Catalysis Today, 9 (1991) 231-254 237

Elsevier Science Publishers B.V., Amstdam

INDUSTRIAL PRODUCTION AN0 USE OF AOIPIC ACID

A. CASTELLAN, J.C.J. BART and S. CAVALLARO

Oipartimento di Chimica Industriale, Universita degli Studi di Messina,

98010 Sant'Agata di Messina (Italy)

SUMMARY

The present report contains an overview of the current status of single-step

and two-step oxidation processes for the production of adipic acid from cyclo-
hexane, which are compared with alternative adipic acid preparation processes.
This is followed by an outline of the industrial and commercial prospects of
adipic acid.

CONTENTS

1 Introduction 238

2 Production processes of adipic acid 238

2.1 Single-step oxidation of cyclohexane 238

2.1.1 Direct oxidation of cyclohexane 238

2.2 Two-step processes 240

2.2.1 Reaction via phenol 240

2.2.2 Oxidation of cyclohexane to cyclohexanol-cyclohexanone (olone) 241

2.2.3 Oxidation of olone with air 241
3 Industrial production of adipic acid 245
4 Alternative processes 247
4.1 Alkoxycarbonylation of butadiene to dimethyladipate in two steps 248
5 Market prospects 248
6 Applications of adipic acid and its derivatives 251
6.1 Polyamides 251
6.2 (Poly)esters 251
6.3 Food additives 253
References 253

0 1991 Elsevier Science Publishera B.V.

288

1 INTRODUCTION

This series of papers examines the current status of adipic acid (AAD) pro-
duction. The present paper contains general technical information on the pro-
duction processes of AA0 (and of the related cyclohexanol-cyclohexanone/olone
mixtures), the relevant patents, the industrial use and the market prospects of
adipic acid. In the three following papers (refs. 1 - 3) the chemistry of the
nitric acid oxidation of cyclohexanol to adipic acid is further examined and
significant technological improvements are indicated for both batch and con-
tinuous processing.

2 PRODUCTION PROCESSES OF ADIPIC ACID

Both single- and two-step oxidation processes have been described for the
production of AAD from cyclohexane (Fig. 1). The first one-step production pro-
cess was described by Loder (ref. 4). Du Pant's original development of a com-
mercial AAD process dates from 1937. The basis for the traditional, industri-
ally applied, two-step procedure (air oxidation of cyclohexane to olone
followed by oxidation of the intermediates with HN03 to AAD) was laid some time
during World War II (refs. 5, 6).

2.1 Single-step oxidation of cyclohexane

The aforementioned production methods include two single-step processes, one

in which only nitric acid is used and one-in which air serves as an oxidizing
agent. The single-step nitric acid oxidation of cyclohexane to adipic acid is
not very promising because of the low yields (25 - 30 %) and the high reagent
costs (ref. 7).

2.1.1 Direct oxidation

--------_------- of cyclohexane

This process was developed around 1940. At first, it led to rather low
yields but it has recently been studied and improved by Asahi Chemical Industry
(refs. 8, 9) and Gulf (ref. 10). According to the present scheme, cyclohexane
is oxidized with air or oxygen in the liquid phase, using acetic acid as a
solvent and a cobalt salt as an oxidation catalyst. The typical reaction con-
ditions given in the literature are temperatures of 70 - 100 OC and residence
times of 2 - 6 h; the values usually given for the selectivity towards AAD
range between 70 and 75 % at a degree of conversion of between 50 and 75 %.
 239

Asahi stresses the importance of using aldehydes or ketones as promoters

because they favour the formation of Co3+ in the reaction medium; Gulf claims
that the presence of H20 improves the adipic acid yields (by 19 %) (Table 1).
The process is not unanimously approved and has not been implemented
industrially.

