °C. Zr used in the form of zirconium acetate solution. Adapted from ref 137.

terephthalic acid solubility, and ionic product of water as a
function of temperature. The disruption of hydrogen bonding
causes the dielectric constant to be very low when compared to
that at room temperature, making supercritical water a suitable
solvent for organic substances, as can be seen from the sharp
increase of terephthalic acid solubility. This means that the
oxidation media for carrying out the reaction and product
recovery from the solvent can be easily adjusted and achieved
by adjusting the temperature.
Table 4 shows results of p-xylene oxidation to terephthalic
acid carried out in sub- and supercritical water.
Manganese bromide is the preferred catalyst in the majority
of the experiments reported in the literature as it yields some of
the best results, some of them compared with the 95% yield
found in the AMOCO process with the Co/Mn/Br catalyst.
HBr, HBr/MnBr2, CoBr2, MnBr2/benzoic acid, CuBr2, and
CuBr2/NiBr2 catalysts have also been used but with lower
yields.127−134 Use of hydrogen peroxide as oxidant is related
with experimental difficulties in controlling a compressed
oxygen feed to the reactor; when fed at the experimental
conditions, hydrogen peroxide decomposes yielding oxygen. A
AM
high yield of terephthalic acid in supercritical water is
achievable and comparable to that achieved in commercial
processes with comparable selectivity, in particular, with low 4-
carboxybenzaldehyde content. Despite being a promising
process, the major drawback of p-xylene oxidation in super-
critical water is the pressure and temperature required to
achieve supercritical conditions, which are extremely high when
compared to those used in the AMOCO process, making the
oxidation process very hazardous.
7.2. Alternative Catalyst Systems and Cocatalysts
Improving the overall yield of a process with formation of less
byproducts due to secondary and decomposition reactions in
terephthalic acid manufacture has been the driving force of
many research efforts for alternative and more selective
catalysts. Use of titanium lining in the equipment due to the
presence of HBr in the catalyst led to research of low bromine
catalysts. Saha and Espenson135 report the use of a low-
bromide-containing catalyst with simultaneous use of Zn-
(OAc)2 and strong acid such as trifluoroacetic acid or
heptafluorobutyric acid, yielding the inorganic bromophilic
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Figure 64. (a) Effect of zirconium addition on aldehyde/(alcohol + acetate) ratio yield as a function of the Co/Mn/Br catalyst concentration at
atmospheric pressure and 95 °C. Zr/Co = 0.17. (b) Correlation of degree of activation caused by zirconium with aldehyde/(alcohol + acetate) ratio.
Aldehyde/(alcohol + acetate) ratio is at a p-xylene conversion of 30%. Adapted from ref 137.
species ZnBr+, which minimizes bromine losses to the
catalytically inactive benzylic bromides. The activating effect
is due to their protonation strength more that the nature of
their anion.136 Li and Li72 completely removed HBr from the
catalyst and achieved a maximum yield of 93.5% of terephthalic
acid at 100 °C and oxygen pressure of 10 atm using CoBr2 and
MnBr2 as catalyst.
7.2.1. Zirconium. Table 1 reports several MC-type catalysts
using other metals than or in addition to cobalt and manganese.
Use of zirconium as cocatalyst has revealed an interesting
potential for p-xylene oxidation, because when added to a Co/
Mn/Br catalyst it increases its activity and selectivity.114,137
Figure 63 shows the rate of p-xylene consumption and
degree of the Co/Mn/Br catalyst activation as a function of Zr/
Co ratio with air oxidation at atmospheric pressure at 95 °C.
At higher cobalt concentrations zirconium does not have an
activating effect as cocatalyst, but at lower cobalt concentrations
zirconium increases the catalyst concentration as the Zr/Co
ratio increases with a more pronounced effect at lower Zr/Co
ratios. The degree of activation, measured by the ratio between
the rate constant with a Zr/Co/Mn/Br catalyst and the rate
constant with a Co/Mn/Br catalyst, i.e., kZr/Co/Mn/Br/k Co/Mn/Br,
at the same Co/Mn/Br catalyst concentration also reflects the
activating effect of the Zr cocatalyst and occurs at an optimum
cobalt concentration.
In addition to increasing activity, zirconium also increases the
catalyst selectivity. The strong activating effect of Zr favors
direct formation of p-tolualdehyde from reaction p-xylene with
the oxygen molecule in 1:1 stoichiometry in relation to
formation of 4-methylbenzyl alcohol in 1:0.5 stoichiometry.
