US006288289B1

(12) United States Patent

(10) Patent No.:

Boyd et al.

(54)

US 6,288,289 B1

(45) Date of Patent:

INTEGRATED EFFLUENT TREATMENT

Sep. 11, 2001

OTHER PUBLICATIONS

PROCESS FOR NITROAROMATIC

MANUFACTURE

Koo Chen, HWahak Konghak, (1994), 32(3), 38592.*

(75) Inventors: David Anthony Boyd, Vancouver;

Stuart Alan Gairns, Burnaby; Alfred
Alexander Guenke], Vancouver, an of
(CA)

* Cited by examiner
Primary ExaminerSreeni Padmanabhan
Assistant ExaminerJ. Parsa
(74) Attorney, Agent, or FirmBreiner & Breiner, L.L.C.

(73) Assignee: Noram Engineering and Constructors

Ltd., Vancouver (CA)
_

( * ) Notlce:

5119151449 any dlsclalmer>_ the term of thls

Patent 15 extended or adlusted under 35
U-S-C- 154(9) by 0 days-

(57)

ABSTRACT

An integrated process for treating alkaline Wash Water

effluent from nitroaromatic manufacture, principally con

taining nitro-hydroxy-aromatic compounds is described.
The integrated process concentrates the alkaline Wash Water
to recover chemicals and Water prior to treating the concen

(21) Appl. No.: 09/492,851

trate through supercritical Water oxidation. The supercritical

Water oxidation step consists of treating the concentrate in
the presence of an oxygen source at conditions, Which are

(22)
(51)
(52)

Flled:
Jan 27 2000
Int. c1.7 ........................... .. c07c 205/00; c021I 1/68
US. Cl. ......................... .. 568/934; 568/932; 210/761

(58)

Field of Search ................................... .. 568/932, 934;

uct effluent includes a gaseous Component and a Clean Water

210/761

component, and in the event that insoluble ash is formed, an

ash component. The neW integrated process results in

(56)

References Cited
U-S~ PATENT DOCUMENTS
4,338,199

5,554,299 *

7/1982

supereritieal for Water to eause a substantial portion of the

ergahie Component of the eeheehtrate to oxidize The pred

reduced chemical and Water consumption compared to exist

ing processes. In addition, the treated Wash Water ef?uent
can be recycled to process or directly discharged.

Modell ............................... .. 210/721

9/1996 Joulak et al. ...................... .. 210/712

16 Claims, 5 Drawing Sheets

U.S. Patent

Sep. 11,2001

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US 6,288,289 B1

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U.S. Patent

Sep. 11,2001

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US 6,288,289 B1

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US 6,288,289 B1
1

2
Direct incineration of redWater. In this case, ammonia is
commonly used as the alkali rather than caustic soda,

INTEGRATED EFFLUENT TREATMENT

PROCESS FOR NITROAROMATIC
MANUFACTURE

since no ash is produced during combustion. HoWever,

incinerators can be unreliable due to high temperature

FIELD OF INVENTION

operation and additionally have high operating costs

The present invention is directed to an integrated process

for treating alkaline Wash Water effluent from nitroaromatic
manufacture. The process concentrates alkaline Wash Water
to recover chemicals and Water prior to treating the concen
trate through supercritical Water oxidation. The neW inte
grated process results in reduced chemical and Water con

rate the redWater and then to raise it to combustion

temperatures. Incineration is limited to ammonia Wash

due to the large amount of fuel required to ?rst evapo

ing since sodium or potassium hydroxide Would react

10

High-pressure, subcritical thermal-treatment. This tech

nique includes Wet air oxidation, pressuriZed thermal

BACKGROUND OF INVENTION

treatment Without addition of an oxidant (US. Pat. No.

15

the production of nitrobenZene and dinitrotoluene, are com

monly carried out in mixed acid, a nitrating solution of

sulfuric acid and nitric acid. There are a number of different

commercially practiced mixed acid nitrations. In the case of

nitrobenZene manufacture, adiabatic nitration is commonly

salts in the incinerator. Incineration also often suffers

from poor public image.

sumption compared to existing processes.

Many industrially important aromatic nitrations, such as

With carbon dioxide to form solid or molten carbonate

20

4,230,567), and thermal treatment With the addition of

an oxidant such as nitric acid (US. Pat. No. 5,232,605)
or oxygen (US. Pat. No. 5,250,193). These processes
are effective at detoxi?cation of redWater, but, due to
the formation of stable intermediates such as carboxylic

acids, further biological treatment is commonly

required before release to a receiving Water. These

used (US. Pat. Nos. 4,091,042, 5,313,009, 5,763,697).

processes typically embody large, high-pressure reac

Dinitrotoluene manufacture is carried out in concentrated

mixed acid under isothermal and adiabatic conditions (US.

tors under exothermic conditions, posing some safety

Pat. Nos. 5,902,910, 5,689,018, 4,496,782).

concerns.

Regardless of the type of aromatic or operating

conditions, a key performance characteristic of mixed acid
nitration processes is the amount and type of nitro-hydroxy

High temperature, alkaline digestion of redWater. US.

aromatic byproducts produced. For example, nitration of

benZene produces nitrophenols, nitration of toluene pro

are converted to less toxic, oxalic acid-like compounds.

The resulting effluent must then be neutraliZed and

Pat. No. 5,221,440 describes an alkaline digestion

process Whereby nitro-hydroxy-aromatic compounds

biologically treated before discharge.
Biological treatment. By blending the redWater With

duces nitroresols, and nitration of xylene produces nitroxy

lenols. The majority of nitrated aromatics are subsequently
hydrogenated to their corresponding amine. It is common
practice to remove nitro-hydroxy-aromatic byproducts from
the nitroaromatic product, as these compounds are believed

to adversely affect hydrogenation catalyst performance.

Nitro-hydroxy-aromatic byproducts are commonly
extracted from the crude nitroaromatic into alkaline Wash
Water through counter-current Washing. A number of differ
ent alkali chemicals are commonly used in Washing, caustic
soda and aqueous ammonia being the most common.
Treatment of the alkaline nitro-hydroxy-aromatic con
taminated Wash Water, commonly called redWater due to its

35

shock to the biological system if nitro-hydroxy

aromatic concentrations are too high. In addition, bio
logical removal efficiencies can be too loW to meet

discharge standards and commonly require the use of

40

activated carbon or another secondary treatment

method.