TABLE 1
Direct oxidation of cyclohexane to adipic acid

Parameter Operating conditions

(a) (b)

C6H1 /catalyst (mole/mole) 32 10.5

AcOH f C6H12 (kg/kg) 10 6.0
H20 (% w.r.t. AcOH) 7.2
AcH/catalyst (mole/mole) 1
MEK/catalyst 90 95
0.75
Reaction temperature ("C)
Reaction time (h) BE 2.5
Conversion of cyclohexane (%)
Selectivity to AAD (%) 73 E.6

(a) According to Asahi (ref. 8)

(b) According to Gulf (ref. 10)
AcOH = acetic acid
AcH = acetaldehyde
MEK = methylethylketone

Under mild conditions, air oxidation tends to stop at cyclohexanol and cyclo-
hexanone. More drastic conditions, however, lead to complete combustion of the
hydrocarbon. This is why intermediate conditions have to be chosen and ade-
quately controlled (ref. 11). It is also rather difficult to obtain a selec-
tivity similar to that of the traditional process with this route (in spite of
what is claimed in the literature) and further research in this direction has
apparently been discontinued. On the other hand, it cannot be denied that this
procedure would lead to considerable savings, provided that an acceptable
selectivity is achieved, because an entire step could then be eliminated from
the overall production process of adipic acid.
According to Suresh et al. (ref. 12), the oxidation of cyclohexane is an
autocatalytic reaction of the first order as regards the concentration of total
products in the conversion range of 1 - 10 %. The kinetic features of the oxida-
tion catalysed by cobalt naphthenate resemble those of the uncatalysed reac-
tion. In spite of the abundant patent literature, the published information is
limited (refs. 8, 9, 13 - 17). Articles have been published on the influence of
240

mass transfer on the processes (refs. 12, 18 - 20). In addition, the literature
includes reports on the overall oxidation of cyclohexane to AAD and information
on the liquid-phase oxidation on a pilot-plant scale of cyclohexane to AAD
using a mixture of cyclohexanol and cyclohexanone (refs. 21, 22). The latter,
relatively slow, reaction is probably the rate-determining step in the overall
oxidation of cyclohexane to adipic acid.

cA~oOOH 6o_,65 oc / ,/ ‘y
“-‘O
Co. Cr. V. Cu, flu, MO COOH

L COOH

OH
H2
CAT
e-
0
Fig. 1. Adipic acid production processes

2.2 Two-step processes

The starting products are efther cyclohexane or phenol, of which the former
is preferred in view of the lower costs involved.

2.2.1 Reaction via phenol

------____

Phenol may be substituted for cyclohexane for various reasons, for example
the availability of starting materials, plant size, investment costs, etc.
(refs. 23 - 25). Phenol can be hydrogenated to form either prevalently cyclo-
hexanol or cyclohexanone, dependent on the type of catalyst used (nickel,
 241

copper or chromium oxide) and on the operating conditions. For the production
of AAD the alcohol is preferred, while cyclohexanone is usually used for the
preparation of caprolactam. More than 99 % of the phenol can be converted into
cyclohexanol with a selectivity of 97 - 99 %. Small amounts of byproducts are
removed by distillation.

2.2.2 Oxidation
__----- of cxclohexane to cyclohexanol-cyclohexanone
-----_------- --------- (olone)

Approximately 98 % of the total output of AAD in the USA and 94 % of that in

Western Europe is produced from cyclohexane (refs. 23, 24). The first oxidation
step of cyclohexane can be effected in three different ways (Fig. '1): in a
solution, with the help of a soluble cobalt-based catalyst (conventional pro-
cess); with the aid of boric acid (according to Halcon, IFP and Stamicarbon
technology); or by first promoting the mass formation of cyclohexyl hydro-
peroxide, which is then decomposed, under controlled conditions, to form olone.
The reaction conditions for the air oxidation of cyclohexane are summarized in
ref. 23. In order to promote the selectivity (85 - 90 %), low conversion levels
are generally maintained in each step (4 - 15 %), the unconverted cyclohexane
being recycled. After distillation, a 99.5 % cyclohexanol-cyclohexanone mixture
is obtained for use in the nitric acid oxidation step in the production of AAD.
The basic acid-assisted process yields principally cyclohexanol.