Note that according to Partenheimer137 formation of p-
tolualdehyde from p-xylene oxidation may involve the
intermediate 4-methylbenzyl alcohol, which upon further
oxidation yields p-tolualdehyde. However, the reactivity of 4-
methylbenzyl alcohol is, according to the same author, 15 times
higher than that of p-xylene and 5 times higher than the
reactivity of p-tolualdehyde .This step was not considered by
Wang et al.69 in their proposed kinetic mechanism, as they did
not detect 4-methylbenzyl alcohol, mainly because their study
was carried out at a higher temperature and high catalyst
concentration, and so the primary hydroperoxide from p-xylene
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is dehydrated directly to p-tolualdehyde by the catalyst metals,
making the reaction rate much faster. The same principle was
considered for the p-toluic acid oxidation mechanism to 4-
carboxybenzyl alcohol. Addition of Zr and subsequent
activation of the catalyst bypasses the chemistry via the benzyl
alcohols.
Figure 64a shows the effect on zirconium addition on the
aldehyde/(alcohol + acetate) ratio yield as a function of p-
xylene conversion. Note that in this ratio acetate refers to 4-
methylbenzyl acetate, formed from esterification between 4-
methylbenzyl alcohol and the acetic acid solvent.
When zirconium activates a Co/Mn/Br catalyst, the ratio
aldehyde/(alcohol + acetate) increases with conversion of p-
xylene. In contrast, at a cobalt concentration of 0.02 M, as
Figure 64a shows, no activation occurs, and for a constant p-
xylene conversion the ratio aldehyde/(alcohol + acetate) suffers
no increase. This is more evident observing Figure 64b, which
shows that, in general, the greater the degree of activation the
greater the aldehyde/(alcohol + acetate) ratio. Figures 63 and
64 show that the activating effect of zirconium does not occur
at the highest cobalt concentration but at intermediate
concentrations instead. This is an indication that adding
zirconium to a Co/Mn/Br catalyst allows one to decrease the
cobalt concentration while maintaining the same catalyst
activity and increased selectivity. The effect of zirconium is
due to its high Lewis acidity in the promotion of hydroperoxide
decomposition via a dehydration reaction: Zr(IV) > Co(III) >
Mn(III) > Co(II) > Mn (II). During the catalytic cycles shown
in Figure 10, cobalt and manganese are present mainly in their
divalent forms, and hence, the promotion effect of their
trivalent forms is small. Addition of Zr(IV) to Co/Mn/Br will
be expected to increase the rate by promoting the benzylic
peroxide to the benzaldehyde, as zirconium is present as
Zr(IV). Zr(IV) will have stronger coordination with the
peroxide, weakening the O−O bond, decomposing it to
aldehyde and water, and thus increasing the aldehyde/(alcohol
+ acetate) ratio, Figure 65.137
Zirconium addition to Co/Mn/Br allows a decrease in the
cobalt concentration in the catalyst, but it should be always
balanced for optimization purposes. It may not be desirable as
cobalt provides other selective pathways, such as avoiding
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causing an explosion or fire, and a higher concentration of O2

could be employed in the absence of an inert gas diluent such
as nitrogen air. The beneficial effect of CO2 as co-oxidant may
be explained by three mechanistic interpretations, independ-
ently or by their combination.140
• The presence of CO2 may have a suppressive effect in
Figure 65. Suggested mechanism of metal-catalyzed dehydration of decarboxylation reactions of intermediates and in
benzoyl peroxide. X = CH3 or COOH. Adapted from ref 137. product, which would improve the overall yield and
appear to enhance the oxidation rate. This effect has also
been used to explain the inhibiting role of CO2 as an
addition of peroxy and alkoxy radicals through their inert gas in acetic acid decomposition.144,145
decomposition, reducing the concentration of hydroxyl radicals
from benzyl hydroperoxide thermal decomposition, and • Improvements in oxidation rate and product selectivity
decreasing formation of phenyl formate, one of the possible might arise from increased solubility of substrate and
products of the Baeyer−Villiger reaction. Phenyl formate is intermediates and, particularly, increased solubility of
undesirable because not only it is a decrease of terephthalic acid oxygen. The effect is due to solvent expansion caused by
yield but also with its hydrolysis it yields its phenol antioxidant CO2, more notorious as CO2 pressure is increased
derivative.107,108 In addition, phenol can be further oxidized, further,145 even at a temperature of 160 °C, a low
yielding the undesirable, color-forming quinone product. temperature when compared to those normally em-
7.2.2. Carbon Dioxide Use as Co-oxidant. Carbon
ployed in commercial processes.