Acid precipitation, extraction and incineration. Nitro

hydroxy-aromatic compounds, such as nitrophenols or
nitrocresols, can be precipitated under acidic condi

characteristic color, remains an active area of research and

development. In the quantities and concentrations generated

another much larger WasteWater stream, the nitro

hydroxy-aromatic toxicity can be reduced to non-toxic
levels. HoWever, there remains the possibility of toxic

45

tions. The precipitates can be extracted from the aque

commercially, these compounds are toxic to most biological

WasteWater treatment systems. Due to its toxicity, nitration

ous phase into an organic phase for subsequent incin

redWater is typically segregated from other plant effluents

Although these processes alloW incineration of a con

eration (US. Pat. Nos. 4,597,567 and 4,925,565).

centrated nitro-hydroxy-aromatic solution, thereby

for separate treatment, usually in a chemical or thermal

treatment process, leaving the majority of the nitration

effluent relatively free of nitro-hydroxy-aromatic com
pounds. In order to reduce the quantity of contaminated
effluent, and thus the cost of the special treatment required,
alkaline Wash Water flow is commonly kept to the minimum

required to achieve adequate product purity. Separation of

50

reducing fuel costs, these processes still suffer from

incinerator permitting issues. Even after the multiple

unit operations of acidi?cation, precipitation,

extraction, concentration and incineration, the redWater
extract typically requires further treatment to meet
55

discharge standards.

inorganic compounds from the redWater is also important for

Chemical oxidation. RedWater treatment processes using

some treatment technologies. For example, many sulfur

oZone, hydrogen peroxide/fentons reagent (US. Pat.

No. 4,604,214) and iron/hydrochloric acid (US. Pat.

compounds Will produce sulfur dioxide upon incineration

and, therefore, redWater should contain loW levels of sulfate
if it is to be incinerated.

60

processing is difficult and chemical reagent costs are

No single redWater treatment technology has achieved

high.

Widespread adoption by the nitration industry. The choice of

Activated carbon. Treatment of industrial scale redWater

a treatment technology is often dependent on local site

Waste With activated carbon is technically feasible, but

conditions, economics and operator preference. The more

common treatment techniques used commercially, and some

previously disclosed processes for treatment of nitration

redWater include:

No. 4,708,806) are knoWn. Achieving required dis

charge standards With these processes Without further

65

is prohibitively expensive.
Deep Well injection. Some facilities dispose of redWater
through deep disposal Wells. This is not acceptable

US 6,288,289 B1
4

3
practice in most jurisdictions and does not reduce the
toxicity of the effluent.

signi?cantly reduced. In the case Where ammonia is used,

recovery alloWs increased ammonia concentrations to be

used in the alkaline Washing, improving nitro-hydroxy

It is clear, therefore, that there remains a need for an
effective redWater treatment process, especially for nitration
aromatic extraction efficiency. In addition, treatment of the
production facilities that do not have access to a biological 5 nitro-hydroxy-aromatic contaminated effluent through
treatment plant. In addition, currently practiced redWater

supercritical Water oxidation, produces a very clean aqueous

treatment technologies are not integrated into the nitroaro-

effluent stream suitable for direct discharge or recycle.

matic Washing process. Integration provides the opportunity

In Comparison With ammonia Washing and Subsequent

to recover and recycle Water, product and chemicals.

incineration of the contaminated effluent, the process offers

SUMMARY OF INVENTION

10 the advantage of substantially lovver energy consumption

and much loWer levels of NOx emissions. It is also believed

The present invention relates to an integrated process to

that the neW process Will be more easily granted environ

treat alkaline Wash Water effluent from nitroaromatic

mental permits, relative to incineration, and enjoy improved
manufacture, for example nitrobenZene, nitrotoluene or 15 public and regulatory agency perception. A further advan
nitroxylene, Wherein the nitrated aromatic is produced in a
tage is that aqueous ef?uent discharge is reduced compared
reaction media of sulfuric acid, nitric acid and Water. Mono-,

With knoWn treatment methods considered hereinbefore.

di- and tri-nitrated nitroaromatic compounds are all com

monly produced by such processes. The process integrates

alkaline Washing, commonly performed to remove nitro
hydroxy-aromatic compounds from the crude nitroaromatic
stream, With an effluent concentrator and supercritical Water
.

BRIEF DESCRIPTION OF THE DRAWINGS

20

In the dIaWIHgS,
FIG 1 is a Schematic representation of the processing

exldanon treatment The process Includes ahead? Contact'

stages of commonly practiced nitroaromatic manufacture.

mg or extraction stage to remove mineral acids prior to the

Table 1 Contains the Stream ?ow data for the Case of

alkahne Washmg Stage

25 mononitrobenZene (MNB) manufacture With sodium
More speci?caul? alkaline Wash Waten Containing nitro'
hydroxide (caustic soda) as the alkali source in Washing.
hydroxy-aromatic compounds,

free

alkali

and dissolved

nitroaromatic, is concentrated in an effluent concentrator,

FIG 2 1S a Sehethahe represehtahoh of the 1hlehheh for

Whereby Water and nitroaromatic product are recovered and

MNB thahhfaehhe> wherelh Sodhhh hydroxlde 15 used as the

recycled. When ammonia is used as the alkali source in 30 eheah Source 1h the alkahhe weshlhg Step' The aheah Value
nitroaromatic Washing, the bulk of the free ammonia is
in the effluent from the supercritical Water oxidation is used
recovered and reused in Washing The effluent Concentrate,

to neutraliZe the Weak effluent. Table 2 contains the stream

containing elevated concentrations of nitro-hydroxy-

how data

aromatic Compounds> is then treated in the Presence of an

FIG. 3 is a schematic representation of the invention for
Oxygen Source at Conditions Supercritical for Water, these 35 MNB manufacture, Wherein ammonia solution is used as the
conditions hereinafter at times referred to as supercritical
alkali Source in the alkaline Washing Step Weak ammonia
Water Oxidation? The resultant effluent includes a gaseous
solution is recovered and recycled back to alkaline Washing.
component and an aqueous component. Asolid or insoluble
Table 3 Contains the Stream ?ow dam
ash can also be formed, as an ash component. Supercritical

Water Oxidation can achieve Such high nitro_hydroxy_ 40

FIG. 4 is a schematic representation of the invention for

aromatic destruction and total Organic Carbon (TOC)

reduction, Without NOx formation, that the resultant ef?uent

MNB manufacture, Wherein ammonia solution is used as the

aheah Seuree _1h the alkahhe Washlhg Step ahdeththehla

can in many Cases be discharged Without further treatment

distillation is included to increase 'the concentration of the

Alternatively, the resultant aqueous effluent can be recycled

ammonia recycled to alkaline Washing. Table 4 contains the

to the nitroaromatic process to further reduce Water and 45 Sheath how data

alkali Consumption

FIG. 5 is a schematic representation of the supercritical

The invention has many advantages. For example, Water

and chemical consumption in nitroaromatic Washing are

Water oxidation pilot plant employed in folloWing Examples

4, 5, 6 and 7.