2.2.3 Oxidation of olone with air

_-------------

In this process cyclohexane is oxidized by air, with a 8 - 10 % yield, at 25

bar and 120 - 130 "C, in the presence of a cobalt naphthenate catalyst;
unreacted cyclohexane is distilled and recycled. This is followed by the air
oxidation of olone in an acetic acid solution in the presence of Cu and Mn ace-
tate catalysts for 6 hours, at 80 - 85 OC and 7 bar, which results in an 80 %
yield of AAO. This process has been tested on a commercial scale by Halcon
Intl. (ref. 26), but seems to have resulted in adipic acid of poor quality
(ref. 23). Rohm & Haas operate a 10,000 tpa plant in the USA. The development
of the boric-acid assisted process led to an improvement of the two-step air
oxidation of cyclohexane.
The mixture of cyclohexanol and cyclohexanone obtained in the usual oxida-
tion can also be subjected to dehydrogenation first to form cyclohexanone,
which is then (catalytically) oxidized to adipic acid in air. The information
available on this process is rather limited though (refs. 27 - 32). The most
suitable process conditions for the conversion of cyclohexanone to adipic acid
in the presence of a cobalt or manganese acetate are reported in ref. 33.
 243

8
x

a
0
244

Table 2 (contd.)
a The calculated yield does not include unconverted cyclohexanol
b The examples show the effect of the purification of the substrate on the
[poor) purity of the fine1 MD product
The pressure is controlled so as to keep the mixture boiling
The temperature Is controlled by means of a cooltng circuit
Parameter k varies between 20 and 40
Countercurrent flows of nitric mother liquor and air
Production of AAD and oxime
Use of V5* as en oxidizing agent; FIN03 reoxidizes V4* to V5+
Use of nitro-derivatives as solvents
High temperature. Reduction of nitrogen to below a valancy of 2 must be
avoided in order to save HNU3.
k Removal of nitrogen-containing organic impurities et 90 - 110 *C.
Excess urea is removed with the aid of HNO2.
The use of O2 leads to a 30 % saving in HNU3 consumption (from 1.227 to
0.869 kg of HN03/kg of AAD; N2 = 24 %, N20 = 72 %, No = 4 %).
Consumption of O2 instead of HN03. Recycling of Off-gas.
Formation of edipomononitrolic acid (AMA) and dione.
Variations in the HN03 concentration and HN03/cyclohexanol rat.10 affect
the yields of AMNA end dione; higher concentrations lead to higher
AMNA yields.
Recovery of NOx (10% of the off-gas mixture).
Removal of nitrous gases from the mother liquor with the aid of a coun-
tercurrent flow of air. 15 % N02, 22 % N20, 63 % 02.
3 % increase obtained by recycling the catalyst.
Nitrogen-containing impurities amount to 0.02 - 0.2 %; recycle of NO2;
low reaction temperatures allowed.
s The amount of by-products formed increases with the contact time.
t Reduced pressure permits operation at high temperatures and the recovery
of the heat of reaction through evaporation.
” Nitrogen-containing products ere recovered as hydroxylamine end
nitrosylchloride.
” Production of MO from cyclohexanone vie the intermediate formation of
s-caprolactone.
w Oione formation is favoured.
x Simulation on a laboratory scale.

Y 2 % of the recycled product is discharged to qeintain a constant by-

product level; re-use of scrubbing waters.
i! Effect of the pressure of cyclohexane on the air oxidation in SOlUtiOn.
aa At 30 ‘C cyclohexenol is preoxidized with 35 % of the HN03 of the mother
liquor, in the presenca of nitric gases formed in the underlying sec-
tions.
* Industrially applied.
01 Cyclohexanol
one Cyclohexanone
olone Cyclohexanol/one mixture

Using air instead of HN03 presents two advantages:

