Chemosphere ± Global Change Science 2 (2000) 425±434

Abatement technologies for N2O emissions in the adipic acid

industry
A. Shimizu *, K. Tanaka, M. Fujimori
Asahi Chemical Industry Co., Ltd., Leona Plant 4-3401, Nagahama-cho, Nobeoka, Miyazaki 882-0854, Japan
Received 21 June 1999; accepted 11 January 2000

Importance of this paper. Plants manufacturing adipic acid (AA), the material for nylon 6, 6, are operating throughout
the world and have been pointed to as one of the sources of nitrous oxide. The capacity of nitrous oxide from all adipic acid
plants in the world is estimated at 576,250 t per year. The major adipic acid manufacturers have now begun to operate nitrous
oxide reduction facilities and these plants now emit only a small part of the nitrous oxide that they produce. Forecasts say
that more than 80% of the nitrous oxide produced by all adipic acid plants in the world will be eliminated by 1999±2000.

Abstract

Adipic acid (AA) is the main intermediate in nylon 6, 6 that is manufactured by polymerization condensation of AH
salt (hexamethylenediammonium adipate). Adipic acid is also an intermediate in the production of polyester-polyol, a
material used in polyurethane.
Annual production capacity of AA for 1998 was estimated to be 2.3 million metric tons and about 80% of that AA is
used to manufacture nylon 6, 6. Almost all AA is produced by nitric acid oxidation of KA oil, a mixture of cyclo-
hexanone and cyclohexanol.
The reaction of nitric acid oxidation unavoidably generates nitrous oxide. The N2 O emission coecient for Japan's
AA plant is approximately 0.25 kg-N2 O/kg-AA. If the N2 O output from all adipic acid plants is calculated using the
N2 O emission coecient described above and the world's AA production capacity then we obtain a ®gure of 576,250
metric tons per year, but if we calculate only that which will be clearly reduced by 1999±2000, a reduction of ca. 80% has
already been achieved. This is because the N2 O abatement equipment of the major AA manufacturers is scheduled to
have completed startup by 1999±2000.
The main technologies used to reduce nitrous oxide in the adipic acid industry are catalytic decomposition and
thermal destruction. These methods convert nitrous oxide into nitrogen and oxygen. Catalytic decomposition operates
at about 500°C and thermal destruction operates at and over 1000°C. Using these reduction technologies allows the
adipic acid manufacturers to reduce N2 O emissions by 90% or more. Ó 2000 Elsevier Science Ltd. All rights reserved.

Keywords: Catalytic decomposition; Thermal destruction; Nitric acid oxidation; Nitrous oxide; Abatement technology

1. Introduction

Literature on nitrous oxide emissions point to

chemical equipment in the adipic acid (AA) process as
generators of nitrous oxide (Thiemens and Trogler,
*
Corresponding author. Fax: +81-982-22-6557. 1991; Reimer et al., 1995, 1994; RITE, 1996, 1997, 1998,
E-mail address: a8012202@msns.ut.asahi-kasei.co.jp (A. 1999). Thiemens and Trogler (1991) have pointed out
Shimizu). the in¯uence of nitrous oxide emission caused by AA

1465-9972/00/$ - see front matter Ó 2000 Elsevier Science Ltd. All rights reserved.
PII: S 1 4 6 5 - 9 9 7 2 ( 0 0 ) 0 0 0 2 4 - 6
426 A. Shimizu et al. / Chemosphere ± Global Change Science 2 (2000) 425±434

plants upon the EarthÕs atmosphere. The 1992 IPCC Table 1

report says that the total N2 O emitted from all natural Production capacities of adipic acid (1998)
and anthropogenic sources is 5.2±16.1 Tg-N/y and the Producer Region Capacity t/yr
nitrous oxide emitted by the AA industry is 0.4±0.6 DuPont North America 695,000
Tg-N/y. UK 205,000
In 1991, the main AA manufacturing companies, Singapore 110,000
Asahi, BASF, Bayer, DuPont, ICI (cf. Appendix A (a)) Solutia USA 320,000
and Rhone-Poulenc (cf. Appendix A (b)) convened a Others USA 15,000
meeting, under their own volition, called the N2 O Inter- Rhodia France 240,000
Industry Group Meeting (cf. Appendix A (d)) and from Brazil 55,000
then on these companies exchanged technology that Korea 50,000
BASF Germany 235,000
accelerated research and development on N2 O abate-
Bayer Germany 50,000
ment techniques. All these companies have already an-
Radici Italy 50,000
nounced the N2 O abatement technologies they are using CIS, East Europe 65,000
and are reporting their schedules for the operation of China 92,000
N2 O abatement processes in the world's major AA Asahi Japan 120,000
plants by 1999±2000 (Reimer et al., 1995, 1994). Others Japan 3000
This paper gives the present state of N2 O abatement
technologies and the future trends in development. Total 2,305,000