TABLE 1
Stream Table for FIG. 1 (Case of MNB manufacture With caustic Washing)
Stream Number

Total FloW
Benzene

Mononitro-

kg/h
kg/h

31,750.2
31,750.2

40,122.2

93.8 5,000.0 154.1

10

7,500.0 495.9 1,900.0 860,861 831.429

225

kg/h

7,500

11

12

13

44,434.4 7,686.6
1,677.4
225.0

52,104.6
1,902.4

42,500.0 7,456.6

49,946.6

benzene

Nitrophenols
Water
Sulfuric Acid
Nitric Acid
Sodium

kg/h
kg/h
kg/h
kg/h
kg/h

Hydroxide
Sodium Sulfate
Sodium

Nitrophenolates

kg/h
kg/h

14,444.0

3.8
90.0

5,000.0 131.0

7,500.0 421.5

23.1

74.4

25,678.2

5
1,900.0 271,122 249,429
582,009 582,000

95.0
81.0
81.0

5.0

100.0
155.5

US 6,288,289 B1
5

6
TABLE l-continued
Stream Table for FIG. 1 (Case of MNB manufacture With caustic Washing)

Stream Number

Total FloW
Benzene

14

15

kg/h
kg/h

52,035.5
1,902.4

49,978.0
0.5

49,977.5

49,977.5

Mononitrobenzene

kg/h

Nitrophenols

kg/h

Water

kg/h

Sulfuric Acid

kg/h

Nitric Acid
Sodium Hydroxide
Sodium Sulfate

kg/h
kg/h
kg/h

Sodium

kg/h

155.5

16

19

20

21,746.0 5,016.5 155.5 1,901.9

1,901.9

53.4

43.4

17

18

10.0

21

23

28,279.5 1,414.8

53.4

21,693.6 4,925.5 155.5

9.0

22

53.4

53.4

28,136.1

1,361.5

81.0

24

25

27,360.5 7,776.6 7,776.6

22.5

22.5

27,229.2 7,640.7 7,640.7

90.0

1.1

1.1

112.2

112.2

40

41

131.3

Nitrophenolates

TABLE 2
Stream Table for FIG. 2 (Invention With caustic MNB Washing plant)
Stream Number

30

31

32

33

34

35

36

21,901.5

53.4

10.0

43.4

53.4

155.5 5,000.0 4,925.5

21,849.2

81.0

9.0

Total FloW
Benzene

kg/h
kg/h

52,121.1
1,902.4

52,104.6
1,902.4

52,057.5 5,000.0 5,016.5

1,902.4

Mononitro-

kg/h

49,956.6

49,946.6

49,999.5

Nitrophenols
Water

kg/h
kg/h

100.0
81.0

100.0
155.5

Sulfuric Acid

kg/h

81.0

Nitric Acid
Sodium

kg/h
kg/h

37

38

39

28,343.0 341.8 1,478.4

53.4

28,643.3 2,000.0

53.4

benzene

28,199.6 290.6 1,425.0

28,499.4 2,000.0

90.0

51.3

Hydroxide
Sodium Sulfate
Sodium

kg/h
kg/h

131.3

Nitrophenolates
Sodium

kg/h

Carbonate

Oxygen
Nitrogen

kg/h
kg/h

Carbon Dioxide

kg/h

12.6

Stream Number

42

43

44

Total FloW
Benzene

kg/h
kg/h

1,243.4 154.1 7,542.6

22.2

Mononitrobenzene

kg/h

Nitrophenols

kg/h

Water
Sulfuric Acid
Nitric Acid

kg/h
kg/h
kg/h

1,243.4 131.0 7,406.5

23.1

45

46

7,542.6 6,044.6
22.2

47

48

49

50

1,498.0 6,300.0

1,498.0

98.9

21.7

0.5

7,406.5 6,022.4

1,384.1

1.1

1.1

112.8

112.8

51

52

53

1,421.5 175.4

290.0

1,390.9

290.0

0.5

6,300.0

1,384.1

Sodium Hydroxide

kg/h

Sodium Sulfate

kg/h

Sodium Nitrophenolates
Sodium Carbonate
Oxygen

kg/h
kg/h

Nitrogen

kg/h

15.3

Carbon Dioxide

kg/h

132.0

0.6

1.1

1.1

112.2

112.2

8.3

30.5

kg/h

98.9

19.8

TABLE 3
Stream Table for FIG. 3 (Invention With ammonia-based MNB Washing plant)
Stream Number

60

61

62

63

64

65

66

21,901.5

53.4

43.4

53.4

Total FloW
Benzene

kg/h
kg/h

52,121.1
1,902.4

52,104.6
1,902.4

52,058.3 5,000.0 5,016.5

1,902.4

Mononitro-

kg/h

49,956.6

49,946.6

49,999.3

benzene

10.0

67

68

69

28,256.7 495.9 1,392.1

53.4

53.4

70

71

29,368.8 2,000.0

US 6,288,289 B1
TABLE 3-c0ntinued
Stream Table for FIG. 3 (Invention With ammonia-based MNB Washing plant)

Nitrophenols
Water

kg/h
kg/h

100.0
81.0

Sulfuric Acid

kg/h

81.0

Nitric Acid
Sodium

kg/h
kg/h

100.0
155.5

1.0
155.5 5,000.0 4,925.5

21,849.2

81.0

9.0

28,113.3 421.5 1,338.7

29,2158 2,000.0

90.0

74.4

Hydroxide
Sodium Sulfate

kg/h

Ammonia

kg/h

Ammonium

kg/h

131.3

21.6

Nitrophenolate
Ammonium
Bicarbonate

Oxygen
Nitrogen

kg/h
kg/h

Carbon Dioxide

kg/h

Stream Number

Total Flow
Benzene

72

kg/h
kg/h

Mononitrobenzene

kg/h

Nitrophenols

kg/h

Water
Sulfuric Acid
Nitric Acid

kg/h
kg/h
kg/h

Sodium Hydroxide

kg/h

Sodium Sulfate

kg/h

Ammonia
Ammonium

kg/h
kg/h

1,947.4

73

74

34.5 7,430.8
28.9

1,947.4

24.1 7,233.0

10.3

58.7
110.1

75

76

7,430.8 5,349.1
28.9

57.5
2.0

78

79

2,081.7 5,500.0

28.2

7,233.0 5,261.4

58.7
110.1

77

80

81

2,008.2 108.4

0.7

82

83

2,008.2 181.8

290.0

1,986.6

290.0

0.7

1,971.6 5,500.0

1,971.6

1.2
108.1

8.8

1.2
108.1

Nitrophenolates
Ammonium Bicarbonate

kg/h

Oxygen

kg/h

21.6

Nitrogen

kg/h

19.8

Carbon Dioxide

kg/h

131.5

108.4

21.7

TABLE 4
Stream Table for FIG. 4 (Invention With ammonia-based MNB Washing plant and ammonia concentration)
Stream Number