dioxide is one of the byproducts formed during p-xylene
oxidation and is formed from degradation of both products and • The increased solubility of oxygen in the presence of
acetic acid solvent. CO2 has been given a new role as co-oxidant CO2 may indeed account for formation of a catalytically
in homogeneous catalytic oxidation of aromatic hydro- active cyclic peroxocarbonate species, CO42−, on the
carbons.138−143
Figure 66 shows the beneficial effect of CO2 when it is
introduced in the gaseous feed stream.
The beneficial effect of CO2 as co-oxidant is clear, as an
increase in carboxylic acid in the product and increase in
oxygen consumption can be observed, showing that the activity
and selectivity toward the carboxylic acid is enhanced, even at
milder conditions. In addition to Co/Mn/HBr catalyst systems,
CO2 also has beneficial effects as co-oxidant in catalyst systems
of the type Co/Mn/HBr/M and Co/Mn/HBr/M−M′, where
M stands for an alkali metal or alkaline earth metal and M′
stands for a transition metal, including Zr, Hf, and Mo and
lanthanides, such as Ce, Pr, and Sm.140 Oxidation of
intermediates, such as p-toluic acid, the rate-determining step, Figure 67. Postulated formation mechanism and form of the
shows a similar behavior, which suggests that the presence of peroxocarbonate species. Oxygen atoms in bold represent those
from the original O2 molecule. M = Co or Mn. Adapted from ref 140.
CO2 yields a product with less intermediate impurities, which in
turn may reduce the demand in the purification step in a
commercial AMOCO process. With the use of CO2, a higher metal center, via a synergistic interaction between the O2
concentration of O2 could be used in the reaction without and the CO2 molecules, as shown in Figure 67.

Figure 66. Effect of CO2 in the liquid-phase oxidation with a Co/Mn/Br catalyst of (a) m-xylene and (b) p-xylene in the presence of 147 ppm of
potassium. Adapted from ref 140.

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Chemical Reviews
The key role of the peroxocarbonate species for oxidation of
alkyl aromatics such as p-xylene is not clear. It may lie in
transferring an oxygen atom bonded to the metal in the
peroxocarbonate complex to the p-xylene molecule to form an
alcohol and then in assisting abstraction of hydrogen to form
aldehyde, forming the p-toluic acid intermediate. The same
mechanism is repeated in oxidation of the other methyl group
of the p-toluic acid molecule to produce terephthalic acid.
However, it may indirectly participate in formation of free
radicals by acceleration of the catalytic pathway shown in
Figure 10, acting in particular in Co2+ oxidation acceleration,
inducing an acceleration in the other steps, Figure 68.140,141
Figure 68. Postulated role of the peroxocarbonate species in the
conventional MC oxidation catalytic pathway. Adapted from ref 140.
7.2.3. N-Hydroxyimides. Organic promoters have been
used in terephthalic acid synthesis and manufacture.48 In the
Teijin process, methyl−ethyl ketone is used as a promoter,2,43
with its principal function to generate peroxy radicals, which in
Figure 69. Postulated mechanism for aerobic oxidation of an aromatic hydrocarbon promoted by NHPI in the presence of a transition-metal catalyst
complex. X = H, CH3, CO2H; LnCo: cobalt or transition-metal complex with n ligands L. Adapted from ref 149.
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turn generate catalytically active Co(III) species, increasing its
concentration, thus promoting oxidation of the aromatic
hydrocarbon.37 More recently, the drive to remove corrosive
bromine from the catalyst and from the process led to research
in transition-metal salt catalytic oxidation of aromatic hydro-
carbons promoted by N-hydroxyphthalimide (NHPI) and
derivatives.146−149 Oxidation of p-xylene yields up to 84% of
terephthalic yield with less than 1% 4-carboxybenzaldehyde
yield when 20 mol % NHPI is used together with cobalt and
manganese acetates in acetic acid at 150 °C and at a pressure of
30 atm for 3 h.147 Figure 69 shows the postulated mechanism
catalyzed by NHPI similar to the classic free-radical oxidation
mechanism. It involves initial in situ NHPI decomposition by a
free-radical chain initiator such as a peroxide compound or a
labile metal complex to the phthalimide N-oxyl (PINO) radical.
