Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
Richard J. Sheehan, Amoco Research Center, Amoco Chemical Company, Naperville, Illinois, United States
1. Introduction . . . . . . . . . . . . . . . . .
2. Physical Properties . . . . . . . . . . . .
3. Production . . . . . . . . . . . . . . . . . .
3.1. Amoco Oxidation . . . . . . . . . . . . .
3.2. Amoco Purification . . . . . . . . . . . .
3.3. Multistage Oxidation . . . . . . . . . . .
3.4. Dynamit-Nobel (Witten) Process . . .
3.5. Esterification of Terephthalic Acid . .
3.6. Hydrolysis of Dimethyl Terephthalate
1. Introduction
Terephthalic acid [100-21-0], and isophthalic
acid [121-91-5], both C8 H6 O4 , have the IUPAC
names 1,4- and 1,3-benzenedicarboxylic acid.
Dimethyl terephthalate [120-61-6], C10 H10 O4 ,
is also known as 1,4-benzenedicarboxylic acid
dimethyl ester. The acids are produced by oxi-
dation of the methyl groups on the correspond-
ing p-xylene [106-42-3] or m-xylene [108-38-3].
After oxidation to a carboxylic acid, reaction
with methanol [67-56-1] gives the methyl ester,
dimethyl terephthalate.
Terephthalic acid and dimethyl terephthal-
ate are used to make saturated polyesters with
aliphatic diols as the comonomer. Isophthalic
acid is used as a feedstock for unsaturated poly-
esters as well as a comonomer in some saturated
products. Structures are as follows:
Terephthalic acid came to prominence
through the work of Whinfield and Dick-
son in Britain around 1940 [4]. Earlier work
by Carothers and coworkers in the United
States established the feasibility of producing
high molecular weight linear polyesters by re-
acting diacids with diols, but they used aliphatic
diacids and diols. These made polyesters which

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a26 193
1
1 3.7. Alternative and Past Technologies . . 8
1 4. Environmental Protection . . . . . . . . 9
2 5. Quality Specifications . . . . . . . . . . . 9
3 6. Storage and Transportation . . . . . . 10
4
7. Uses . . . . . . . . . . . . . . . . . . . . . . 10
5
5 8. Economic Aspects . . . . . . . . . . . . . 11
7 9. Toxicology and Occupational Health . 12
7 10. References . . . . . . . . . . . . . . . . . . 12
were unsuitable to be spun into fibers. Whin-
field and Dickson found that symmetrical aro-
matic diacids yield high-melting, crystalline,
and fiber-forming materials; poly(ethylene tere-
phthalate) has since become the largest volume
synthetic fiber. Worldwide, terephthalic acid
plus dimethyl terephthalate ranked about 25th
in tonnage of all chemicals produced in 1992,
and about tenth in terms of organic chemicals.
2. Physical Properties
Terephthalic acid, M r 166.13, is available acom-
mercially as a free-flowing powder composed of
rounded crystals. It forms needles if recrystal-
lized slowly. Vapor pressure is low: 0.097 kPa at
250 ◦ C, with sublimation at 402 ◦ C and atmo-
spheric pressure. Melting has been reported at
427 ◦ C.
Dimethyl terephthalate, M r 194.19, melts at
140.6 ◦ C and has sufficient vapor pressure for
vacuum distillation. The molten form is pre-
ferred commercially, but flakes and briquettes
are available when long transport distances are
required.
Isophthalic acid, M r 166.13, melts at 348 ◦ C.
Vapor pressure is 0.61 kPa at 250 ◦ C.
Both terephthalic and isophthalic acid are sta-
ble, intractable compounds with low solubil-
ities in most solvents; isophthalic acid is 2 –
5 times more soluble than terephthalic acid in
the same solvent. Terephthalic acid solubilities
> 10 g per 100 g solvent at room temperature oc-
cur with ammonium, potassium, or sodium hy-
2 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
Table 1. Physical properties of terephthalic acid and isophthalic Table 2. Solubility of terephthalic acid and isophthalic acid
acid (g/100 g solvent)

Terephthalic Isophthalic 25 ◦ C 150 ◦ C 200 ◦ C 250 ◦ C

3 ◦
Crystal density, g/cm , 25 C 1.58 1.53 Terephthalic acid solubility, g/100 g solvent
Specific heat, J g−1 K−1 , to 100 ◦ C 1.20 1.22 Water 0.0017 0.24 1.7 12.6
Heat of formation, kJ/mol − 816 − 803 Methanol 0.10 3.1
Heat of combustion, kJ/mol, 25 ◦ C 3189 3203 Acetic acid 0.013 0.38 1.5 5.7
First dissociation constant 2.9×10−4 2.4×10−4
Isophthalic acid solubility, g/100 g solvent
Second dissociation constant 3.5×10−5 2.5×10−5 Water 0.012 2.8 25.2
Ignition temperature in air, ◦ C 680 700 Methanol 1.06 8.1
Acetic acid 0.23 4.3 13.8 44.5
droxide, dimethylformamide, and dimethyl sulf-
oxide. Tetramethylurea and pyridine each dis-
solve ca. 7 g per 100 g. xylene is used for all isophthalic acid. Oxida-
Dimethyl terephthalate is also stable, and tion catalysts and conditions have been devel-
more soluble in common organic solvents than oped which give nearly quantitative oxidation
the acids. Its main physical properties are a melt- of the methyl groups, leaving the benzene ring
ing point below the point of degradation, and a virtually untouched. These catalysts are com-
vapor pressure which allows for purification by binations of cobalt, manganese, and bromine,
distillation. or cobalt with a co-oxidant, e.g., acetaldehyde
Other physical properties of terephthalic acid [75-07-0]. Oxygen is the oxidant in all pro-
and isophthalic acid are listed in Tables 1 and cesses. Acetic acid [64-19-7] is the reaction sol-
2. Some physical properties of dimethyl tere- vent in all but one process. Given these constant
phthalate are listed below: factors, there is only one industrial oxidation
process, with different variations, two separate
Solubility, g/100 g solvent purification processes, and one process which
Methanol, 25 ◦ C 1.0 intermixes oxidation and esterification steps.