100

101

102

103

104

105

106

21,901.5

54.8

10.0

43.4

54.8

4,925.5

21,849.2

81.0

9.0

Total Flow
Benzene

kg/h
kg/h

52,121.1
1,902.4

52,104.6
1,902.4

52,058.3 5,000.0 5,016.5

1,902.4

Mononitrobenzene
Nitrophenols
Water

kg/h
kg/h
kg/h

49,956.6
100.0
81.0

49,946.6
100.0
155.5

49,9993
1.0
155.5 5,000.0

81.0

Sulfuric Acid

kg/h

Nitric Acid
Sodium Hydroxide
Sodium Sulfate

kg/h
kg/h
kg/h

Ammonia
Ammonium

kg/h
kg/h

107

108

28,256.7 495.9
53.4

28,113.3 421.5
90.0

74.4

Nitrophenolates
Ammonium Bicarbonate

kg/h

Oxygen
Nitrogen

kg/h
kg/h

Carbon Dioxide

kg/h

Stream Number

109

110

34,198.8

Total Flow
Benzene

kg/h
kg/h

1,393.5

Mononitrobenzene

kg/h

54.8

Nitrophenols

kg/h

Water

kg/h

Sulfuric Acid
Nitric Acid

kg/h
kg/h

1,338.7

111

112

1,900.0 6,766.8

113

114

Sodium Hydroxide

kg/h

Sodium Sulfate
Ammonia

kg/h
kg/h

131.3
2.8

Ammonium

kg/h

2.0

Ammonium Bicarbonate

kg/h

21.2

Oxygen

kg/h

Nitrophenolates

1,900.0 6,766.8

116

117

43.8 7,295.9 7,295.9 5,252.7 2,043.2

28.4

34,041.4

115

28.4

27.7

0.7

30.7 7,101.6 7,101.6 5,166.5 1,935.1

13.2

57.7
108.1

57.7
108.1

56.5
2.0

1.2
106.1

US 6,288,289 B1
10
TABLE 4-continued
Stream Table for FIG. 4 (Invention With ammonia-based MNB Washing plant and ammonia concentration)

Nitrogen

kg/h

Carbon Dioxide

kg/h

Stream Number

118

Total FloW

kg/h

Benzene

kg/h

Mononitrobenzene

kg/h

Nitrophenols

kg/h

Water
Sulfuric Acid
Nitric Acid

kg/h
kg/h
kg/h

Sodium Hydroxide

kg/h

Sodium Sulfate

kg/h

Ammonia
Ammonium

kg/h
kg/h

5,400.0

119

120

2,043.2 106.4

121

122

123

124

125

1,971.1 178.4

290.0

4,868.6

384.1

800.0 384.1

1.4

26.3

26.3

4,862.4

304.1

800.0 304.1

2.8
2.0

53.7

53.7

0.7

5,400.0

1,935.1

1,949.9

8.6

1.2
106.1

290.0

126

127

Nitrophenolates
Ammonium Bicarbonate

kg/h

Oxygen

kg/h

21.2

Nitrogen

kg/h

19.5

Carbon Dioxide

kg/h

129.1

106.4

21.3

The crude MNB from nitration (stream 11) is contacted

DETAILED DESCRIPTION OF PREFERRED

EMBODIMENT

With Water to remove mineral acids, principally sulfuric and

nitric acids, in an acidic Washing stage
Either fresh or
process generated Water can be used. If the Wash Water is

The features and details of the integrated process of the

present invention Will noW be described With reference to

the attached ?gures. Three examples of the invention used in

mononitrobenzene (MNB) manufacture are given. Example
1 uses sodium hydroxide as the alkali source in Washing.
Examples 2 and 3 use an ammonia solution in Washing. The
same letter in the different ?gures represents the same

30

nols. The acidic Wash Water is typically combined With other

low-nitrophenol Water
and steam stripped to remove and

process unit operation. The stream numbers given on the

?gures refer to Tables 11 containing stream compositions
and ?oWs. Examples 47 are set forth to illustrate super
critical Water oxidation of an ammonium dinitrophenolate
stream, representative of redWater from an ammonia-based

recover benzene and MNB

35

The stripped effluent, often

called Weak effluent because of the loW concentration of

nitrophenols, is normally neutralized and discharged to a

biological treatment process or to receiving Waters.

From the acidic Washing stage (C), crude MNB (stream

MNB Washing system.

The principal features of the invention can be employed
in various embodiments, including adiabatic or isothermal

maintained suf?ciently acidic, the great majority of the

nitrophenols Will remain in the organic phase, leaving the
acidic Wash Water (stream 17) With loW levels of nitrophe

13), Which noW has the bulk of the mineral acids removed,
40

nitrations of benzene, toluene and xylene, Without departing

is sent to a multistage, counter-current alkaline Wash stage

(D). Under alkaline conditions, nitrophenols in the crude

MNB are extracted into the aqueous phase. The Washed

from the scope of the invention.

organic (stream 14) is then stripped of excess benzene

FIG. 1 illustrates the processing stages typical of nitroaro

to

produce product MNB (stream 15).

matic manufacture. FloW rates and compositions of the

various streams for the case of a 50 metric ton per hour MNB 45

As treatment of nitrophenol Water is costly, Water make

up (stream 6) to the alkaline Wash stage (D) may be

minimized in order to reduce the strong effluent (stream 25)

plant are shoWn in Table 1 and are representative of actual

plant operating conditions, although conditions vary from

plant to plant. The invention integrates the treatment of

treatment costs

nitro-hydroxy-aromatic effluent, commonly called strong

be used as make-up to alkaline Washing. The alkali source

effluent or red Water, With acidic extraction or Washing

50

stripping/neutralization (stage G).