1) there is no risk of corrosion;
2) no nitrogen oxides need to be recovered, which implies lower investment
costs.
Significant amounts of succinic and glutaric acid are always formed together
with adipic acid. The purification of adipic acid to obtain polymer-grade pro-
duct poses considerable problems. For this reason only applications that do not
require adipic acid of high purity can be considered.
 246

3 INUUSTRIALPRODUCTION
OF AOIPIC ACIO

Practically the entire world output of adipic acid (of Du Pont, Monsanto,
Rh6ne Poulenc, ICI, BASF, UCB and others) is produced via the liquid-phase oxi-
dation of cyclohexane by air to a mixture of cyclohexanol and cyclohexanone,
which is further oxidized to adipic acid with the aid of nitric acid (Table 2).
Only in a few cases is cyclohexanol or cyclohexanone obtained through catalytic
hydrogenation of phenol.
Typical reaction conditions are: a HN03 concentration of 50 - 60 %; reaction
temperatures of 60 - 80 OC; a pressure of 1 - 3 atm.; and the use of copper and
vanadium as catalysts, in concentrations of 0.1 - 0.5 % and 0.05 - 0.6 %,
respectively (Table 3).

TABLE 3

Nitric acid oxidation of cyclohexanol-cyclohexanone.

Reaction conditions and resultsa.

Consumption (kg/kg)
Patentee Temp. b HND3 Catalyst “*3/ Feed HNoJ/ alone/ Refe-
(“C) (wt %I V (wt %) Cu (wt %) olona type* AAD AAD rence

BASF 75- 80 50- 65 0.09 0.11 20 ol-one 1.12 0,730 44

SASF 65 75 55-65+NDx 0.05 0.17 340 01 0.719 45
Du Pant 75 115c 50 0.1 0.5 lo- 15 cl-one 0.6-0.8 0.740 46

I.C.I. 75-8od 40- 50 0.02 0.2 7 ol-one 1.42 0.769 47

1.G.I. 73 66 0.11 0.28 ol-one 0.988 48
Scholven-Chenie 60 59 0.21 0.11 9 01 0.724 49
HDlS 40 64*NDx 0.3 - 12 01 0.699 50
Vickers-Zinmer 60 3D+NOx 0.6 0.1 5.5 01 0.98 0.704 51
RhBne-Poulenc 15-90 50 IMDx) 0.2 4-6 ol-one 0.6-0.7 0.704 52

(U.S.S.R.) 60- 90 56+NDx 0.6 0.1 3-6 ol-one 1.20 1.02 53

kiontedfson 75-80 55-58 0.05 0.3 11 01 0.88 0.724 (f)

a Patent literature
b Atmospheric pressure, unless otherwise indicated
c 2 ata.
d 0.1 - 1 atm.
e 01, cyclohexanol; one, cyclohexanone
f Laboratory experiments carried out in industrial operating conditions.

The following observations are made in the literature:

a) in practice, the average specific consumptions of olone and AAD vary from
0.740 to 0.714 kg/kg (which corresponds to an AAD yield of 92 - 96 % of the
theoretical value);
b) the HN03 consumption (kg of HN03/kg of AAD produced) varies from 0.65 to
0.8 according to Du Pont and Rhane-Poulenc's patents; ICI claims a value of
around 1.42;
246

TABLE 4
Process for the production of adipic acid. Main characteristics.

P,ocII
P.wnm, uon@aiin Rhbrn-PwJ*m n&SF D" PO"vuO~ulm
 241

c) the best yields (particularly those of Chemische Werke Hills and of Rhdne
Poulenc) were obtained by oxidizing cyclohexanol at low temperatures.
Since the reaction is very exothermal, an AAD plant based on the nitric acid
oxidation of olone must be equipped with an efficient heat-exchanging system
and must be capable of processing solutions with high HN03/olone ratios in a
manner enabling efficient thermal control (ref. 23).
Adipic acid is usually recovered from the oxidation solution via crystalli-
zation at 30 - 70 OC and the mother liquors are recycled after having been con-
centrated at reduced pressure (Table 4). A fraction is drained to avoid accumu-
lation of glutaric and succinic acid. Various methods have been investigated
for the recovery of the adipic acid, HN03 and the catalysts from this drained
mixture. The only disadvantage of this excellent process, which leads to a high
yield of product of high purity, is the substantial nitric acid consumption.
The HN03 consumption is discussed further in refs. 2 and 3.