Methanol, 60 ◦ C 5.7
Ethyl acetate, 25 ◦ C 3.5
Ethyl acetate, 60 ◦ C 16.0
Trichloromethane, 25 ◦ C 10.0 3.1. Amoco Oxidation
Trichloromethane, 60 ◦ C 23.0
Benzene, 25 ◦ C 2.0
Benzene, 60 ◦ C 14.0 About 70 % of the terephthalate feedstock used
Toluene, 25 ◦ C 4.3 worldwide is produced with a catalyst system
Toluene, 60 ◦ C 10.4
Dioxane, 25 ◦ C 7.5
discovered by Scientific Design [5, 6]. Almost
Dioxane, 60 ◦ C 26.5 100 % of new plants use this reaction. A sep-
Vapor pressure, kPa arate company, Mid-Century Corporation, was
140 ◦ C 1.58 established to market this technology, and subse-
160 ◦ C 2.62
200 ◦ C 10.88
quently purchased by Amoco Chemical. Amoco
250 ◦ C 42.60 developed a commercial process, as did Mitsui
Density at mp 1.07 g/cm3 Petrochemical, now Mitsui Sekka. Mitsui was an
Viscosity, 180 ◦ C 0.0071 Pa · s
early licensee of Mid-Century. Both Amoco and
Viscosity, 200 ◦ C 0.0060 Pa · s
Specific heat, solid 1.55 J g−1 K−1 Mitsui participate in joint-venture companies,
Specific heat, liquid 1.94 J g−1 K−1 and both have licensed the process. Licensees
Heat of fusion 159.1 kJ/Kg are distributed around the world, and some have
Heat of vaporization 355.5 kJ/Kg
Heat of formation −740.2 kJ/mol
relicensed the process to other companies.
Heat of combustion, 25 ◦ C 4660 kJ/mol A soluble cobalt – manganese – bromine cat-
Flash point, DIN 51 758 141 ◦ C alyst system is the heart of the process. This
yields nearly quantitative oxidation of the p-
xylene methyl groups with small xylene losses
3. Production [7]. Acetic acid is the solvent, and oxygen in
compressed air is the oxidant. Various salts
p-Xylene is the feedstock for all terephthalic of cobalt and manganese can be used, and
acid and dimethyl terephthalate production; m- the bromine source can be HBr, NaBr, or
 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
Figure 1. Catalytic, liquid-phase oxidation of p-xylene to terephthalic acid by the Amoco process
a) Oxidation reactor; b) Surge vessel; c) Filter; d) Dryer; e) Residue still; f) Dehydration column
tetrabromoethane [79-27-6] among others. The
highly corrosive bromine – acetic acid environ-
ment requires the use of titanium-lined equip-
ment in some parts of the process.
A feed mixture of p-xylene, acetic acid, and
catalyst is continuously fed to the oxidation re-
actor (Fig. 1). The feed mixture also contains
water, which is a byproduct of the reaction. The
reactor is operated at 175 – 225 ◦ C and 1500 –
3000 kPa. Compressed air is added to the re-
actor in excess of stoichiometric requirements
to provide measurable oxygen partial pressure
and to achieve high p-xylene conversion. The re-
action is highly exothermic, releasing 2×108 J
per kilogram p-xylene reacted. Water is also
released. The reaction of 1 mol p-xylene with
3 mol dioxygen gives 1 mol terephthalic acid
and 2 mol water. Only four hydrogen atoms, re-
presenting slightly over 2 wt % of the p-xylene
molecule, are not incorporated in the terephthal-
ic acid.
Owing to the low solubility of terephthalic
acid in the solvent, most of it precipitates as it
forms. This yields a three-phase system: solid
terephthalic acid crystals; solvent with some dis-
solved terephthalic acid; and vapor consisting of
nitrogen, acetic acid, water, and a small amount
of oxygen. The heat of reaction is removed by
solvent evaporation. A residence time up to 2 h
is used. Over 98 % of the p-xylene is reacted,
and the yield to terephthalic acid is > 95 mol %.
Small amounts of p-xylene and acetic acid are
lost, owing to complete oxidation to carbon ox-
ides, and impurities such as oxidation intermedi-
ates are present in reactor effluent. The excellent
3
yield and low solvent loss in a single reactor pass
account for the near universal selection of this
technology for new plants.
The oxidation of the methyl groups occurs
in steps, with two intermediates, p-toluic acid
[99-94-5] and 4-formylbenzoic acid [619-66-9].
While 4-formylbenzoic acid is the IUPAC name
of the intermediate, it is customarily referred to
as 4-carboxybenzaldehyde (4-CBA).
4-Formylbenzoic acid is troublesome, owing
to its structural similarity to terephthalic acid.
It co-crystallizes with terephthalic acid and be-
comes trapped and inaccessible for completion
of the oxidation. Up to 5000 ppm 4-formylben-
zoic acid can be present, and this necessitates
a purification step to make the terephthalic acid
suitable as a feedstock for polyester production.
The slurry is passed from the reactor to one
or more surge vessels where the pressure is re-
duced. Solid terephthalic acid is then recovered
by centrifugation or filtration, and the cake is
dried and stored prior to purification. This is typ-
ically referred to as crude terephthalic acid, but
is > 99 % pure.