incinerated as no ash is produced from combustion. Since

ammonia is a Weaker base compared With sodium

With reference to MNB manufacture, crude MNB is

55

strength (B) and recycled back (stream 10) to the nitration

60

5,313,009, and 5,763,697). In the case of isothermal

in a separate acid concentration plant.

stage (C), alkaline Washing (D) and subsequently passed to

MNB condensate (stream 12) from acid concentration (B)

(stream 16) from acid concentration (B) is typically routed

to effluent stripping and neutralization

Caustic Soda Based MNB Washing

FIG. 2 shoWs an example of the present invention inte
grated With a MNB plant using sodium hydroxide as the base

in alkaline Washing. Crude MNB (stream 30) from nitration

(A) is processed through an acidic extraction or Washing

nitration, the spent sulfuric acid is brought back to strength

is recovered and routed to Washing. Aqueous condensate

hydroxide, ammonia Washing systems typically exhibit

reduced nitrophenol extraction stage ef?ciency.
EXAMPLE 1

stage. The sulfuric acid concentration step can be thermally

integrated into the nitration step, as in the case of the

adiabatic processes (US. Pat. Nos. 4,021,498, 4,091,042,

(stream 5) in alkaline Washing is commonly sodium hydrox

ide. Ammonia solution is also used in alkaline Washing
instead of sodium hydroxide Where the strong effluent is

(stage C), alkaline Washing (stage D) and Weak effluent

produced in a nitration stage (A) by nitrating benzene in a
mixture of nitric acid and sulfuric acid. Commonly the spent
sulfuric acid (stream 9) is concentrated back to process

Fresh or process generated Water may

65

benzene stripping (stream 32).

The acidic Wash stage (C) is an important feature of the
presently disclosed integrated process as it removes sulfuric

US 6,288,289 B1
11

12

acid from the crude MNB. If sulfuric acid Were to reach

(stream 45) Where the nitrophenol concentration in the

tion under supercritical conditions is very high, over

99.99%. TOC reduction of 99.9% is also readily achievable.
Supercritical Water oxidation of nitrophenol ef?uent is
described in Examples 4, 5, 6 and 7 beloW.
The strong ef?uent concentrator (I) shoWn in FIG. 2 is an
atmospheric evaporator using steam as the heat source.
Commercial hydrogenation processes of nitroaromatic com

effluent is raised from about 2% by Weight to about 6 to 8%

pounds commonly produce signi?cant excess quantities of

alkaline Washing (D), the strong effluent Would contain

sulfate, a compound that Will form a scale under supercriti
cal Water oxidation conditions.

Strong effluent (stream 44) from alkaline Washing (D) is

sent to storage

and then to an effluent concentrator (I)

by Weight. Nitrophenol concentrations in industrial Washing

loW-pressure steam, Which is suitable for use in effluent

acceptable Washing ef?ciency. Asimple atmospheric evapo

concentration, much of Which is normally vented. Another

possible concentration process is membrane separation, such

rator using loW or medium pressure steam is preferred. The

as reverse osmosis.

systems are typically maintained beloW 1 to 2% to maintain

10

concentrate (stream 47) ?oWs to storage (J) and subse

quently (stream 49) to supercritical Water oxidation
To

The ef?uent concentrate (stream 49) is fed to the super

nitrophenol concentrations are beloW the solubility limits,

critical Water oxidation unit

The feed stream in the
presence of an oxygen source is exposed in the supercritical
Water oxidation unit to temperatures and pressures Which are

but slurries could also be handled With the current invention.

ShoWn beloW in Table 5 are experimentally determined

supercritical for Water, typically 500 to 600 C. at 25 MPa,

Which result in a substantial portion of the nitrophenols and

ease handling and safety concerns, it is desirable that the

solubility data at 100 C. for sodium and ammonium 2,4

dinitrophenolate at 100 C. 2,4-Dinitrophenol is the most

15

20

prevalent nitrophenol compound produced during conven

tional adiabatic MNB manufacture.
TABLE 5
25

Experimentally determined sodium and ammonium

dinitrophenol at 1000 C.

Sodium 2,4-

Dinitrophenolate at pH Dinitrophenolate With

Solubility expressed
as dinitrophenol (Wt %)

0.5% excess NH3

6.9

5.2

effluent, reacts With carbon dioxide to form sodium carbon

ate. Due to the fouling nature of sodium carbonate in a
supercritical Water oxidation reactor, a special reactor con
?guration or cleaning system is used in order to prevent the
reactor from plugging. Examples of suitable reactor con

?gurations and cleaning systems for use in the present

invention, Which may be applied in combination, are
described in US. Pat. Nos. 4,543,190, 4,338,199, 5,252,224,

Ammonium 2,4

11

other organics being oxidiZed to carbon dioxide, Water,

nitrous oxide and nitrogen. organically bound sodium is
released and, along With free sodium hydroxide in the strong

30

4,543,057, 5,560,823, 5,620,606, 5,570,889, and 5,890,531,

the teachings all of Which are incorporated herein by refer
ence. Gaseous and aqueous ef?uents are formed upon cool

at 1000 C.

ing. The gaseous effluent (stream 52) is rich in carbon

dioxide and oxygen, and can likely be vented directly to

The concentrator overheads (stream 46) contain Water,

MNB and traces of nitrophenols. In the example provided,
75% of the feed Water is evaporated, condensed and recycled
back to alkaline Washing. As the vapor pressure of nitro
phenols in alkaline solution is very loW, only trace amounts
of nitrophenols are taken overhead in the effluent concen
trator. Due to this recycle of relatively clean Water, fresh
Water make-up to alkaline Washing can be signi?cantly
reduced. Water make-up to industrial nitrobenZene alkaline

Washing systems is typically 0.150.25 kg per kg of

nitrobenZene. Wash Water make-up to alkaline Washing is
often demineraliZed or other high purity Water. Recycle of

35

purposes of this example, the former con?guration is

40

The treated ef?uent (stream 51) contains sodium carbon

45

acidic Wash Water (stream 34), thus reducing alkali make-up

50

NitrobenZene solubility in Water is temperature dependent

and ranges from about 0.2% to 0.5% for conditions present
55

60

dation treatment. Firstly, it reduces the volume of the

effluent, reducing equipment siZe and cost. Secondly, an

effluent containing from 610% nitrophenol has a suf?cient
higher heating value of 1400 to 1850 kJ/kg of solution to
critical Water oxidation unit, While alloWing energy to be

critical Water oxidation treatment.