Nitrous oxide is a byproduct in the course of nitric

2. The adipic acid business
Adipic acid is an important monomer that is an
intermediate of nylon 6, 6, made by polymerization
condensation with hexamethylene diamine (HMDA)
and as an intermediate in the polyester polyol that
makes up polyurethane. The world's AA production
capacity for 1998 is estimated at 2.3 million tons per
year. About 80% of that AA goes into the production
of nylon 6, 6. Nylon 6, 6 is used to make the widely
used products of tire cord, carpets, textiles, upholstery
and auto parts.
Table 1 shows the estimated manufacturing capacity
of all AA manufacturers in the world and that the ca-
pacity in the entire world is 2,305,000 t/yr in 1998 (PCI,
1996; cf. Appendix A (e)).
3. The mechanism by which N2 O is emitted from adipic
acid plants
Reactions (1) and (2) indicate the nitric acid oxida-
tion reaction.
acid oxidation as reactions (1) and (2) show. The logical
emission coecient in reaction (2) is 0.30 kg-N2 O/kg-
AA, but the emission coecient actually measured at the
Nobeoka Works of Asahi Chemical was 0.25 kg-N2 O/
kg-AA (survey by Miyazaki Prefecture in 1994), which is
because in the actual reaction, part of the nitric acid
becomes NOx and N2 (Thiemens and Trogler, 1991).
4. N2 O generated quantities
Table 2 shows the estimates for manufacturing ca-
pacity of nitrous oxide by all AA manufacturing plants
and the estimated reductions in nitrous oxide for 1999±
2000.
When we use the 0.25 nitrous oxide emission coe-
cient described above, the total nitrous oxide capacity for
AA manufacturing plants is 576,250 t/yr (0.37 Tg-N/y).
These ®gures are in good accordance with ®gures in
the previous paper by Thiemens and Trogler (1991). In
short, if there were absolutely no abatement of N2 O by
AA plants this is the quantity of N2 O that would be
emitted, but because the N2 O abatement of the major
manufacturers has proceeded to the great extent that it
has at present, as will be described later, the numbers for
actual N2 O emissions are quite a bit below this. If we
take the rate of decomposition for the N2 O decompo-
sition process to be an average of 90% (cf. Appendix A
(f)), then the total N2 O reduction quantities for 1999±
2000, for just the main companies, is a total 520,000 t/yr,
and 81% of the entire N2 O generation capacity is re-
duced for 1999±2000. It probably understates the num-
ber of N2 O reduction quantities because the announced
 A. Shimizu et al. / Chemosphere ± Global Change Science 2 (2000) 425±434 427

Table 2
Estimated amount of N2 O abatementa
Capacity t/yr N2 O t/yr
AA N2 O Reduced Emitted
Major producers 2,080,000 520,000 >468,000 <52,000
Others 225,000 56,250 No information

World total 2,305,000 576,250 >468,000

0.37 Tg-N/y Reduction rate >81%
a
Major producers: Asahi, BASF, Bayer, DuPont, Rhodia, Solutia.
Premises: Proportion of N2 O generation ˆ 0.25 kg-N2 O/kg-AA. Decomposition rate of N2 O ˆ 90%.
Reduced N2 O ˆ N2 O Capa. ´ 0.9 Emitted N2 O ˆ N2 O Capa. ± Reduced N2 O.
Announced decomposition values of the actual processes: Asahi 98%, BASF 90±95%, Dupont 98%. No information on other plants.