4 ALTERNATIVE PROCESSES

In the past, much research has been done on alternative starting materials,
but so far no other procedure has been applied on a commercial scale. Numerous
alternative processes have been suggested (for a survey see Vesel'chakova et
al. (ref. 34) and Leitner (ref. 35)), for example:

a) HN03 oxidation of cyclohexene (90 % yield);

b) HN03 oxidation of a cyclohexane/nitrocyclohexane mixture (88 % yield);

cl HN03 oxidation of caprolactone;

d) ozonisation of cyclohexene;

e) photochemical interaction of cyclohexane and NO2 (82 % yield);

f) electrochemical oxidation of 6-hydroxycaproic acid;

9) reaction of butadiene with CO or CO2;

h) carbonylation of butanediol;

i) reaction of acetylene or vinyl acetic acid with di-t-butyl peroxide in

the presence of acetic acid, etc.
248

After the direct oxidation of cyclohexane with air and the oxidation of the
olone mixture with air the most interesting alternative procedures are hydra-
tion followed by oxidation of cyclohexene and carbonylation of butadiene.

4.1 Alkoxycarbonylation of butadiene to dimethyladipate in two steps

Two BASF patents, issued in 1978 (refs. 36, 37), open new perspectives for a
potentially very interesting way of producing adipic acid. In this process
butadiene is reacted with carbon monoxide and methanol in two separate reac-
tors. In the first reactor methyl-3-pentenoate is formed at a pressure of 600
atm. and a temperature of 120 'C, in the presence of cobalt and tertiary amine
(pyridine, picoline, quinoline, etc.) catalysts:

CH3

CH2=CH-CH=CH2 + CO + CH30H + CH3-CH=CH-CH2COOCH3 + CH2= 1-CH2-COOCH3

98 % <l%

In the second reactor the pentenoate is once again reacted with CO and metha-
nol, at 30 atm. and a temperature of 185 "C, to form dimethyladipate (75 %),
dimethyl and methyl glutarate and dimethyl ethyl succinate. The costs envisaged
for a plant producing 100 ktpa according to the BASF process are slightly lower
than those required for the construction of a new plant operated on the basis
of the traditional process, i.e. the two-step oxidation of cyclohexane (ref.
38).
The costs involved in producing adipic acid from butadiene are the same as
or less than those of the process starting from cyclohexane even though the new
process uses a more expensive starting material and requires more sophisticated
equipment in the first step. A particular disadvantage of the traditional pro-
cess is the necessity of recovering the nitrogen oxides.

5 MARKET PROSPECTS

In January 1986 the world output of adipic acid amounted to 1597 ktpa, of
which 42 % was produced in the USA and 37 % in Western Europe (ref. 24). Since
76 % of the U.S. output (1986) is used for nylon 6.6 fibres, the manufacturers
of synthetic fibres are usually also the main producers of adipic acid (ref.
23). Tables 5, 6 and 7 show the major producers in the USA, in Western Europe
and in Japan, and some investment projects. Nylon 6.6, produced from adipic
acid and hexamethylene diamine (HMDA), and nylon 6, manufactured from caprolac-
 249

TABLE 5

U.S. producers of adipic acida

Producer Location Raw material Capacity (ktpa)b

Allied- Hopewell (VA) phenol 14

Signal
Du Pont Sabine (TX) cyclohexane 180
Victoria (TX) 310
Maitland (Ont) 100
Singaporec unknown 110
Monsanto Pensacola (FL) cyclohexane 254

Total 968c

a Ref. 24
b As of Jan. 1, 1986
c Scheduled for 1993

TABLE 6

Capacity of adipic acid in W. Europea

Country Capacity Raw material World capacity

Company, Location (ktpa) (%)