Vapor from the reactor is condensed in over-
head heat exchangers, and the condensate is re-
4 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
Figure 2. Purification of terephthalic acid by the Amoco process
a) Slurry drum; b) Hydrogenation reactor; c) Crystallizers; d) Centrifuge; e) Dryer
fluxed to the reactor. Steam is generated by the
condensation and is used as a heating source in
other parts of the process. Oxygen-depleted gas
from the condensers is scrubbed to remove most
uncondensed vapors. Similar to the reactor con-
densate, liquid from centrifuges or filters is sent
to solvent recovery. Since the centrifugate or fil-
trate contains dissolved species, it is first sent
to a residue still. Vapor from the still and other
vents from throughout the oxidation process are
sent to a solvent dehydration tower. The tower
removes the water formed in the reaction as the
overhead stream, and the acetic acid from the
tower bottom is combined with fresh acetic acid
to make up for process losses, and returned to
the process.
Isophthalic acid is also produced by this pro-
cess from m-xylene. Because isophthalic acid
is several times more soluble than terephthal-
ic acid, much less precipitates in the reactor.
Consequently, isophthalic acid from this process
contains much less 3-formylbenzoic acid, since
it tends to stay in solution where complete ox-
idation can occur. Further purification was not
carried out in the past, but a purified grade that
is now being produced will become the standard.
3.2. Amoco Purification
The purification process developed by Amoco
Chemical [8] and used on terephthalic acid from
the Amoco oxidation process supplies over 60 %
of the terephthalate feedstock for polyester pro-
duction (Fig. 2).
Crude terephthalic acid is unsuitable as a
feedstock for polyester, primarily owing to the
4-formylbenzoic acid impurity concentration.
There are also yellow impurities and resid-
ual amounts of catalyst metals and bromine.
The Amoco purification process removes 4-
formylbenzoic acid to < 25 ppm, and also gives
a white powder from the slightly yellow feed.
It is necessary to make all impurities accessi-
ble to reaction, so the crude terephthalic acid is
slurried with water and heated until it dissolves
entirely. A solution of at least 15 wt % is ob-
tained, and this requires a temperature ≥ 260 ◦ C.
The solution passes to a reactor where hydro-
gen is added and readily dissolves. The solution
is contacted with a carbon-supported palladium
catalyst. Reactor pressure is held above the va-
por pressure of water to maintain a liquid phase.
The 4-formylbenzoic acid is converted to p-
toluic acid in the reactor, and some colored
impurities are hydrogenated to colorless com-
pounds. The reaction is highly selective; loss of
terephthalic acid by carboxylic acid reduction or
ring hydrogenation is < 1 %.
After reaction, the solution passes to a series
of crystallizers where the pressure is sequen-
tially decreased [9]. This results in a stepped
temperature reduction, and crystallization of the
terephthalic acid. The more soluble p-toluic acid
formed in the reactor, and other impurities, re-
main in the mother liquor. After leaving the final
crystallizer, the slurry undergoes centrifugation
and/or filtration to yield a wet cake, and the cake
is dried to give a free-flowing terephthalic acid
powder as the product. Over 98 wt % of the in-
coming terephthalic acid is recovered as purified
product.
As with the Amoco oxidation, this purifica-
tion process is also used with isophthalic acid.
 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
3.3. Multistage Oxidation
Several companies, mostly in Japan [10, 11],
have developed processes to reduce the 4-
formylbenzoic acid content to 200 – 300 ppm by
more intensive oxidation. A separate purifica-
tion step is eliminated; the concentration of 4-
formylbenzoic acid is low enough for the tere-
phthalic acid to be suitable as a feedstock for
some polyester products where high feedstock
purity is not critical. The product is often called
medium-purity terephthalic acid, and accounts
for about 11 % of the terephthalic acid produced.
Most of these processes also use the catalyst sys-
tem discovered by Scientific Design.
Most medium-purity terephthalic acid is pro-
duced by Mitsubishi Kasei and its licensees.
They have named this product Q-PTA, and it
has a typical 4-formylbenzoic acid level of ca.
290 ppm [10]. Mitsubishi has also developed a
still more intensive oxidation process where the
4-formylbenzoic acid level is further reduced.
The product is called S-QTA.
The oxidation of p-xylene in acetic acid with
a cobalt – manganese – bromine catalyst is car-
ried out as in the Amoco oxidation. The slurry
is heated to 235 – 290 ◦ C and oxidized further in
another reactor. More catalyst can be added in
addition to the temperature increase [12].
Heating gives increased terephthalic acid
solubility, and as crystals dissolve, some 4-
formylbenzoic acid and colored impurities are
released. Although the terephthalic acid is not
completely soluble at the higher temperature,
the crystals can digest. Digestion is a dynamic
equilibrium process wherein crystals constantly
dissolve and reform. This increases the release
of 4-formylbenzoic acid into solution where ox-
idation can be completed. While the need for a
separate purification process is eliminated, an-
other reactor is needed in the oxidation process.
Also, at higher temperature, acetic acid tends to
be oxidized to a larger extent to carbon oxides
and water [12].
The rest of the Mitsubishi process consists
of solid – liquid separation and drying to obtain
the powdered product. Acetic acid must be de-
hydrated and recycled to the process.