values of the N2 O reduction processes at the actual

plants are between 90% and 98% (Reimer et al., 1994,
1995; cf. Appendix A (g)). Since it is possible, in prin-
ciple, to reach a rate of N2 O decomposition of close to
100%, there is also a possibility that future technological
development will increase the mean rate of decomposi-
tion of these processes even further.
The emissions from AA plants were calculated to be
less than 5% of all N2 O generated by natural and an-
thropogenic sources in the entire world in the 1992 IPCC
report. With the current abatement technologies this
Scheme 1. Elementary reactions of N2 O decomposition.
value falls to 1%, or less, by 1999±2000.
The industrial source of N2 O except AA plant is
dodecanedioic acid plant (Thiemens and Trogler, 1991)
Dodecanedioic acid is a material for nylon 6, 12, and
manufactured by nitric acid oxidation of cyclododecanol
and cyclododecanone (Weissermel and Arpe, 1994).
Compared with AA plant, production capacities of
dodecanedioic acid are small. Therefore, the N2 O gen-
erated from dodecanedioic acid plant may be negligible. Scheme 2. Reaction network for N2 O decomposition reaction.

5. Technology for reducing N2 O in the adipic acid
industry
5.1. Mechanisms for decomposing N2 O
Many scholars have been examining the chemistry
for the decomposition of N2 O (Loirat et al., 1985;
Kuratani and Tsuchiya, 1978). Scheme 1 shows the el-
ementary reactions of N2 O decomposition. Eq. (1)
shows the initial reaction. M signi®es many di€erent
kinds of compounds such as N2 O, N2 O or O2 . Eq. (2)
shows that the major reaction generating material in the
decomposition of N2 O is N2 and O2 . Eqs. (3) and (6) are
for the NO generation reaction and Eq. (5) is the NO2
generation reaction.
Scheme 2 shows the mutual relationship between the
elementary reactions. N2 O and NO are mutually con-
verted by Eqs. (3), (6) and (5). N2 O is converted into N2
and O2 as indicated by Eq. (2). NO generation is not
important until the reaction temperature goes over
800°C. The generation of N2 and O2 is exothermic, and
the heat of reaction is calculated from Eqs. (1) and (2) as
ÿ8:5 kJ/mol. The NO generation reaction is endother-
mic and its heat of reaction is calculated from Eqs. (1)
and (3) as +8.5 kJ/mol.
5.2. The processes of decomposing N2 O by the companies
The N2 O abatement technology of the major AA
manufacturers is chie¯y the catalytic decomposition
process or the thermal destruction process (Reimer et al.,
1994, 1995). Other than these processes, there are
reports of a method that consumes N2 O as an oxidant
for phenol synthesis (cf. Appendix A (g)). Table 3 brings
together all the processes used by the companies (Reimer
et al., 1994, 1995). Below we will give a general de-
scription of the technology for each company that has
been made known through their patent applications.
428 A. Shimizu et al. / Chemosphere ± Global Change Science 2 (2000) 425±434