1
wstendeb 27 cyclohexane

France 12
RhBnePoulenc, Chalampg 230 cyclohexane

3
si Chimica, Novara 50 (phenol)

13
migshafen 2ooc cyclohexane
Bayed, Leverkusen 40 cyclohexane

Great Britain 16
I 9 Wiltond- cyclohexane

W. Europe (total)

a Ref. 24 (Jan. 1986)

b Production will probably be discontinued in near future.
c Debottlenecking to 240 ktpa is envisaged (1990).
d ICI intends to adopt the adiponitrile technology for nylon 6.6 production.
250

TABLE 7

Japanese producers of adipic acida

Producer Plant location Raw material Capacity

(ktpa)

Asahi Chemical Industry Nobeoka cyclohexanol/oneb 60

(Miyazaki Prefecture)
Kanto Denka Kogyo Shibukawa cyclohexane 9.6
(Gumma Prefecture)
Honshu Chemical Industry Wakayama cyclohexane 6c
(Wakayama Prefecture)
Sumitomo Chemical Company Niihama cytlohexane 2
(Ehime Prefecture)
Ube (Yamaguchi Prefecture) ;;:;;:exane/ 2

Toray Industries d
Mitsubishi Petrochemical - e

Estimated total production 106f

a Reference year: 1989

b Purchased from Nippon Lactam (Sumitomo Chemical). Asahi (Mirushima) is now
constructing a 60 ktpa cyclohexanol plant (cyclohexene hydration technology)
for use as a raw material for adipic acid. HN03 oxidation technology.
c Production uncertain
d Toray purchased adipic acid probably from Honshu Chemical
e Construction plans
f Reference year: 1991

tam, together account for the greater part of the world market of synthetic
fibres. In the USA, nylon 6.6 is used twice as much as nylon 6. In England and
France too the use of nylon 6.6 predominates, whereas in Japan, Brazil, Italy
and other European countries nylon 6 has the largest market share (ref. 23).
One of the factors which has had a great influence on the European adipic
acid market over the past years is the decline in the use of AA0 as an inter-
mediate in the production of HHDA (refs. 23, 24). Until the 196Os, practically
all of the diamine used for the production of nylon 6.6 was obtained by con-
verting AA0 and ammonia into adiponitrile, which was then hydrogenated to form
HMDA. But Llu Pant's processes based on furfural (1948) and, later, butadiene
and Monsanto's commercial electrochemical process for the hydrodimerization of
acrylonitrile provided alternatives for AA0 in the production of HMOA (ref.
25). When the production of adiponitrile from butadiene was started in 1977 at
ChalampB, France (in a 104-ktpa plant jointly operated by Ou Pont and RhBne-
Poulenc) and the Monsanto~ontefibre joint venture started to produce adipo-
nitrile from acrylonitrile at Seal Sands (England) in 1978, a large stock of
alternative starting material for the production of HMOA was formed in Europe,
 251

which resulted in a temporary overproduction of adipic acid (refs. 23, 24).

Also ICI has recently announced its intention to switch its nylon 6.6 produc-
tion from the traditional cyclohexane-AAD route to the adiponitrile (from
acrylonitrile) technology (ref. 54). In 1981 Celanese shut down a plant for the
production of HMDA from adipic acid (via 1,6-hexanediol instead of adipo-
nitrile). From 1982 through 1986 the average annual growth rate of adipic acid
production world-wide amounted to 2.0 - 2.5 %, as compared with an annual
growth rate of 6.0 - 6.5 % in the period from 1971 to 1981. Similar figures are
envisaged for the period until 1991 on the basis of, primarily, the increased
use of nylon 6.6 resin in fibres and plastics. Du Pont's projected Singapore
adipic acid plant (1993) will position this company as a major nylon 6.6
supplier in the Asia Pacific in the 1990s.