PINO radical abstracts a hydrogen atom from the hydrocarbon,
generating an alkyl radical which will react with the oxygen
molecule to yield a peroxy radical. The PINO radical is
regenerated back to NHPI through hydrocarbon hydrogen
abstraction. Peroxide radicals yield alkyl peroxide molecules,
which will be decomposed by the transition-metal complex to
the oxygenate product.
The mechanism above follows a classical free-radical chain
reaction, and when fast oxygen consumption occurs, both
NHPI and the PINO radical decompose, decreasing the overall
oxidation rate of the substrate.148 This means that to keep a
steady oxidation rate NHPI needs to be continuously added to
the reaction medium. To reduce the amount of NHPI required,
N-acetoxyphthalimide (NAPI) can effectively achieve a similar
yield on terephthalic acid (80%) with only 5 mol % together
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Chemical Reviews
with 0.5 mol % of both cobalt and manganese acetates. NAPI
can be prepared according to eq 193.
The time dependence of the aerobic oxidation of p-xylene
catalyzed by NHPI or NAPI combined with cobalt acetate is
shown in Figure 70.
From the figure it can be seen that p-xylene oxidation in the
presence of NAPI is slower and also that the yield in
terephthalic acid is higher. It has been suggested that the
early stage of p-xylene oxidation NHPI is rapidly decomposed
to phthalimide and phthalic anhydride. NAPI is considered to
be resistant to this rapid decomposition when violent chain
reactions take place, since it is gradually hydrolyzed to NHPI by
water present in acetic acid as well as the water resulting from
oxidation.146,148
7.2.4. Guanidine. Cheng and co-workers150 studied the
effect of guanidine as promoter in Co/Mn/Br p-xylene
oxidation. The high basicity of guanidine (pKa = 13.6) and
the exceptional “Y-aromacity” resonance stabilization of the 6 π
electrons of guanidine and of its conjugated acid ion are
responsible for its thermodynamic stability, Figure 71.151
Figure 72 shows the effect of guanidine addition to the Co/
Mn/Br catalyst in the rate constants on stepwise oxidation of p-
xylene to terephthalic acid, as per eq 48, and on formation of
carbon dioxides.
Concerning rate constants, guanidine appears to have an
inhibiting effect on the first two steps of the oxidation and a
clear promoting effect on oxidation of the second methyl group,
as happens with the influence of water in the catalyst activity,
which is an indication of guanidine influence on catalyst
structure. In addition, a clear effect in carbon oxides formation
decreases is observed, indicating higher catalyst selectivity when
compared with the normal Co/Mn/Br catalyst. Being a
Figure 70. Time-dependence concentration of p-xylene, p-toluic acid, and terephthalic acid in the aerobic oxidation of p-xylene catalyzed by (a)
NHPI and (b) NAPI combined with cobalt acetate. Adapted from ref 146.
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Figure 71. Resonance stabilization of (a) guanidine and (b) guanidine
ion.
stronger electron donor than water, guanidine can progressively
replace aqua and acetic ligands in the catalyst structure and
bridge metal ions, as shown in Figure 73. The Y-shaped
aromatic structure disperses the π electrons in the transition
state of the complex, stabilizing it, and lowering the activation
energy of the electronic transfer reaction in the inner
coordination, effectively enhancing the rate. This means that
addition of guanidine to the catalyst will make structures II and
III in Figure 72 more active than structure I.
Coordination of guanidine to the inner coordination sphere
is limited, and thus, high outer-sphere formation of the ion pair
guanidine ion−acetate ion, {Gua+OAc−}, will occur. This ion
pair will go through ion exchange reactions with HBr
molecules, either free or bonded to the catalyst, yielding the
ion pair {Gua+Br−}. This will cause a depletion of Br− ions on
the catalyst coordination sphere (see Figure 14), decreasing its
catalytic activity, as formation of bromine free radical via the
synergy cycle of Figure 10 is lessened. Concerning formation of
carbon oxides, the positive effect of guanidine is also due to an
increase of catalyst inner-sphere electron-transfer reaction rates.