Eastman Chemical has also developed a
medium-purity terephthalic acid product. The
process does not employ manganese, only cobalt
and bromine. Two oxidation stages are used,
5
both at 175 – 230 ◦ C [13]. Instead of heating bet-
ween stages to obtain increased solubility, as
performed by Mitsubishi, the contents of the first
reactor are sent to hydroclones where hot, fresh
acetic acid displaces the mother liquor. Samar-
ium may be added to the catalyst. A residence
time up to 2 h with air addition provides suf-
ficient digestion of the crystals to yield a 40 –
270 ppm level of 4-formylbenzoic acid [13].
Downstream recovery of the terephthalic acid
crystals by solid – liquid separation and drying
must again be performed.
3.4. Dynamit-Nobel (Witten) Process
Most dimethyl terephthalate is made by a pro-
cess first developed by Chemische Werke Wit-
ten, with work also being done at a division
of Standard Oil of California. Modifications
were made by Hercules and Dynamit-Nobel.
Hüls Troisdorf licensed the process with fur-
ther modifications [14]. Dimethyl terephthalate
is formed in four steps. First, p-xylene is passed
through an oxidation reactor, where p-toluic acid
is formed. It then passes to an esterification reac-
tor, the second step, where methanol is added to
form methyl p-toluate [99-75-2]. The methyl p-
toluate is isolated and returned to the oxidation
reactor for oxidation to monomethyl terephthal-
ate [1679-64-7], the third step, followed by the
fourth step, esterification to dimethyl terephthal-
ate. The sequence is as follows:
The process as licensed by Hüls Troisdorf is
illustrated in Figure 3. Fresh and recovered p-
6 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid

Figure 3. Production of dimethyl terephthalate by the Dynamit Nobel process

a) Oxidation reactor; b) Esterifier; c) Expansion vessel; d) Methanol recovery column; e, f) Methyl p-toluate and dimethyl
terephthalate columns; g, j) Dissolvers; h, k) Crystallizers; i, l) Centrifuges

xylene, along with catalyst (mostly cobalt with
some manganese) are combined with methyl p-
toluate and fed to the liquid-phase oxidation re-
actor. Because bromine and acetic acid are not
used, vessels lined with titanium or other ex-
pensive metals are not necessary. Oxygen sup-
plied by compressed air is added at the bottom.
Oxidation conditions are 140 – 180 ◦ C and 500 –
800 kPa. The heat generated by oxidation is re-
moved by vapors of unreacted p-xylene and the
water of reaction. Cooling coils in the reactor are
used to generate steam. The steam and reactor
vapors are condensed and combined to recover
p-xylene for recycle.
The oxidation effluent is then heated and
sent to the esterification reactor, operated at
250 ◦ C and 2500 kPa. Excess vaporized meth-
anol is sparged into the esterifier, where the p-
toluic acid and monomethyl terephthalate are
converted noncatalytically to methyl p-toluate
and dimethyl terephthalate, respectively. Over-
head vapors from the esterification reactor are
condensed and fed to a distillation system, where
the water from the esterification is separated
from methanol, which is recycled.
The remainder of the process separates the di-
methyl terephthalate from methanol and methyl
p-toluate, which are recycled, and residue and
wastewater, which go to waste treatment.
The product from the esterifier goes to an ex-
pansion vessel. Vapor from this vessel feeds a
methanol recovery column, where the metha-
nol overhead goes to methanol recovery, and the
methyl p-toluate bottoms are recycled to the ox-
idation reactor. Liquid from the expansion ves-
sel feeds two vacuum distillation columns in se-
ries, which yield crude dimethyl terephthalate.
The first column recovers more methyl p-toluate
overhead for recycle to oxidation, and the bot-
toms feeds the crude dimethyl terephthalate col-
umn, where the product is taken overhead. The
bottoms from the dimethyl terephthalate col-
umn, containing heavy byproducts and catalyst
metals, can be mixed with water from the oxida-
tion, which dissolves the catalyst. The resulting
slurry is centrifuged; the catalyst solution is re-
cycled, and the cake is sent to disposal.
The crude dimethyl terephthalate goes
through two stages of crystallization. It is slur-
ried with the methanol mother liquor from the
second crystallization stage and dissolved by
heating. Dimethyl terephthalate is crystallized
from this solution on cooling, by flashing the
methanol. The dimethyl terephthalate cake is
separated by centrifugation, dissolved in fresh
methanol, and crystallized in the same way. The
wet dimethyl terephthalate cake can be melted
and stored molten, or dried and flaked. There
is usually a distillation column after the second
centrifuge for further purification.
Mother liquor from the first centrifugation is
sent to the methanol recovery system. The cen-
trifugation yields a cleaner mother liquor which
is combined with methanol recovered from the
melting operation for use in dissolving the crude
dimethyl terephthalate entering the crystalliza-
tion section. Side-streams from throughout the
process are recycled to appropriate points to
maximize yield and to minimize methanol and
catalyst use.
 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
Figure 4. Esterification of terephthalic acid and separation of purified dimethyl terephthalate
a) Esterifier; b) o-Xylene scrubber; c) Methanol column; d) o-Xylene recovery column; e) 4-Formylbenzoic ester stripper;
f) Purification column
3.5. Esterification of Terephthalic Acid
Terephthalic acid can be produced and, in a sep-
arate process, esterified with methanol to di-
methyl terephthalate which is then purified by
distillation (Fig. 4) [15, 16]. This process can be
used on highly impure terephthalic acid, because
of the purification achievable by distillation.