6 APPLrCATIONS OF ADIPIC ACID AND ITS DERIVATIVES

Adipic acid is an intermediate used in the chemical, pharmaceutical, food

and perfume industries (refs. 23, 39).

6.1 Polyamides

A large proportion of the total output of adipic acid is used as an inter-

mediate in the production of nylon 6.6 (Table 8), especially via the conden-
sation of hexamethylenediamine. This application requires material of very high
quality. A new development in nylon polymers, the synthesis of high-molecular
weight poly(tetramethylene adipamide) (nylon 4.6), is based on the polyconden-
sation of adipic acid with diaminobutane (refs. 40, 41) and this will have some
impact on the AAD market from 1990 onwards. The commercial product (STANYL,
registered trade-mark of DSM) is very suitable for applications requiring
resistance to high temperatures and excellent mechanical properties, such as
industrial yarns and engineering plastics for the automotive and electrical &
electronic industries (ref. 42).

6.2 Polyesters

AAD is not only used to manufacture polyamide but also plasticizers (3 %),
polyurethanes (5 %) and a variety of other industrial products (2 %) (Table 8).
About 90 % of the esters is marketed as plasticizers for PVC, natural and
synthetic adhesives, polystyrene and cellulose derivatives, the other 10 %
being used for synthetic ester lubricants (hydraulic liquids). Of course, this
262

market segment is greatly dependent on the commercial prospects of polyamides.

Linear and complex polyesters are used for the production of polyurethane
resins (flexible and semi-rigid foams), elastomers, adhesives and coatings.
In particular, AAD is used to manufacture:
- monomeric and polymeric ester plasticizers;
- polyester resins for

(i) surface coating applications;

(ii) polyurethane formulations for rigid and flexible
urethane foams;
(iii) urethane rubbers;

(iv) special polyester resins for electrica 1 insu 1,

ation;

(v) resins for resin/fibre-glass mouldings (e.g. car bodies, boats,

etc.);

(vi) wet strength paper resins;

- synthetic ester lubricants or lubricant additives.
Esterification with polyalcohols leads to polymeric plasticizers that are
insoluble in hydrocarbons and do not tend to migrate. The esters obtained with
glycerine, glycols, butanediols, trimethylolpropane, triethanolamine, etc.,
serve as the basis for a series of alkyd resins. Adipic acid can also be com-
bined with trimethylolpropane to obtain a basis for floor coverings. Adipic
acid polyesters react with diisocyanites to form excellent rubber-like
materials and lacquers. The iso-propylester and amylester of adipic acid are
widely used as fixatives in the perfume industry. In addition, AAD is used to

TABLE 8

U.S. consumption (ktpa) of adipic acida

Final product b Year

1977 1982 1986 1991c

Nylon-6.6d 539.0 450.3 608.8 701.4

Adiponitrile/HMDA 126.2
Polyurethanes 26.3 25.0 29.6 34.0
Plasticizers 22.7 18.2 21.3 24.5
Others 15.9 18.2 15.0 18.2

Total 730.1 511.7 674.7 778.1

a Ref. 24
b In most cases the AAD production is for captive use, U.S. merchant market
is negligible.
c Estimate
d Fibers and resins
 253

produce ketone, nitrile, diamine and diamide intermediates for pharmaceutical

products, insecticides and fungicides.

6.3 Food additives

Adipic acid is one of the many food additives approved by the Food and Drug
Administration as 'generally recognized as safe'. As such, it may be used as a
substitute for the more common food acidulants citric and tartaric acid (ref.
43). Adipic acid is now used in gelatine-based desserts, powdered concentrates
for fruit-flavoured beverages, bottled beverages, non-standardized jams and
jellies, sweets, precooked food, canned vegetables and flavourings.
As the greatest part of the adipic acid output is used for applications out-
side the food-processing industry, little attention has so far been paid to the
production of adipic acid of the high purity required by food processors. Also
Du Pont's projected 'Adi-Pure' high purity adipic acid plant in Singapore is
expected to serve mainly the region's automotive, electronics, appliance and
electrical industries.

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1940.
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