Ammonia Based MNB Washing

In addition to recovery of Water and nitrobenZene, ef?uent

recovered as medium pressure steam. Nitrophenol destruc

(stream 38) to Weak effluent neutraliZation

Thus, one
surprising result of this invention is that the alkali value in
the caustic soda fed to alkaline Washing is utiliZed tWice;
?rstly to neutraliZe nitrophenol and secondly to neutraliZe
sulfuric acid, as it is effectively regenerated by the super
EXAMPLE 2

product.

alloW self-sustaining (autogenous) operation of the super

oWned treatment (POT) facility after pH adjustment.

51) can be used to neutraliZe sulfuric acid present in the

the same amount.

concentration facilitates subsequent supercritical Water oxi

ate and very loW levels of organics. The treated ef?uent can
be discharged directly to receiving Waters or a publicly

Alternatively, the alkali value of the treated effluent (stream

the effluent concentrator overheads reduces the Wash Water

in industrial nitrobenZene Washing systems. The bulk of

soluble nitrobenZene in the strong effluent (stream 44) is
stripped overhead in the effluent concentrator (I) and
recycled back to alkaline Washing, thus recovering valuable

assumed, Which can be achieved by the combination of a

tubular reactor and a cleaning system such as that described

in US. Pat. No. 5,890,531.

input to 0.040.06 kg per kg of nitrobenZene, and corre

spondingly reduces the total aqueous ef?uent discharge by

atmosphere. Depending on the reactor con?guration chosen,

the sodium carbonate is either recovered With the aqueous
effluent, With ?ushing Water, or in a concentrated brine. For

FIG. 3 illustrates a second example of the present inven

tion integrated With a MNB plant. The process is essentially
the same as that described in Example 1, With the exception
that aqueous ammonia is used as the alkali source for

Washing. Ammonia is generally used Where the spent alka

65

line Wash Water (strong effluent) is incinerated. In contrast to

caustic soda, ammonia and the resulting ammonium salts
produce no ash upon incineration, or other forms of oxida
tion.

US 6,288,289 B1
14

13

ammonia level in the feed to supercritical Water oxidation

has at least tWo advantages: reduced oxygen consumption
and reduced residual ammonium concentration in the ?nal
effluent.
In this example, due to the volatile nature of ammonia and

There are a number of notable differences between caustic

and ammonia Washing:

1. Ammonia is a Weaker base than caustic and thus

ammonia based Washing systems generally have loWer nitro

hydroxy-aromatic extraction ef?ciencies. In MNB
manufacture, extraction of mononitrophenol in ammonia
Washing is especially poor compared to caustic based Wash

ammonium salts, special supercritical reactor designs or

reactor cleaning methods are not required to cope With

ing.

fouling, since the there are no signi?cant levels of fouling

compounds in the feed.

2. Greater molar excess of ammonia is required than

caustic for ef?cient nitro-hydroxy-aromatic extraction.

10

EXAMPLE 3

Spent ammonia Wash Water may have from 0.2 to 1% free

NH3. As this free ammonia is generally lost through

Ammonia Based MNB Washing With Ammonia

Concentration

incineration, ammonia consumption in Washing is signi?

cantly higher than caustic on a molar basis.

3. Ammonium nitro-hydroxy-aromatic salts generally

15

have loWer aqueous solubility compared to sodium based

salts. This often requires that the alkaline Washers using
ammonia run Warm (5080 C.) to maintain nitro-hydroxy

aromatic salt solubility. For example, in conducted experi

mental tests, the solubility of ammonium 2,4

20

dinitrophenolate in Water at 100 C. Was determined to be

5.2% as dinitrophenol, While the solubility of sodium 2,4

dinitrophenolate at 100 C. Was determined to be 6.9% as

dinitrophenol (see Table 5).

4. Ammonia has a signi?cant vapor pressure, Which
permits recovery of excess ammonia from ef?uent streams.

25

cases at greater levels than can be tolerated in the Weak

effluent system. In this case, it is convenient to use the
stripper condensate as make-up Water to the alkaline Wash

ers. The ratio of stripper condensate to crude MNB typically

ranges from about 0.05 to 0.09 kg/kg, much higher than the
fresh Water make-up rate shoWn in Examples 2 and 3.
As in example 2, FIG. 4 illustrates the present invention
integrated With a MNB plant Which utiliZes ammonia in

alkaline Washing. HoWever, ammonia distillation (L) has

As noted previously, the process unit operations for the

ammonia-based Washing example (FIG. 3) are essentially

identical to the caustic-based example (FIG. 2). HoWever,

In the manufacture of MNB, folloWing Washing, benZene

is stripped from the crude MNB. If a live steam stripper is
used, a signi?cant amount of aqueous condensate is pro
duced that can contain loW levels of nitrophenols, in some

30

been added to the overheads from the strong ef?uent con

centrator
In recovering a relatively concentrated ammo

nia solution, for example 10 to 15% by Weight ammonia, a

larger Water make-up is alloWed to the alkaline Washers.

there are a number of signi?cant, non-obvious differences

betWeen the invention With ammonia-based Washing system

and With caustic-based Washing, Which are described beloW.

This permits disposal of nitrophenol containing process

The primary role of the strong ef?uent concentrator (I) is

to reduce the throughput and cost of supercritical Water
oxidation
Surprisingly, the concentration of ammonia

Water, such as the stripper condensate mentioned above, in

the alkaline Washers.

35

In Table 4, the overheads (stream 116) from the strong

Wash Waters also provides a number of additional bene?ts.

The bulk of the free ammonia in the strong effluent is

effluent concentrator (I) are shoWn to contain about 1%

stripped in the strong ef?uent concentrator (I) and recycled

spheric distillation column to 10 to 15% using an indirect

reboiler and a re?ux condenser. The rich ammonia solution

back to the alkaline Washers

In addition to recovering
MNB and Wash Water, this reduces the fresh ammonia

ammonia. This stream can be concentrated in an atmo

40

(stream
The ammonia
125) isstripper
then recycled
bottomsback
(stream
to alkaline
124) contains
Washingtraces

make-up (stream 71) to about the stoichiometric alkali

demand of the nitrophenols. Recovery of excess ammonia
can reduce overall ammonia consumption by 75% or higher.
Another important bene?t of the recovery of excess
ammonia in the strong ef?uent concentrator is that higher

of ammonia, MNB and nitrophenols. This stream can be

processed through the Weak ef?uent stripper

45

centrated nitro-hydroxy-aromatic effluent is replaced by

excess ammonia concentration may be used in the ammonia

Wash Water Without an increase in ammonia consumption.