Crude terephthalic acid and excess methanol
are mixed and pumped to the esterification reac-
tor. In this example, o-xylene [95-47-6] is used
to enhance the subsequent separations. The tere-
phthalic acid is rapidly esterified by the metha-
nol at 250 – 300 ◦ C without catalysis, although a
catalyst can be used. Methanol vapor carries di-
methyl terephthalate and o-xylene from the reac-
tor to a column where o-xylene is added to scrub
out monomethyl terephthalate and return it to the
reactor for completion of the esterification. The
vapor contains the dimethyl terephthalate prod-
uct as well as methanol, o-xylene, water from
the esterification, and esterified impurities in the
terephthalic acid feed. Several distillation steps
are needed to separate out the dimethyl tere-
phthalate and to process the separated streams
for recovery of valuable components for recy-
cle.
The reactor overhead vapor first goes to a
methanol column where methanol is removed
overhead, water and some methanol form a side-
draw, and the bottoms contain the dimethyl tere-
phthalate, o-xylene, and impurities.
7
Next, in the o-xylene recovery column, di-
methyl terephthalate purification is started; it
operates at 10 – 20 kPa absolute so that a tem-
perature of 200 – 230 ◦ C can be used. o-Xylene
is removed overhead, the methyl esters of 4-
formylbenzoic acid and p-toluic acid are re-
moved in the middle, and dimethyl terephthal-
ate forms the bottoms. A 4-formylbenzoic acid
stripping column follows, where the middle
stream from the previous column is sent, so that
4-formylbenzoic ester can be removed overhead.
Finally, the bottoms from both the o-xylene re-
covery column and the 4-formylbenzoic acid
stripper are sent to a purification column, where
the dimethyl terephthalate product is taken over-
head.
Methanol from the top of the methanol recov-
ery column is sent to a purification column where
the overhead contains low boilers, and the meth-
anol from the bottoms is recycled. The methanol
and water from the side-draw of the methanol
recovery column are sent to a methanol dehy-
dration column, where the water is removed and
the dehydrated methanol recycled.
3.6. Hydrolysis of Dimethyl
Terephthalate
High-purity terephthalic acid can be produced
by hydrolysis of dimethyl terephthalate. Slightly
over 2 % of terephthalate feedstock is produced
by this route.
8 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
Dimethyl terephthalate and recovered
monomethyl terephthalate are combined with
water from the methanol recovery tower of the
dimethyl terephthalate process and heated to
260 – 280 ◦ C at 4500 – 5500 kPa in a hydroly-
sis reactor, where the methyl esters are hydro-
lyzed. The overhead methanol plus water vapor
is returned to the methanol recovery tower for
separation. The hydrolysis reactor liquid is sent
to a series of crystallizers and cyclones. Af-
ter cooling to crystallize the terephthalic acid
at ca. 200 ◦ C, washing cyclones are used to re-
move mother liquor which contains monomethyl
terephthalate. The cyclone underflow is further
cooled to 100 ◦ C, and final crystallization oc-
curs. This slurry is centrifuged and dried to give
the final product.
Monomethyl terephthalate from the cyclone
overflow is recovered, again by cooling to
100 ◦ C and centrifuging, and the cake is recy-
cled to the hydrolysis reactor.
3.7. Alternative and Past Technologies
Oxidation of p- or m-xylene is also possible with
acetic acid solvent and a cobalt catalyst with an
acetaldehyde activator. Reaction temperature is
120 – 140 ◦ C, and as a result the oxidation re-
quires a residence time ≥ 2 h. Titanium-lined
vessels are not required because bromine is not
used. The acetaldehyde is converted to acetic
acid as it promotes the reaction. After reaction,
the terephthalic or isophthalic acid is recovered
by centrifugation or filtration and drying, much
like the Amoco process, and acetic acid is reco-
vered for recycle by distillation.
With isophthalic acid, which has a lower con-
centration of 3-formylbenzoic acid, consider-
able purification is possible by slurrying in wa-
ter to ca. 20 – 25 wt %, heating to 240 – 260 ◦ C
to dissolve, and crystallizing by cooling in batch
mode. Recovery of the crystals is again by cen-
trifugation or filtration and drying.
Eastman Chemical in the United States also
used an acetaldehyde activator with a cobalt cat-
alyst to produce terephthalic acid. Bromine is
now being used in place of acetaldehyde [17].
Mobil Chemical in the United States had a
commercial terephthalic acid operation which
has since been abandoned [18]. As with the
above processes, a cobalt catalyst was used with
acetic acid solvent; the activator was 2-butanone
[78-93-3]. After reaction, the crude terephthal-
ic acid was leached by adding pure acetic acid
and heating to achieve partial solubility; this re-
moved gross impurities. Final purification was
by sublimation and catalytic treatment of the va-
por. Impure terephthalic acid was vaporized in
a steam carrier, and catalyst and hydrogen were
added to convert undesirable organic impurities.
Subsequent cooling of the stream condensed the
terephthalic acid, leaving impurities in the vapor.
Product crystals were removed by cyclones.
A process no longer practiced is based
on Henkel technology. Starting with phthalic
anhydride [85-44-9], the monopotassium and
dipotassium o-phthalate salts were formed in se-
quence. The dipotassium salt was isolated from
solution by spray drying, and isomerized to
dipotassium terephthalate under carbon dioxide
at 1000 – 5000 kPa and 350 – 450 ◦ C. This salt
was dissolved in water and recycled to the start
of the process, where terephthalic acid crystals
formed during the production of the monopotas-
sium salt. The crystals were recovered by filtra-
tion.
Two proposed processes which were never
commercialized were by Lummus, using a dini-
trile route [19] and by Eastman, using the forma-
tion of 1,4-diiodobenzene [624-38-4] with car-
bonylation to aromatic acids [20].