As these electron-transfer rates increase stationary Co(III)
concentration decreases. Cobaltic ions are responsible for
decarboxylation reaction of acetic acid as per eqs 154 and 155.
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Chemical Reviews
Figure 72. Effect of guanidine composition on rate constants (black lines) and in COx generation (gray line). Adapted from ref 150.
Figure 73. Suggested structures for the Co/Mn/Br/guanidine catalyst
system. M, M′ = Co(II), Co(III), Mn(II), Mn(III). Adapted from ref
150.
In addition, acetic ligand substitution by guanidine also keeps
them away from the metal, avoiding their decarboxylation in
the inner sphere of the catalyst. In conclusion, an optimized
amount of guanidine promoter will increase the reaction rate
and decrease solvent burning.150
7.3. Oxidation in Ionic Liquids
Most of chemical reactions are performed in molecular
solvents. Recently, ionic liquids have emerged as alternative
solvents for several chemical reactions. Ionic liquids are often
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fluids at room temperature. They have very low or no
measurable vapor pressure and thus at ambient temperature
are effectively nonvolatile. Because they consist of at least of
one anion and one cation, properties such as melting point,
viscosity, density, and hydrophobicity can be adjusted to a
particular purpose simply by changing the nature of one of the
components of the ion pairs. They are immiscible with some
alkane solvents and so can be used in two-phase systems. Their
composing anions are often weakly coordinating ligands, such
as BF4− and PF6−, and, hence, have the potential to be highly
polar yet noncoordinating solvents. They can be expected,
therefore, to have a strong rate-enhancing effect on reactions
involving cationic intermediates. Ionic liquids can dissolve a
wide range of organic inorganic and organometallic compounds
and also gases such as H2, CO, and O2, which makes them
suitable for catalysis of several reactions.152,153 Ionic liquids can
be used in catalysis as either catalyst or solvent or a
combination of these, as catalyst activator, or as cocatalyst for
reaction, as a catalyst ligand source, or as solvent alone for
several reactions, including aerobic oxidation reactions, as they
are stable to oxidation.154 Saleh155 patented a process to
produce aromatic aldehydes from carbonylation of suitable alkyl
aromatic compounds with pyridine or imidazole derivative ionic
liquids in a pressure range from 4 to 100 bar and temperature
range from 10 to 100 °C. The carbonylation reaction of toluene
in those experimental conditions can achieve a conversion of
66% with p-tolualdehyde selectivity up to 89.3%. Subsequent
oxidation of p-tolualdehyde with air in acetic acid with a Co/
Mn/Br catalyst provides an alternative route from toluene to
terephthalic acid. Howarth156 achieved oxidation of several
aromatic aldehydes catalyzed by nickel acetylacetonate in
[bmim][PF6] at 60 °C and atmospheric pressure. In oxidation
of benzaldehyde, p-tolualdehyde, and terephthaldicarboxyalde-
hyde, yields of 66%, 63%, and 47% of the respective aromatic
acids, benzoic acid, p-toluic acid, and terephthalic acid, were
achieved. Earle and Katdare157 patented a process in which
toluene is oxidized with nitric acid and air with pyridine or
imidazole derivatives ([bmim][NO3]) as the ionic liquid from
atmospheric pressure up to 100 bar in the ideal temperature
range from 100 to 120 °C. Benzoic acid yield was between 70%
and 90%. When p-xylene is used as feedstock in [bmim][OMs],
terephthalic acid yield is low, 4.8%, with a low selectivity,
11.5%, with the other products formed in the reaction, p-toluic
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Chemical Reviews
acid, with 36.4% yield, and with a higher selectivity of 88.5%.
The nature of the ionic liquid also has a decisive influence on
the outcome of a reaction, as Earle and co-workers158 have
shown for oxidation of toluene with nitric acid, Figure 74.
Figure 74. Influence of the ionic liquid nature on the outcome of the
oxidation of toluene with nitric acid. Adapted from ref 158.
Terephthalic acid can be obtained directly from oxidation of
p-xylene using NHPI/O2/HNO3 as oxidative system in
[bmim][OMs] at 110 °C and 1 bar.159 The maximum p-xylene
conversion achieved was 98%, with a 96% terephthalic acid
yield and 98% selectivity. The proposed mechanism is shown in
Figure 75.