This is signi?cant because nitro-hydroxy-aromatic extrac

tion ef?ciency improves With increasing ammonia concen

incinerationalso knoWn as thermal oxidationor by an

50

tration in the Wash Water. For example, in conducted tests,

extraction efficiency of 2-nitrophenol from crude MNB Was
found to increase by 50% When the free ammonia concen

aqueous phase thermal treatment processes. Examples of

such aqueous phase processes include: Wet air oxidation,
Wherein the treatment pressure and temperature, in the
presence of air or oxygen, are sub-critical for Water; the

processes of Baur et al (US. Pat. No. 5,232,605) and Carr

et al (US. Pat. No. 5,762,802), Wherein nitric acid is used to

tration in Wash Water Was increased from 0.2% to 1%. Thus,

operation With higher free ammonia concentrations signi?

The methods described above in examples 2 and 3 can be

equally applied When the ?nal treatment step for the con

55

cantly improves MNB product quality by reducing residual

digest and oxidiZe the nitro-hydroxy-aromatic compounds in

pressuriZed thermal treatment; the process of SaWicki et al

nitrophenols.

(US. Pat. No. 5,250,193), Wherein thermal oxidation is

Yet another bene?t of recovery of excess ammonia in the

strong effluent concentrator is that the total ammonia con
centration in the feed to supercritical Water oxidation is

carried out at a pressure supercritical for Water, but at a

greatly reduced. From supercritical Water oxidation tests

With ammonia redWater, it has been found that approxi
mately 50% of the ammonia is converted to nitrogen, nitrous
oxide and Water. The remaining ammonia combines upon

dation is carried out under pressures and temperatures

sub-critical for Water, Without the addition of an oxygen
scurce. These methods, although they are not as advanta
geous as treatment by supercritical Water oxidation, preserve
many of the novel features of the integrated process
described above such as recovery of Water and chemicals;
loWer treatment plant costs due to reduction of the volume

cooling With carbon dioxide and Water to form ammonium

bicarbonate in the aqueous effluent. The bicarbonate in the
effluent buffers the pH to typically about 7 to 8. Reducing the

temperature sub-critical for Water; and the process of Larbig

et al (US. Pat. No. 4,230,567), Wherein the thermal degra

65

US 6,288,289 B1
15

16

of effluent by the concentration stage; and reduced energy

costs for heating, or evaporating and heating, the nitro
hydroxy-aromatic aqueous effluent to treatment tempera

TABLE 6-continued
Feed and effluent analysis of ammonia redWater

tures.

supercritical Water oxidation tests

EXAMPLE 4

Test

Supercritical Water Oxidation Treatment of

Example #6

Variable

Ammonium 2,4 Dinitrophenolate Solution

10

In this example, a synthetic solution containing 1.12 Wt %

2,4-dinitrophenol and about 0.5 Wt % free ammonia in Water

Feed (ppm)

TOC

4,3281

<54

2,4-Dinitrophenol

11,0562

<0.5

NH3 as Nitrogens

4,483

2,101

pH
Nitrate

8.9
<0.254

8.0
0.4

n.d.
n.a.

n.d.
9,2463

Nitrite
Bicarbonate

Was treated at about 25 MPa and 600 C., With feed ?oW rate
of 0.26 liters per minute and an oxygen ?oW rate of 1.30

Effluent (ppm)

redWater from an ammonia-based Washing system. The test

1Calculated from dintrophenol analysis

2Average of 3 analyses, 11051, 11188, 10930 ppm
3Calculated from inorganic carbon, assuming all present as bicarbonate

Was performed in a pilot plant With a tubular reactor as

depicted in FIG. 5. The residence time in the reactor Was

4Less than the detection limit at the analysis dilution ratio

5Includes ammonia and ammonium

about 70 seconds. Feed and aqueous ef?uent analysis results

n.d. = none detected flat baseline on chromatograph

n.a. = not analyzed

kg/h. This ef?uent is representative of unconcentrated MNB

are summariZed in Table 6. Carbon monoxide Was not

detected in the vent gas. Both TOC and dinitrophenol are

beloW detection limits in the effluent.

EXAMPLE 7

EXAMPLE 5

Supercritical Water Oxidation Treatment of

Ammonium 2,4 Dinitrophenolate Solution

Supercritical Water Oxidation Treatment of

25

In this example, a solution of 1.40% 2,4-dinitrophenol

Ammonium 2,4 Dinitrophenolate Solution

In this example the same solution as in example 4 Was
treated at about 25 MPa and 500 C. With a feed ?oW rate
of 0.61 liters per minute and an oxygen ?oW rate of 1.17
kg/h. The residence time in the reactor Was about 30
seconds. Feed and aqueous ef?uent analysis results are
summariZed in Table 6. No simultaneous gas analysis Was

taken. Again, both TOC and dinitrophenol are beloW detec

tion limits in the effluent.

and about 1.1% free ammonia in Water Was treated at about

25 MPa With a feed ?oW rate of 1.0 liters per minute and an
30

oxygen ?oW rate of 2.5 kg/h. Due to heat losses, the reactor
temperature varied from about 600 C. at the inlet to about
470 C. at the outlet. In this test, particular attention Was

paid to the analysis of nitrogen compounds in the aqueous

35

EXAMPLE 6

and gaseous ef?uents. The analysis results are presented in

Table 7 and demonstrate that even Without complete destruc
tion of dinitrophenol, no measurable amount of NOx gases
is formed and that ammonia content in the vent gas is very
loW. The loW nitrate and non-detectable nitrite levels in

examples 4 through 7 further demonstrate that NOx gas

Supercritical Water Oxidation Treatment of

Ammonium 2,4 Dinitrophenolate Solution

40

In this example, the same solution as in examples 4 and

formation and subsequent nitrate formation are not evident

to any appreciable extent in the supercritical Water oxidation
treatment of either dinitrophenolate or of ammonia.

5 Was treated at about 25 MPa and 600 C. With a feed ?oW

rate of 1.33 liters per minute and an oxygen ?oW rate of 6.08
kg/h. The residence time in the reactor Was about 10

Distribution of nitrogen species after

seconds. Feed and aqueous ef?uent analysis results are

supercritical Water oxidation treatment of 2,4

summariZed in Table 6. Carbon monoxide Was not detected

ammonium dinitrophenolate

TABLE 7

in the gaseous effluent. Again, both TOC and dinitrophenol

Test

are beloW detection limits in the effluent.