Toluene [108-88-3] is a potential feedstock
for manufacture of terephthalic acid and is
cheaper than p-xylene. Mitsubishi Gas Chem-
ical has researched a process where a complex
between toluene and hydrogen fluoride – boron
trifluoride is formed, that can be carbonylated
with carbon monoxide to form a p-tolualdehyde
[104-87-0] complex [21]. After decomposition
of the complex, p-tolualdehyde can be oxi-
dized in water with a manganese – bromine cat-
alyst system to terephthalic acid. While cheaper
toluene is the feedstock and acetic acid is not re-
quired, the complexities of handling hydrogen
fluoride – boron trifluoride and the need for car-
bon monoxide add other costs. This process has
not been commercialized.
4. Environmental Protection
The three chemicals discussed here consist only
of carbon, hydrogen, and oxygen, so carbon
 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
dioxide and water are the final effluents of oxida-
tive degradation. There are traces of the cobalt –
manganese – bromine catalyst in waste streams,
however.
Effluents from the terephthalic acid process
include water generated during oxidation and
water used as the purification solvent. Gaseous
emissions are mostly the oxygen-depleted air
from the oxidation step. Volumes are large, but
the chemicals in the streams can be effectively
destroyed and removed.
Water effluents are subjected to aerobic
wastewater treatment, where the dissolved
species, mostly terephthalic acid, acetic acid,
and impurities such as p-toluic acid, are oxidized
to carbon dioxide and water by the action of bac-
teria which are acclimated to these chemicals.
The bacterial growth is a sludge which can be
dried and burned or spread on land. An anaerobic
process has been developed to treat the waste-
water [22]. Advantages include much less waste
sludge production, less utility consumption, and
the generation of methane, which can be burned
for energy recovery.
Waste gas is scrubbed in process equipment
to remove acetic acid vapors for recovery. Trace
amounts of other compounds formed in the re-
actor can be removed by catalytic oxidation, fol-
lowed by scrubbing to meet the most demanding
regulations for process vents [23].
Waste streams from distillation in the di-
methyl terephthalate process can be burned for
energy recovery.
Another aspect of environmental protection
is the recyclability of polyesters. Post-consumer
containers can be ground and cleaned, and then
extruded and spun into fiber to fill bedding, and
quilted clothing. Textile fibers can also be made.
The polyester can also be reacted to regener-
ate the terephthalate feedstock. High-tempera-
ture hydrolysis yields terephthalic acid. Reac-
tion with methanol yields dimethyl terephthal-
ate.
5. Quality Specifications
Feedstocks for polyester production must be
extremely pure; they are among the purest
high-volume chemicals sold by industry. If
certain impurities are present in high enough
concentrations, harmful effects can be mea-
9
sured, e.g., monofunctional compounds can
cap the polyester chain and limit molecular
mass buildup. Trifunctional carboxylic acids can
cause chain branching which leads to undesir-
able rheological and spinning properties. Col-
ored impurities can be incorporated into the
polyester. In particular, 4-formylbenzoic acid
limits polyester molecular mass and causes yel-
lowness [24]. The particle size of terephthalic
acid determines how the powder flows, and the
viscosity of the slurry when mixed with 1,2-
ethanediol [107-21-1].
Owing to the consistent high purity of these
products and the different effects of impurities,
specifications put limits on specific impurities or
color, rather than overall purity (Table 3). Trends
in quality specifications are away from maxi-
mum or minimum values, toward a target value
with an allowable range. This has been instituted
to some extent by Amoco Chemical for the p-
toluic acid content, for example.
Table 3. Specifications and typical analyses of purified terephthalic
acid
Property Specification Typical value
Acid number, mg KOH/g 675 ± 2 673 – 675
Ash, ppm ≤ 15 <3
Metals,∗ ppm ≤9 <2
Water, wt % ≤ 0.2 0.1
4-Formylbenzoic acid, ppm ≤ 25 15 ∗∗
p-Toluic acid, ppm 125 ± 45 125 ∗∗
∗ Co + Mn + Fe + Cr + Ni + Mo + Ti.
∗∗ Medium-purity terephthalic acid typically has 250 ppm
4-formylbenzoic acid and <50 ppm p-toluic acid.
In Table 3, acid number, determined by titra-
tion, is an overall purity measurement. A per-
fectly pure sample will have an acid number of
675.5 mg KOH/g, but the low impurity levels
make the acid number meaningless as a quanti-
tative indication of purity, and it is being phased
out.
Impurities specified include p-toluic acid and
4-formylbenzoic acid, residual water, and trace
metals, the ash being trace metal oxides. There
are also color and particle size measurements.
Polyester producers often have specific tests
which they prefer for color or particle size.
Medium-purity terephthalic acid specifica-
tions address the same impurities, except that
10 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
4-formylbenzoic acid concentrations are up to
300 ppm, and residual acetic acid is present.
Typical dimethyl terephthalate specifications
are shown in Table 4. Freezing point is an
extremely sensitive purity indicator. Since di-
methyl terephthalate is often shipped and stored
in molten form, color measurements are made
on the melt. A color stability test can determine
the sample’s resistance to degradation. This re-
sistance is reduced by the presence of unester-
ified acid groups, so these residual groups are
measured.
Table 4. Specifications and typical analyses of dimethyl
terephthalate
Property Specification Typical value
◦
Freezing point, C ≥ 140.62 140.64
Acid number, mg KOH/g 0.03 0.01
Molten color, APHA ≤ 25 10
Color stability,∗ APHA ≤ 25 15
Water, wt % ≤ 0.02 0.01
∗ 4 h at 175 ◦ C
Specifications for isophthalic acid are similar
to those of terephthalic acid, m-toluic acid and
3-formylbenzoic acid being the impurities.
