Tkk Projek

8/17/2019 Tkk Projek

1/6

United S t a t e s

Patent [ 1 9 1

H i l l

e t

a l .

[ 1 1 1 3 , 7 9 9 , 9 9 3

[ 4 5 ]

Mar.

2 6 , 1974

[54] PROCESS FOR THE MANUFACTURE OF 2 , 4 7 5 , 0 9 5 7/1949 Hoek . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260/645

TRINITROTOLU N

2,934,571

4/1960

Bonetti

.

.

. .

. .

. .

.

. . . .

. .. 260/645

3,708,546 1/ 1973 Coon t a l . . . . . . . . . . . . . . . . . . . . . . . . . . 2 6 0 / 6 4 5

[ 7 5 ]

I n v e n t o r s :

Marion

E .

H i l l ,

P a l o

A l t o ;

W e s l e y

E .

T o w e l - g , A t h e r t o n ;

G e r a l d

J _ FOREIGN PATENTS OR APPLICATIONS

McDonald,

Menlo

Park, a l l

of

C a l i f .

752,608

7/1956

Great

B r i t a i n . . . . . . . . . . . . . . . . . . . . . 260/645

1,054,571

1

1967

G

B

'

.................... . 260 645

[ 7 3 ]

A s s i g n e e : The U n i t e d S t a t e s

o f America

a s /

rem

mam /

r A e g r l e s e w z g h l g

‘ t 2 :

s l e j c l é m r y o f t h e P r i m a r y E x a m i n e r - L e l a n d A . S e b a s t i a n

y ’ g ’

Attorney, Agent, or

Firm-Edward J . Kelly; He rbe r t

[ 2 2 ] F i l e d : A u g .

2 5 , 1 9 7 2

B e r l ;

A . V i c t o r

E r k k i l a

' [ 2 1 ] A p p l .

N o . 1

2 8 3 , 6 9 4

[ 5 7 ] ABSTRACT

[ 5 2 ] 0 . 5 .

C I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 6 0 / 6 4 5 ,

260/688

P r o c e s s f o r P r e p a r i n g

TNT o m p r i s e s

n i t r a t i n g

t o l u e n e

[ 5 1 ] I n t .

C l .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

C07c

79/ 10 w i t h

an anhydrous n i t r a i i n g

agent

NOZHSO4

obtained

{ 5 8 ]

F i e l d o f

Search

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260/645 by

mixing

HNOQ and

oleum-

The

P r o c e s s

e l i m i n a t e s

p o l l u t i o n

problems

a s s o c i a t e d w i t h

c o n v e n t i o n a l

m a n

[ 5 6 ] R e f e r e n c e s C i t e d u f a c t u r i n g p r o c e s s e s a n d p r o d u c e s TNT n h i g h y i e l d s

UNITED STATES PATENTS

and

r a p i d

r e a c t i o n

r a t e s .

2 , 2 9 7 , 7 3 3

10/1942 Wyler

e t

a 1 .

. . . . . . . . . . . . . . . . . . . . . .

. .

260/645 1 4 Claims, 1 Drawing

Figure

T O L U E N E

H N O 3 + 8 0 3

l D N T

+ H

2 5 0 4

l

80 TNT

DINITRATOR r

TRINITRATOR ——> To

‘ r W O R K U P

NITRATING

ACID

ONT

20

'

RECYCLE

ACIDS

SOLVENT I

EXTRACTION

,.___>

SURPLUS

H 2 s o 4 r o

ACID

RECOVERY


2/6

P M E N T E D H A R Z S

m 4 3 7 9 9 . 9 93

T O L U E N E

H N O 3 + 8 0 3

l D N I + H 2 3 0 4 8 0 l

T N T

DINITRATOR

RINITRATOR ->T°

WO R K U P

A

NITRATING

ACID MT

20

RECYCLE

ACIDS

SOLVENT

,

EXTRACTION

‘_____>

SURPLUS

H 2 504 T O

ACID

RECOVERY


3/6

3 , 7 9 9 , 9 9 3

1

PROCESS FOR THE MANUFACTURE

OF

TRINITROTOLUENE

The

i n v e n t i o n d e s c r i b e d

h e r e i n

m a y be

manufac

t u r e d , u s e d and l i c e n s e d b y o r f o r t h e Government f o r

governmental purposes

without

t h e

p a y m e n t

t o

u s

of

a n y

r o y a l t i e s

t h e r e o n .

BACKGROUND OF

THE

INVENTION

The i n v e n t i o n r e l a t e s t o a

p r o c e s s

f o r producing TNT

( 2 , 4 , 6 - t r i n i t r o t o l u e n e ) . I n p a r t i c u l a r t h e

i n v e n t i o n

r e

l a t e s

t o

a

p r o c e s s

f o r

n i t r a t i n g

t o l u e n e

t o produce

TNT.