NHPI and nitric acid react to yield the PINO radical, water,
and NO2 radical. The PINO radical then abstracts a hydrogen
atom from the methyl group of p-xylene, initiating the chain
reaction. NO2 radical decomposes the peroxide radical,
regenerating HNO3 and yielding the oxygenate product. Ionic
liquids present themselves as a promising research field for
oxidation of alkyl aromatics to produce alternative routes to
aromatic carboxylic acids like terephthalic acid, with the
important advantage of use of nonvolatile recyclable solvents,
Figure 75. Proposed mechanism for oxidation of p-xylene to terephthalic acid by the NHPI/O2/HNO3 system in [bmim][OMs] at 110 °C and 1
bar. Adapted from ref 159.
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attainable yields, and selectivity close to that used in the
conventional MC AMOCO process and are bromine-free
catalysts.
7.4. Heterogeneous Systems
Like with research in homogeneous systems, research on
heterogeneous systems is also motivated by efforts to improve
yields, achieve higher selectivity, and replace of hazardous
chemicals of softening process conditions.
In their 1986 paper, Hronec and Hrabě160 review briefly
efforts of hydrocarbons liquid-phase oxidations catalyzed by
heterogeneous catalysts, including oxidation of p-xylene over
CoY and MnY zeolites, but with very low yields and oxidation
in only one methyl group. In the same paper, the results are
reported for oxidation of p-xylene in water medium catalyzed
by metal oxides such as lead, cerium chromium, silver nickel,
manganese, and silver oxides. These metal oxides show little or
no activity as catalysts for p-xylene oxidation to p-toluic acid or
terephthalic acid in the absence of p-toluic acid. Addition of p-
toluic acid increases activity, but only the cobalt and manganese
oxides show activity to yield terephthalic acid. With the other
metal oxides p-xylene conversion ceases at 5−10%. These
observations led the authors to the conclusion that the
catalytically active species are not heterogeneous metal oxides
but the homogeneous toluate salts. The activity of cobalt and
manganese oxides is strongly dependent on calcination
temperatures and shows both a critical concentration above
which terephthalic acid yield is maximum and optimum water
content. Only Co−Cr and Mn−Ce bimetallic catalysts show a
higher activity than single metal catalyst, which is ratio
dependent, as there are both antagonistic and synergistic
effects.
Chavan and co-workers161 reported high activity and
selectivity toward terephthalic acid when p-xylene is oxidized
in acetic acid−water liquid medium at normal industrial process
temperature and pressures between 14 and 38 barg using as
heterogeneous catalyst neat and μ3-oxo-bridged Co/Mn cluster
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Chemical Reviews
Figure 76. Proposed catalytic oxidation of p-toluic acid over CoMn2(O)−Y catalyst. Adapted from ref 161.
complexes encapsulated in Zeolite−Y. Using such catalyst, with
heteronuclear complexes, 100% conversions of p-xylene were
achieved and distributions in the product being between 98.9%
and 99.4% for terephthalic acid and 0.01% or less for 4-
carboxybenzaldehyde. These results were, however, obtained at
38 barg, a much higher pressure that the 14−16 barg used in
commercial processes. In commercial processes 4-carboxyben-
zaldehyde is present in 0.1−0.5% in the crude product before
the hydrogenation purification process. The reasoning behind
these results is in the low redox potentials shown by the cluster
complexes, indicating easier electron transfer between Co2+/
Co3+ redox states in the oxidation and reductions steps of the
proposed mechanism of catalytic oxidation, as shown in Figure
76.
Due to the close dimensions of catalyst cluster and zeolite,
leaching is difficult and hence catalyst is stable and can be
separated and recycled. Washing the solid mixture with 0.1 N
NaOH is required to recover the carboxylic acids in the form of
water-soluble salts, and the catalyst is recovered by filtration.
No plugging due to build-up in the catalyst is reported. Indeed,
heterogeneous catalyst may be deactivated by solids which
block the active sites. This was reported by Kim et al. in their
studies of p-xylene oxidation using transition metals supported
SBA-15,162 by Das and Chakrabarty in the oxidation catalyzed
by Co(III)−oxo cubane clusters,163 and by Bastock et al. using
Envirocat EPAC as catalyst with a terephthalic acid yield of
only 37.5%.164 This effect constitutes a barrier when develop-
ment of a commercial process is desired.