Table 3 the ¯ow system requires rarefying the process gases to

N2 O abatement technologies maintain the catalyst temperature at optimum level. The
Producer Technology Start up improved method introduces the process gas containing
Asahi Thermal 1999 N2 O into several stages of a ®xed bed plug ¯ow reaction
BASF Catalytic 1997 column that reduces the quantity of rare®ed gases to
Bayer RFBa 1993 control the reaction temperature and maintains the N2 O
DuPont Catalytic 1997 decomposition reaction at the prescribed temperature to
RFBa 1958, 1976, reduce energy costs. Fig. 1 shows the reactor described
1994 in the patent. Numbers 17, 18, 24 and 25 are inlets for
Rhone-Poulenc Thermal 1997 the process gas, 19 is the preheating chamber, 22 is the
Catalytic 1998 catalyst layer and 26 is the outlet for generated gas.
Solutia Phenol production 2000
Descriptions of patents other than those that have
a
Reducing ¯ame burner. been submitted by the AA manufacturers are given here.
Air Products & Chemical and Engelhard (1993, 1991)
has reported a hydrotalcite catalyst that contains metal
5.2.1. Catalytic decomposition process and a metal-ion-exchanged zeolite catalyst, Grande
BASF announced in 1997 that it would introduce Paroisee (1993) has reported on a moldenite/NH4 /Fe
N2 O decomposition equipment that uses the catalytic catalyst, and Agency of Industrial Science and Tech-
method (cf. Appendix A (f)). It then completed N2 O nology (1996) has reported on a catalyst that is Rh2 O3
decomposition equipment for an AA 240,000 t/yr plant supported on Al2 O3 .
at 13 million Deutsche Marks and announced that it had Table 5 gives a summary of the reaction conditions
achieved a decomposition rate of 95% (cf. Appendix A and results for using the above catalysts.
(g)). The catalyst used in the patent application is either Fig. 2 shows the process that was made public by
a spinel type CuAl2 O4 , a catalyst that are Ag and CuO BASF (1997). Exhaust gases 1 and 3 containing N2 O
supported on Al2 O3 , or a catalyst that is Ag supported and NOx from the plant pass through compressor V1
on Al2 O3 . When the catalysis is around 500°C using the with air ¯ow 2 to increase the pressure. That makes the
o€ gas which contains 23% N2 O, from the actual AA temperature of mixed air ¯ow 4 250±350°C. Heat ex-
process, all of these catalysts give a decomposition rate changers WT1 and WT2 cool air ¯ow 4 to 30±40°C, it
of 99% or higher. Table 4 shows the major gas compo- then becomes air ¯ow 5 that passes through absorption
sitions that have been emitted from the AA process column K1 to recover NOx as nitric acid. Air ¯ow 6 that
(BASF, 1991, 1993, 1994a,b). exits absorption column K1 is heated to 450±500°C by
DuPont announced that its catalytic process worked heat exchangers WT1 and WT3 and is then supplied to
in 1997 and that the catalyst was CoO and NiO sup- decomposition reactor C1. WT3's heat source is the gas
ported on ZrO2 (cf. Appendix A (d)). When N2 O of after N2 O decomposition. The catalyst in reactor C1
100% concentration is processed at a reaction tempera- decomposes N2 O and discharges air ¯ow 9 at approxi-
ture of 402°C, the N2 O decomposition rate is 98.5%. mately 800°C temperature. The air ¯ow after decom-
When ZrO2 is used as the support, it has good low position is cooled to 260±300°C by heat exchangers
temperature activity compared to Al2 O3 , with degrada- WT3 and WT4 to become air ¯ow 10. Heat exchanger
tion also decreased (DuPont, 1993). WT4 recovers the decomposition heat from N2 O as
Asahi Chemical (1993) has proposed a catalyst that is steam. Air ¯ow 10 is introduced into adiabatic reactor
CuO supported on Al2 O3 . According to our investiga- C2, that contains an NOx reduction catalyst which re-
tion, processing the AA plant emission gases that con- duces the NOx to N2 and O2 . The temperature of air
tain 34% N2 O at a reaction temperature of 620°C gives ¯ow 11 at exit C2 is 265±310°C, and turbine T1 gives
an N2 O decomposition rate of 99.5% and higher. Asahi adiabatic expansion of the air ¯ow and discharges it into
(1999) has also proposed a further improved catalytic the atmosphere at 100°C.
decomposition device. The catalytic decomposition in Either the isothermal reactor or the adiabatic reactor
is believed appropriate to use as the decomposition re-
actor in catalytic decomposition of N2 O, but it is not
Table 4
clear what type of reactors the AA manufacturers are
O€-gas analysis of ADA plant
actually using. The form of the adiabatic reactor is one
Component Mol/% in which the reaction device is a ¯ow system column type
N2 O 23 ®xed bed. With the isothermal reactor, a reactor device
NO2 17 is used that has a structure made from a cooling agent
N2 47 and a heat exchanger and a ¯ow system multi-duct
O2 7.5 catalyst ®lled layer (BASF, 1997). The N2 O emitted
H2 O 3.0
from an AA plant has high concentration, thus
 A. Shimizu et al. / Chemosphere ± Global Change Science 2 (2000) 425±434 429

Fig. 1. Reactor for the catalytic decomposition.