6. Storage and Transportation
Terephthalic acid powder is stored in silos and
transported in bulk by rail hopper car, hopper
truck, or bulk container with a polyethylene
liner. Hopper cars and trucks should be dedi-
cated to this service, because of the extreme pu-
rity requirements. Shipment is also in 1 t bags,
or paper bags containing ca. 25 kg. Isophthalic
acid, being a much lower volume chemical, has
a higher proportion shipped in bags.
Dimethyl terephthalate is stored molten in
insulated heated tanks, and is preferentially
shipped molten in insulated rail tank cars or
tank trucks. It is also solidified into briquettes
or flakes, and shipped in 1 t or 25 kg bags.
The huge production volume of terephthal-
ic acid and dimethyl terephthalate favors the
use of bulk shipment with minimized packag-
ing costs. Rail cars are preferred where possible,
and they can accommodate up to 90 t. Containers
with plastic liners hold 20 t terephthalic acid, and
these are the preferred ocean shipping method.
7. Uses
Terephthalic acid and dimethyl terephthalate are
used almost exclusively to produce saturated
polyesters. Poly(ethylene terephthalate), the al-
ternating copolymer of terephthalic acid and 1,2-
ethanediol, accounts for > 90 % of this use, with
a worldwide demand of 12.6×106 t in 1992. Tex-
tile and industrial fiber accounted for 75 % of
this demand. Polyester is the largest volume syn-
thetic fiber. Food and beverage containers ac-
counted for 13 %, and constituted the fastest
growing segment. Film for audio, video, and
photography took 7 %.
Other uses are for poly(butylene terephthal-
ate), a high-performance molding resin made
by reaction with 1,4-butanediol [74829-49-5],
and for special industrial coatings, solvent-free
coatings, electrical insulating varnishes, aramid
fibers, and adhesives. A small amount of bis(2-
ethylhexyl) terephthalate [6422-86-2] is pro-
duced as a plasticizer, and some dimethyl tere-
phthalate is ring-hydrogenated to produce the
cyclohexane analog, 1,4-cyclohexanedicarbox-
ylic acid [1076-97-7], for specialty polyesters
and coatings. Isophthalic acid is used as a
comonomer with terephthalic acid in bottle and
specialty resins. It is also a feedstock for coat-
ings and for high-performance unsaturated poly-
esters, being first reacted with maleic anhydride
[108-31-6] and then this resin is cross-linked
with styrene [100-42-5].
8. Economic Aspects
Together, terephthalic acid and dimethyl tere-
phthalate rank about 25th in tonnage of all chem-
icals, and about tenth for organic chemicals. The
rapid growth of polyester use has led to an above-
average growth for these feedstocks, and this is
projected to continue as deeper penetration into
fiber and container markets is made. The versa-
tility of terephthalate and isophthalate polyesters
is projected to drive growth in the foreseeable
future.
Capacity for the three types of terephthalate
feedstocks since 1980 is given in Table 5. Pu-
rified terephthalic acid has grown rapidly, and
is projected to supply virtually all the growth
 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
for polyesters, about 7 % annually to the year
2000. Medium-purity terephthalic acid capacity
has grown by construction of a few new plants,
and by conversion of some dimethyl terephthal-
ate capacity. Dimethyl terephthalate has shown
little change in capacity since 1980, and essen-
tially none is expected in the future.
Table 5. Capacity of terephthalate feedstocks (103 t/a)
Feedstock ∗ 1980 1986
PTA 2800 4000
MTA 420 580
DMT 3300 3600
∗ PTA purified terephthalic acid; MTA medium-purity
terephthalic acid; DMT dimethyl terephthalate.
The Far East contains most of the world’s
population and most of the garment manufac-
turing industry. As a result, it is experiencing
most of the growth in manufacturing capacity
for polyester fibers, and most of the growth for
terephthalic acid production (Table 6). Approxi-
mately 75 % of the growth in terephthalate feed-
stocks in 1986 – 1992 was due to purified tere-
phthalic acid plants built in the Far East.
Table 6. Geographical distribution of terephthalate production
(103 t/a)
1980 1986
North America 3300 3400
Europe 1500 2100
Far East 1500 2300
Rest of World 220 380
Pricing is often determined in conjunction
with long-term contracts, and is most influ-
enced by the cost of p-xylene. In 1992, prices
were about $ 0.60/kg for terephthalic acid and
$ 0.57/kg for dimethyl terephthalate [25]. Be-
cause a given mass of terephthalic acid produces
17 % more polyester than the same mass of di-
methyl terephthalate, the dimethyl terephthalate
price must be adjusted downward, and allowance
is made for the value of the methanol generated
during transesterification.
The major producer of purified terephthal-
ic acid is Amoco Chemical, with over 17 % of
the world’s production in 1992. Joint ventures of
Amoco, the largest being China American Petro-
chemical in Taiwan and Samsung Petrochemical
in Korea, also produce about 17 %. Other major
11
producers are Mitsui Sekka in Japan and Impe-
rial Chemical Industries in England and Taiwan.
China is certain to become a major producer, and
large plants are being planned in Southeast Asia.
Larger producers of medium-purity terephthalic
acid are Mitsubishi Kasei in Japan, and Eastman
and DuPont in the United States. Some polyester
producers have licensed technology to supply
their own feedstock. All licensors are themselves
producers of terephthalic acid, or have obtained
1992
the technology from a producer.
8100 Major dimethyl terephthalate producers are
1300 DuPont, Eastman Chemical, and Hoechst
3300
Celanese in the United States, Hoechst in Eu-
rope, and Teijin Petrochemical in Japan. There
are several small, older plants, mostly in Europe
and China.
Isophthalic acid production capacity is
250×103 t/a, ca. 2 % of the terephthalate total.
Amoco Chemical is the major producer.