More recently, patents have been filed claiming development
of heterogeneous catalysts consisting of cobalt and manganese
heteronuclear complexes encapsulated in a zeolite and
conceptual design of a process using solvent consisting of a
mixture of p-xylene and water.165−170 Oxidation is done in a
series of four reactors which operate at progressively increasing
temperature from 256 to 300 °C and 50 bar absolute.
Conversion of p-xylene in the four reactors is extremely low,
1.5%, but the formed terephthalic acid remains in solution as
well as 4-carboxybenzaldehyde. In commercial processes, once
formed terephthalic acid as 4-carboxybenzaldehyde both
precipitate, making their separation difficult and creating the
need for a purification unit. Remaining in solution, 4-
carboxybenzaldehyde is converted to terephthalic acid; in
addition, because both substances are in the liquid phase, no
blocking of the catalyst is expected. Process conditions are
maintained such that terephthalic acid is precipitated from
solution only when it leaves the reaction system, and the
solvent is recycled to the reactors, being undersaturated
terephthalic acid. The terephthalic acid product may contain
less than 0.005 w/w % of 4-carboxybenzaldehyde. The low p-
xylene conversions and high temperatures and pressures are
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Review
constrains that may also constitute a barrier to a viable, full-
scale commercial process.
8. CONCLUSIONS
In this paper, p-xylene oxidation is reviewed with particular
emphasis on the AMOCO MC method, giving a historical
evolution of the processes of terephthalic acid manufacture
from the early days’ difficulties inherent to the p-xylene
resistance toward oxidation to the breakthrough of the
AMOCO MC cobalt/manganese/bromine catalyst system.
The main state of the art detailed kinetics are presented,
which are a useful tool for investigation of mechanisms of new
catalyst and byproducts, but a lumped kinetic mechanism
proves to account effectively for the main intermediates during
p-xylene oxidation to terephthalic acid. The actual chemistry
proves to be very complex, and the literature gives evidence
that changes in catalyst composition cause changes in its
structure which account for different behavior in terms of
activity and selectivity, which in turn are important when it is
desirable to correlate this change with industrial process control
variables. Optimization of an industrial process is thus
intimately related with optimization of the catalyst. Notwith-
standing its high yield and widespread use, the current
dominant process of terephthalic acid manufacture using the
AMOCO MC Method catalyst still has some handicaps related
with the aggressive nature of its components and required
investment in specialized equipment. These handicaps are
drives to the study of new catalyst, promoters, and solvents,
some of which are presented in this paper, and are an object of
interest. Further research efforts and process development are
necessary to shift from the current mainstream technology to
more environmentally friendly and equally effective technolo-
gies.
ASSOCIATED CONTENT
*
S Supporting Information
This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: jgomes@deq.isel.ipl.pt.
Notes
The authors declare no competing financial interest.
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Chemical Reviews
Biographies
Rogério A. F. Tomás holds a B.Sc. degree in Chemical Engineering
from the Technical University of Lisbon and a M.Sc. degree in
Management and Industrial Strategy also from the Technical
University of Lisbon. He was responsible for start-up of the new
producing PTA plant from Artlant in Sines, Portugal, and is now
responsible for design and start-up of a pilot plant in The Netherlands.
He is also studying for his Ph.D. degree on optimization of the PTA
production process.
João C. M. Bordado holds a B.Sc. degree in Chemical Engineering and
a M.Sc. degree in Chemical Engineering and was awarded his Ph.D.
degree in Chemical Engineering, all from the Technical University of
Lisbon. After several years working in industry on polymer plants and
developing R&D projects, he is now Full Professor with the Chemical
Engineering Department of IST, Technical University of Lisbon, and a
researcher of IBB.
João F. P. Gomes holds a B.Sc. degree in Chemical Engineering and
was awarded his Ph.D. degree in Chemical Engineering, both from the
AU
Review
Technical University of Lisbon. He worked for several years in
Portuguese National Laboratories, supporting industry and developing
R&D projects, and is now a Habilitated Coordinating Professor with
the Chemical Engineering Departmental Area at ISEL, Lisbon
Polytechnic, and a researcher of IBB.
ACKNOWLEDGMENTS
R.A.F.T. thanks ARTLANT PTA SA for all the training and
support given which allowed this paper to be written and also
Instituto Piaget−Pólo de Santo André for logistical support
during the literature research.
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