Table 5
Reaction conditions and results of catalytic decomposition
Cat Metal Temperature Conv. SV (1/h) N2 O conc. Experimental
(wt%) (°C) (%) of inlet (%) term (h)
ZnO, CuAl2 O4 /Al2 O3 480 > 99:9 4000 23 1036 BASF
MgO, CuAl2 O4 /Al2 O3 480 > 99:9 4000 23 1025 BASF
CaO, CuAl2 O4 /Al2 O3 480 > 99:9 4000 23 1013 BASF
Ag, CuO/Al2 O3 Ag:14.9 490 > 99:9 4000 23 242 BASF
Ag/Al2 O3 Ag:14.2 550 > 99 4000 23 550 BASF
CoO, NiO/ZrO2 Co:0.916 402 98.5 600 100 DuPont
Ni:0.908
CuO/Al2 O3 Cu:2.4 620 > 99:5 3350 34 2400 Asahi
Co±Al-hydrotalcite Co/ 450 99 30,000 0.1 Air products,
Al:2.2 Engelhard
Cu±ZSM-5 Cu:4.0 400 95 30,000 0.1 Air products,
Engelhard
Mordenite/NH4/Fe 540 99.7 13,300 50 Grande Paroisse
Rh2 O3 /ZnO Rh:0.5 500 100 40,000 0.1 MITI

presenting the possibility of temperatures rising higher
than the temperature tolerances of the reactor and the
catalyst and this requires special caution when an adia-
batic reactor is used. It is important that the temperature
at the reactor outlet will have to be held to about 800°C.
The temperature of the adiabatic reactor is controlled by
the quantity of rare®ed gases that are supplied with the
process gas and the temperature of the isothermal re-
actor is controlled by the reactor coolant (molten salt).
A method has been proposed for controlling reactor
temperature by returning UOP to the reactor after de-
composition and after the gas has cooled (UOP, 1993).
Fig. 3 shows the process ¯ow in that method. In the
diagram, 1 is the ¯ow of gas containing N2 O, 2 is the
NOx removal process, 14 is the N2 O decomposition
section, 30 is the heat exchanger, 55, 56 and 57 are the
recycle lines, and 25 and 50 are the discharge lines. There
are also methods for controlling reactor temperature by
inserting external air, but this method is thought to be
advantageous in heat terms because the gas is recycled
after the reaction.
The heat of the reaction of N2 O decomposition is
comparatively high at ÿ81:5 J/mol, and the generated
heat can be used in steam generation by process gas
preheaters and boilers. The ability to recover heat is an
advantage of the decomposition processing of N2 O
generated from the AA process.
There is a possibility of the life of the catalyst be-
coming a problem with catalytic decomposition. The
deterioration of catalysts, for example Pd/Al2 O3 and
CuO/ZnO, have been reported in the patent application
(Asahi, 1993). The detailed data of deterioration for the
catalyst in Table 5 have not been disclosed. We are
awaiting further data in order to obtain knowledge on
this point.
Fig. 4 is a conceptual diagram of the catalytic pro-
cess.
5.2.2. Thermal destruction process
The thermodynamics and kinetics on the elementary
reactions of N2 O decomposition have been studied in
detail (Loirat et al., 1985; Kuratani and Tsuchiya, 1978)
430 A. Shimizu et al. / Chemosphere ± Global Change Science 2 (2000) 425±434

Fig. 2. Catalytic decomposition process.

Table 6
Thermal destruction of N2 Oa
Component Concentration
Feed (mol/%) Product (mol/%)
N2 O 51.0 0
NO 0.02 2.63
NO2 0.20 8.28
CO2 5.52 4.57
Fig. 3. Temperature control of the catalytic decomposition O2 5.57 16.21
process. N2 37.7 68.31

Total ¯ow rate 2.87 Nm3 /h 3.46 Nm3 /h

a
Reaction conditions: Temperature: 1054°C. Pressure: 1.5 kg/cm2 .
LV:44.7 cm/s. Residence time: 1.2 s.