9. Toxicology and Occupational
Health
Terephthalic acid, dimethyl terephthalate, and
isophthalic acid all have low toxicity and cause
only mild and reversible irritation to skin, eyes,
and the respiratory system.
1992 For oral ingestion of terephthalic acid, LD50
3600
values for rats have been reported as 18.8 g/kg
2700 [26], and for mice as 6.4 g/kg [27], or > 5 g/kg
5800 [28]. Dimethyl terephthalate LD50 values for
600 rats are 6.5 g/kg [29] and 4.39 g/kg [26]. Some
mortality was found at 5 g/kg oral ingestion [30],
and with a 28-day oral uptake of 5 % in the feed,
ca. 2.5 g/kg. For isophthalic acid, LD50 for rats
was reported as 10.4 g/kg [26].
Interperitoneal administration of terephthal-
ic acid in rats showed LD50 values > 1.43 g/kg
[28] and 1.9 g/kg [31], with LD100 = 3.2 g/kg
[31]. Mortality was found at 0.8 g/kg in mice and
1.6 g/kg in rats [27]. For dimethyl terephthalate,
an LD50 of 3.9 g/kg has been reported [29], and
for isophthalic acid, 4.3 g/kg [26].
Ingestion of terephthalic acid or dimethyl
terephthalate results in rapid distribution and ex-
cretion in unchanged form [32]. In rats, at high
ingestion rates of about 3 % terephthalic acid or
dimethyl terephthalate in the feed, bladder cal-
culi are formed which are mostly calcium tere-
phthalate; these injure the bladder wall and lead
12 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
to cancer. Calculi cannot form unless the calcium
terephthalate solubility is exceeded (threshold
effect) [33]. Neither compound has been found
to be genotoxic (Ames test) [34].
Inhalation of terephthalic acid dust appears
to pose no clear hazards. Inhalation by rats for
6 h/d, 5 d/week, for 4 weeks at 25 mg/m3 pro-
duced no fatalities [35]. Dimethyl terephthalate
dust at 16.5 and 86.4 mg/m3 for 4 h/d caused no
toxicological effects after 58 days [29]. The rats
intermittently reacted to the nuisance dust levels
at the higher concentration.
Irritation of the skin, eyes, and mucous mem-
branes by any of these chemicals is mild and
reversible. In rabbits, the FHSA test for tere-
phthalic acid for eyes gave scores of 14.0/110.0
and 3.5/110.0 at 1 and 24 h after exposure. The
FHSA skin test score was 0.4/8.0 [35]. For isoph-
thalic acid, eye and skin irritancy scores were
5.3/110.0 and 0.2/8.0 [36]. Irritation due to di-
methyl terephthalate has also been reported to
be mild [30].
Terephthalic acid, dimethyl terephthalate,
and isophthalic acid can all form dust clouds.
As with any flammable substance, an explosion
can occur, given proper dust and oxygen concen-
trations. Reported limits on the explosive region
for terephthalic acid dust clouds are minimum
dust content of 40 g/m3 and minimum oxygen
content 12.4 % at 20 ◦ C. At 150 ◦ C, minimum
oxygen is 11.1 % [37]. The maximum concen-
tration of an explosible dust cloud has been cal-
culated as 1400 g/m3 [38].
Dimethyl terephthalate and isophthalic acid
have a more stringent oxygen limit. In tests
with carbon dioxide diluent, the minimum oxy-
gen content was 12, 14, and 15 % for dimethyl
terephthalate, isophthalic acid, and terephthalic
acid [39]. The oxygen content is higher for car-
bon dioxide diluent than for nitrogen, owing to
the higher heat capacity of carbon dioxide (the
12.4 % minimum oxygen content reported above
for terephthalic acid was for nitrogen diluent).
For molten dimethyl terephthalate, the flash
and fire points, determined by the Cleveland
open-cup method, are 146 and 155 ◦ C [1].
10. References
General References
1. Kirk-Othmer, 18, 732 – 777.
2. P. Raghavendrachar, S. Ramachandran, Ind.
Eng. Chem. Prod. Res. Dev. 31 (1992)
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3. J. E. McIntyre, Chem. Eng. Monogr. 15 (1982)
400 – 444.
Specific References
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Barker, S. A. Soffer).
6. Mid-Century Corp., US 3 089 906, 1958 (R. S.
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7. W. Partenheimer in D. W. Blackburn (ed.):
Catalysis of Organic Reactions, Marcel
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8. Standard Oil Company (Indiana), US
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13. Eastman Kodak Company, US 4 447 646, 1983
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PTA Process of Hüls Troisdorf AG,” AIChE
Summer National Meeting, Denver, Co. 1988.
15. E. I. DuPont de Nemours, US 2 491 660, 1949
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16. Standard Oil Company (Indiana), US
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18. H. S. Bryant, C. A. Duval, L. E. McMakin, J. I.
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22. S. Shelley, Chem. Eng. (N.Y.) 98 (1991)
no. 12, 90 – 93.
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Catalytic Oxidation System for PTA Plant CO
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25. Chem. Markt. Rep. 242 (1992) no. 4, 42.
26. J. V. Marhold, Sb. Vys. Toxicologickeho
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 Terephthalic Acid, Dimethyl Terephthalate, and Isophthalic Acid
27. A. E. Moffitt et al., Am. Ind. Hyg. Assoc. J. 36
(1975) 633 – 641.
28. A. Hoshi, R. Yanal, K. Kuretani, Chem.
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30. Haskel Laboratories, unpublished data,
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Terpene Resins → Resins, Synthetic
13
34. E. Zeiger, S. Haworth, W. Speck, K.
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