Variable

Feed (ppm)

Effluent (ppm)

TABLE 6

50

Example #7
Feed and effluent analysis of ammonia redWater
supercritical Water oxidation tests

Test

Variable

Feed (ppm)

Effluent (ppm)

TOC

4,3281

<54

2,4-Dinitrophenol

11,0562

<14

NH3 as Nitrogen5

4,735

2,164

pH

10.2

7.5

Nitrate
Nitrite

1.6
n.d.

0.13
n.d.

2,4-Dinitrophenol
NH3 as Nitrogen1

14,000
10,406

9.8
3,491

Nitrate
Nitrite

n.d. < 5
n.d. < 5

n.d. (<5)
n.d. (<5)
Gaseous

Effluent

Example #4

Bicarbonate

Example #5

Nitrogen

25 v/v %

Nitrous Oxide
Ammonia

3.6 v/v %
3.55 ppmv

Nitrogen Oxides

n.d. (<0.6

(NO and N02)

ppmv)

n.a.

8,1283

TOC

4,3281

<54

1Includes ammonia and ammonium

n.d. beloW the analytical detection limit at the analysis dilution ratio

2,4-Dinitrophenol

11,0562

<14

NH3 as Nitrogen5

4,735

2,858

pH

10.2

7.5

Nitrate
Nitrite

1.6
n.d.

0.46
n.d.

EQUIVALENTS

Bicarbonate

n.a.

10,9983

Those skilled in the art Will recogniZe, or be able to

ascertain using no more than routine experimentation, many

US 6,288,289 B1
17

18

equivalents to the speci?c embodiments of the invention

ammonia solution, Which is recycled to alkaline Washing,

described herein. Such equivalents are intended to be

and a Water stream, Which is not recycled.

encompassed in the following claims.

6. Amethod according to claim 1, 2, 3, 4 or 5, Wherein the

nitroaromatic is mononitrobenZene and the nitro-hydroxy
aromatic compounds are mono-, di- and tri-nitrophenols.
7. Amethod according to claim 1, 2, 3, 4 or 5, Wherein the

It is claimed:

1. A method of integrating nitroaromatic Washing With

supercritical Water oxidation treatment of the effluent, com

nitroaromatic is mono- or dinitrotoluene and the nitro

prising the steps of:

(a) Washing of the crude nitroaromatic product from a
nitroaromatic synthesis process, Whereby the synthesis

hydroxy-aromatic compounds are mono-, di- and tri

nitrocresols.

8. Amethod according to claim 1, 2, 3, 4 or 5, Wherein the

nitroaromatic is mononitroxylene and the nitro-hydroxy

occurs in a mixture of sulfuric and nitric acid, With

acidic Water to remove the majority of the mineral

acids, folloWed by separation of the nitroaromatic from

the acidic Water;

(b) Washing of the nitroaromatic product from the acidic

Washing step in alkaline Water to remove substantially

15

all of the nitro-hydroxy-aromatic byproducts, folloWed

by separation of the nitroaromatic from the aqueous

effluent;
(c) concentration of the aqueous effluent from the alkaline
Washing step by removal of Water and volatile compo

is achieved by evaporation.
12. A method of claim 1, Wherein the concentration step

is achieved by membrane separation.

13. Process of producing nitroaromatics comprising the
steps of:

nents to near or above the nitro-hydroxy-aromatic

solubility;
(d) recycle of Water and volatile components removed in
the effluent concentrator to the alkaline Washing step to

aromatic compounds are mono-, di- and tri-nitroxylenols.

9. Amethod of claim 3 or 4, Wherein step (e) of treatment
of the concentrated nitro-hydroxy-aromatic effluent is incin
eration.
10. A method of claim 3 and 4, Wherein step (e) of
treatment of the concentrated nitro-hydroxy-aromatic ef?u
ent is thermal treatment in the aqueous phase.
11. A method of claim 1, Wherein the concentration step

25

recover Water and product;

(a) contacting an aromatic With a nitrating solution of

sulfuric acid and nitric acid to produce a nitroaromatic;

(b) subjecting the nitroaromatic reaction product of (a) to

(e) treatment of the concentrated nitro-hydroxy-aromatic

effluent in the presence of an oxygen source at condi

an alkaline Wash to provide a Washed nitroaromatic

tions supercritical for Water, to thereby oxidiZe a sub

product and an aqueous concentrate containing organic

stantial portion of the nitro-hydroxy-aromatic and other

components, including nitro-hydroxy-aromatic

organic compounds.

by-products, mixed With said nitroaromatic, Wherein

2. A method of claim 1, Wherein sodium or potassium

the concentrate is prepared to a concentration of solu

hydroxide is used as the base in the alkaline Washing step,

bility of the nitro-hydroxy-aromatic by-products; and

and the alkali value of the effluent from supercritical Water

oxidation treatment is used for neutraliZation of the effluent

(c) subjecting the aqueous concentrate of (b) to super

critical Water oxidation to oxidiZe said organic compo

35

from the acidic Washing step.

nents.

14. Process of claim 13 Wherein the reaction product of

3. A method of claim 1, Wherein ammonia is used as the

base in alkaline Washing and is recovered in the effluent
concentration step and is recycled together With the Water
and volatile compounds to the alkaline Washing step.
4. A method of claim 3, Wherein 0.5 to 1.5% by Weight
free ammonia is present in the alkaline Water used in the

(a) is subjected to a Wash With acidic Water to remove

mineral acids before performing the alkaline Wash of step

(b).
15. Process of claim 13 or 14 Wherein said aromatic is
benZene and said nitroaromatic is mononitroberZene.
16. The process of claim 13 or 14 Wherein said aromatic
is toluene and said nitroaromatic is a dinitrotoluene.

alkaline Washing step.

5. A method of claim 3, Wherein the recovered ammonia,
Water and nitroaromatic from the concentration step is
further treated by distillation to produce a concentrated

45

UNITED STATES PATENT AND TRADEMARK OFFICE

CERTIFICATE OF CORRECTION
PATENT NO.
DATED

: 6,288,289 B1

Page 1 of l

'. September 11, 2001

INVENTOR(S) : David Anthony Boyd et a].
It is certi?ed that error appears in the above-identified patent and that said Letters Patent is
hereby corrected as shown below:

Column 8
Table 3, Total Flow under Stream Number 79 should read -- 2,081.7 -- instead of

2,008.2.
Column 14
Line 44, insert -- (G). -- after stripper.
Line 63, source" should read -- source --.

Column 18
Line 42, mononitroberzene should read -- mononitrobenzene --.

Signed and Sealed this

Twenty-eighth Day of May, 2002

Attest:

JAMES E. ROGAN

Attesting O?i'cer

Director of the United States Patent and Trademark Office