recovered as nitric acid. The air ¯ow from which NO2

Fig. 4. Conceptual diagram of catalytic process.
and a reaction simulation is feasible. Because the de-
composition reaction of N2 O into N2 and O2 is an
exothermic reaction, if the decomposition is done on
adiabatic condition, the heat of the reaction will con-
tinue the decomposition.
Asahi Chemical (1986) has proposed a method of
decomposing N2 O into nitrogen and oxygen and one
that recovers NO generated as nitric acid. Table 6 shows
that allowing the N2 O in the gas emitted from an AA
plant to remain in a reaction furnace for 1.2 s at 1054°C
decomposes the N2 O 100% and converts 21% of the
N2 O supplied into NOx . Fig. 5 shows the process ¯ow
described in the published patent. The exhaust gas
generated from AA reaction process 8 is ®rst pressurized
to 1±2 kg/cm2 by water-sealed pump 16 and after the
NO contained is oxidized into NO2 in oxidation column
17, it is fed into absorption column 18 and the NO2 is
has been removed is fed into the plug ¯ow reactor 19
where thermal destruction reaction is performed on the
N2 O. After thermal destruction, air ¯ow feeds into a
plug ¯ow reactor tube so that it can be heated externally
and used to heat process gas. The air ¯ow then feeds into
boiler 20 to be heat-recovered, it is then cooled to room
temperature by heat exchanger 24, and then feeds to
absorption column 27 where the NOx is recovered as
nitric acid. Asahi Chemical (1999) has also applied for a
patent on an improved N2 O processing equipment. This
method heats part of the gas, which contains N2 O,
supplied to the reactor to start a decomposition reaction
and the remaining gas that contains N2 O is supplied in
several stages to the decomposition reactor to be de-
composed. Fig. 6 shows the reactor that is described in
the patent description. Numbers 1 and 4 in the diagram
are the entrances for the process gas 2 is the preheating
chamber, 5 is the thermal destruction chamber, 6 is the
exit for the generated gas. In this method, the quantity
of energy that is supplied to the reactor to sustain the
N2 O decomposition reaction is kept extremely low. For
energy input a combustible gas such as hydrogen or
methane is used, and the amount of heat input required
for 1 Nm3 decomposition of the 550°C process gas that
 A. Shimizu et al. / Chemosphere ± Global Change Science 2 (2000) 425±434 431

Fig. 5. Thermal decomposition process.

Fig. 6. Reactor for the thermal destruction.

contains 33.9 mol% N2 O is 46.0 kJ and the decompo-
sition rate is given as 99% or higher.
The thermal destruction method has the advantage of
being able to recover NO as nitric acid. It is also supe-
rior on the point of given o€ with almost no industrial
waste discharge because there is no replacement of cat-
alyst. Asahi Chemical began the operation of its thermal
destruction method in 1999 at an investment cost of 600
million yen to achieve a 98-plus-percentage rate of de-
composition.
DuPont (1995) has proposed a method of sponta-
neously maintaining the thermal destruction of N2 O,
by starting the destruction by placing methane com-
bustion of process gas containing N2 O in contact with
a ¯ame. This method mixes methane gas with a gas
containing 660°C N2 O in a mixing tee and heats it to
850°C or higher to create a decomposition reaction.
Using this method to process the exhaust gas from an
AA plant that contains 57% N2 O gives an N2 O con-
centration at the reactor exit of 200 ppm or less at
1050±1254°C of decomposition temperature. It also
generates about 10% NOx from the N2 O which can be
recovered as nitric acid. The amount of methane for
processing gas 20 SCFM (ft3 /min) containing 57 mol%
N2 O is 30,000 BTU/h (1 BTU ˆ 1.055 J) by conversion
of heat volume.
Hoechst (1992) has proposed a method of decom-
position that sprays the process gas containing N2 O into
432 A. Shimizu et al. / Chemosphere ± Global Change Science 2 (2000) 425±434

a ¯ame created by combustion of natural gas. This

method uses ¯ame temperature to decompose the N2 O,
but it uses more fuel than the DuPont method described
above. Processing 240 m3 /h cubic meters per hour of
N2 O, for example, takes 15.2 m3 /h of natural gas and
113 m3 /h of air. The concentration of N2 O in the gas
after it has passed the reactor is 80 ppm.
Bayer does its processing using a reducing ¯ame
burner (RFB) (Reimer et al., 1994, 1995). A patent has
been applied for the combustion device (Bayer, 1991) for
achieving the reducing atmosphere, but it is not clear
whether this method will be used in the processing of
N2 O. Fig. 8. Conceptual diagram of thermal process.
Rhone-Poulenc (1995) has proposed a method that
uses plasma to convert N2 O into NOx . This method
discharges an arc into the air ¯ow containing N2 O to able to recover NOx because its decomposition temper-
generate plasma and convert that N2 O into NOx . Fig. 7 ature is higher than the catalytic process.
shows the device. The air ¯ow containing N2 O is pre-
heated in gas preheater 7 to pass out of nozzle 3, be-
5.2.3. Phenol synthesis
comes plasma by the discharge of an arc across
Monsanto (cf. Appendix A (c)) has announced its
electrodes 10, converts to NOx in area 6, and then exits
schedule of placing in operation by a target date of
from 17. In radiation form, the six electrodes are set in
1999±2000 a process for processing N2 O as the result of
opposition so that there are three pairs each. The
using zeolite as the catalyst and causing benzene to react
amount of electricity required to process gas containing
with N2 O and producing phenol (cf. Appendix A (h)).
31.6±50.9% N2 O at 22.0±81.8 Ndm3 /min is 0.8 to
This method takes as its base the technology from the
2.1 kW. The reaction rate when process gas containing
Boreskov Institute of Catalysis (1995). When a reaction
50.9% N2 O is supplied at 25°C and an equivalent of
is made at SV 600 hÿ1 and a reaction temperature of
37.4 Ndm3 /min is 26.1%, and the NOx selection rate is
430°C using a ZSM-5 zeolite catalyst that contains
55.7%.
0.45% Fe2 O3 , they have achieved results of a 98% phenol
Fig. 8 shows a conceptual diagram of the thermal
selection rate and a 100% N2 O reaction rate. The se-
destruction process. It has the major feature of being
lectivity with the cumene method is reportedly about
93%, so that the selection rate with the N2 O oxidation
method is much better. This method might be dependent
on location and production quantity of the AA plant so
that it places restrictions on the freedom of plant design
but a lot of attention is being given to it as a method of
N2 O decomposition and phenol production.

6. Future trends

Because of the high 20±60% N2 O concentration in

Fig. 7. Plasma chemical reactor.
exhaust gas from the AA process, N2 O decomposition
heat can be recovered and reused in N2 O decomposition
or it can be used as steam for other processes in the
factory. Taking into consideration the large e€ect that
these processes have on reducing the environmental
burden, the capital costs are relatively low. However,
there are problems with the heat source in the abatement
of exhaust gases with low N2 O concentration in pro-
cesses other than AA, because of the low quantity of
heat generated along with the decomposition and the
need to heat the large quantity of gases that coexist with
N2 O to a temperature sucient for decomposition. If
petroleum products are used for the heating source, then
 A. Shimizu et al. / Chemosphere ± Global Change Science 2 (2000) 425±434
carbon dioxide will be produced. This is why it is
thought that highly active low temperature catalysts will
have to be developed. Caution must be given to carbon
dioxide generated from the heating source and the
quantity of N2 O that is decomposed in the thermal de-
struction processes.
The technologies for N2 O abatement in AA manu-
facturing seem generally to be complete but it is be-
lieved that there is still room for improvement. It is
hard to discuss the question of catalyst deterioration
because few data on this subject have been released,
but if we assume that catalyst deterioration is a general
phenomenon, there will be costs for new purchases of
replacement catalyst. The thermal destruction process
generates relatively large amount of NO in high tem-
perature decomposition. Therefore, it is hoped that
equipment materials with high temperature resistance
will be developed because if the furnace's ability to
withstand heat increases, the amount of recovered ni-
tric acid increases.
Since new AA plants are scheduled to be built in
various parts of the world (cf. Appendix A (i)) and it can
be predicted that some of the plants do not have N2 O
decomposition processing, there should be continued
improvement in the technology to introduce it into those
plants.
N2 O is a gas with the properties of an oxidizing
agent so that one of the future means of N2 O abate-
ment will be the development of technologies for sep-
arating and recovering N2 O cheaply from exhaust gases
and the development of technologies for using N2 O in
a way that will take advantage of these features
(BASF, 1982).
Acknowledgements
Contained in this paper are results from surveys
made by the Research Institute of Innovative Technol-
ogy for the Earth (RITE) and the New Energy and In-
dustrial Technology Development Organization
(NEDO). The authors wish to thank both organizations
for giving the opportunity to participate in their com-
mittees.
Appendix A
Adipic acid (AA) business was restructured as fol-
lows: (a) The AA business of ICI was succeeded by
DuPont, (b) the AA business of Rhone-Poulenc was
succeeded by Rhodia, and (c) the AA business of
Monsanto was succeeded by Solutia. The authors have
referred to the following industrial information: (d) 1992.
European Chemical News May 25, p. 35, (e) 1997. Asian
433
Chemical News Decmber 1, 4, p. 38, (f) 1997. Financial
Times February 3, p. 20, (g) 1998. European Chemical
News 12±18 January, p. 43, (h) 1996. Chemical Market
Reporter December 30, p. 1, (i) 1997. Chemical Week
November 5, 159, p. 22.
References
Agency of Industrial Science and Technology, Japan, 1996.
Kokai H8-224474.
Air Products & Chemical and Engelhard, 1991. US07/790611,
Kokai H5-245384.
Air Products & Chemical and Engelhard, 1993. US08/113023,
Kokai H7-163870.
Asahi Chemical, 1986. Kokai S61-257940, 1993. Kokoku H5-
79657.
Asahi Chemical, 1993. Kokai H5-4027.
Asahi Chemical, 1999. WO99/25461.
BASF, 1982. DE3244370.6, Kokai S59-109226.
BASF, 1991. DE4029061.1, Kokai H4-247238.
BASF, 1993. WO93/04774, Kohyo H6-509984.
BASF, 1994a. WO94/16798, Kohyo H8-505567.
BASF, 1994b. WO94/02244, Kohyo H7-509398.
BASF, 1997. WO97/10042.
Bayer, 1991. DE4116950.6, Kokai H5-253446..
Boreskov Institute Catalysis and Solutia, 1995. WO95/27691,
Kohyo H9-511518.
DuPont, 1993. WO93/15824, Kohyo H7-503653.
DuPont, 1995. WO95/20541.
Grande Paroisse, 1993. FR9305573, Kokai H7-68131.
Hoechst, 1992. FR9201413, Kokai H5-339003.
Kuratani, K., Tsuchiya, S., 1978. Shock Wave in Chemistry and
Physics; Butsurikagaku Sensho 3. Shokabo, Tokyo, pp. 170±
178.
Loirat, H., Caralp, F., Forst, W., Schoenenberger, C., 1985.
Thermal unimolecular decomposition of nitrous oxide at
low pressures. J. Phys. Chem. 89, 4586.
PCI, 1996. World Nylon 6 and 66 Supply/Demand Report, PCI
Fibers and Raw Materials, pp. 49±50.
Reimer, R.A., Slaten, C.S., Seapan, M., Lower, M.W., Toml-
inson, P.E., 1994. Abatement of N2 O emissions produced in
the adipic acid industry. Environmental Progress 13 (2),
134±137.
Reimer, R.A., Slaten, C.S., Seapan, M., Lower, M.W., Toml-
inson, P.Ez., 1995. Abbattimento di N2 O nellÕ industria dellÕ
acido adipico. Tecnologie Chimiche 6, 81.
Rhone-Poulenc, 1995. WO95/07234, Kohyo H8-501769.
RITE, 1996. Survey on Nitrous Oxide Abatement, The
Research Institute of Innovative Technology for the Earth
(RITE), Japan, pp. 68±70.
RITE, 1997. Survey on Nitrous Oxide Abatement, The
Research Institute of Innovative Technology for the Earth
(RITE), Japan, p. 16.
RITE, 1998. Survey on Nitrous Oxide Abatement, The
Research Institute of Innovative Technology for the Earth
(RITE), Japan.
RITE, 1999. Survey on Nitrous Oxide Abatement, The
Research Institute of Innovative Technology for the Earth
(RITE), Japan.
434 A. Shimizu et al. / Chemosphere ± Global Change Science 2 (2000) 425±434

Thiemens, M.H., Trogler, W.C., 1991. Nylon production: an un-
known source of atmospheric nitrous oxide. Science 251, 932.
UOP, 1993. US 5, 200, 162.
Weissermel, K., Arpe, H.-J., 1994. Industrielle Organishe
Chemie. VCH Verlagsgesellschaft, Germany.
The authors as a group investigate a new production process of
nylon 6, 6 intermediates. The backgrounds of authors, Shimizu,
Tanaka and Fujimori, are physical organic chemistry, chemical
engineering and organic chemistry respectively.