TNT s

c o n v e n t i o n a l l y

manufactured

b y

a

m u l t i s t e p

p r o c e s s , wherein toluene i s ? r s t n i t r a t e d with a mixture

o f

n i t r i c a c i d and s u l f u r i c a c i d t o produce

MNT

(mononitrotoluene),

t h e MNT s t h e n n i t r a t e d t o DNT

( d i n i t r o t o l u e n e ) and

t h e

DNT

s

? n a l l y n i t r a t e d t o

TNT,

t h e

a c i d s t r e n g t h and t e m p e r a t u r e

b e i n g i n

c r e a s e d f o r each

n i t r o

group i n t r o d u c e d . The TNT b

t a i n e d c o n t a i n s s ma l l

amounts

of

o t h e r

TNT

s o m e r s

i n

addition

t o

t h e desired

2,4,6-isomer a s w e l l a s DNT s o

mers,

which must

be

r e mo v e d i n order t o produce a

TNT

f s u f f i c i e n t

p u r i t y f o r u s e a s

a m i l i t a r y

e x p l o s i v e .

S u c h

p u r i f i c a t i o n i s u s u a l l y a c c o m p l i s h e d b y

a s e l l i t i n g

p r o c e s s ,

which

i n v o l v e s t r e a t i n g t h e c r u d e

TNT i t h

aqueous sodium

b i s u l f i t e

s o l u t i o n , which s e l e c t i v e l y

e x

t a c t s t h e

undesired

TNT

i s o m e r s from

t h e

d e s i r e d

2 , 4 , 6 ~ i s o m e r . The w a s t e l i q u o r s r e s u l t i n g from s u c h s e l

l i t i n g

o p e r a t i o n s ,

c a l l e d

“red w a t e r , cannot be

eco

n o m i c a l l y

p u r i ? e d

w i t h o u t

c r e a t i n g a s e r i o u s p o l l u t i o n

p r o b l e m . I n

a d d i t i o n , l a r g e amounts

o f

n i t r o g e n

o x i d e

fumes a r e

evolved

from

the

n i t r a t i o n reactors a n d cre

a t e

a s e r i o u s a t m o s p h e r i c p o l l u t i o n p r o b l e m , w h i c h i s

c o s t l y

t o a l l e v i a t e .

SUMMARY OF

THE

INVENTION

An b j e c t o f t h e

p r e s e n t

i n v e n t i o n i s

t o

p r o v i d e a

p r o

c e s s

f o r n i t r a ti n g

t o l u e n e

t o

TNT

n

h i g h

y i e l d s and

r a p i d r e a c t i o n

r a t e s .

Another o b j e c t i s t o provide

a n o v e l

p r o c e s s f o r n i

t r a t i n g DNT o TNT

n

h i g h y i e l d s .

A u r t h e r

o b j e c t

i s

t o

p r o v i d e a p r o c e s s f o r n i t r a t i n g

t o l u e n e

t o TNT, which

p r o d u c e s

TNT f

m i l i t a r y

s p e c i

f i c a t i o n

g r a d e , e l i m i n a t e s

t h e p o l l u t i n g n i t r o g e n o x i d e

fumes emanated from t h e

conventional

n i t r a t i o n r e a c

t i o n s and

e l i m i n a t e s

t h e s e l l i t e process

w i t h

i t s a t t e n

d a n t r e d w a t e r

d i s p o s a l

p r o b l e m .

A t i l l f u r t h e r

o b j e c t

i s

t o provide

a

p r o c e s s f o r n i t r a t

i n g t o l u e n e which m i n i m i z e s t h e f o r m a t i o n o f m e t a l i s o

m e r s , maximizes

t h e r a t i o

o f 2 , 4 -

t o

2,6-DNT

i s o m e r s

p r o d u c e d a n d

m a x i m i z e s

t h e

y i e l d o f

d e s i r e d

2 , 4 , 6

TNT

s o m e r .

Another

o b j e c t i s t o p r o v i d e a c o n t i n u o u s , c l o s e d

l o o p p r o c e s s f o r n i t r a ti n g

t o l u e n e

t o TNT.

These

and o t h e r o b j e c t s and

a d v a n t a g e s a r e a c h i e v e d

b y

t h e

p r o c e s s o f t h i s

i n v e n t i o n , which

i s based

on

t h e

u s e o f an

e x t r e m e l y

a c t i v e anhydrous

n i t r a t i n g

m i x t u r e

p r e p a r e d from HNO3

and

o l e u m .

I n

a c c o r d a n c e w i t h

t h e p r o c e s s

o f t h i s

i n v e n t i o n , t o l u e n e

i s

n i t r a t e d

t o DNT

b y r e a c t i n g i t a t

t e m p e r a t u r e s

below about

4 0 °

C

i t h

a n anhydrous m i x t u r e

o f

I - I N O a

and

o l e u m ,

and

t h e

DNT h u s produced

i s n i t r a t e d t o TNT,

w i t h o u t i s o l a

t i o n from t h e

d i n i t r a t i o n

r e a c t i o n m i x t u r e , by t r e a t m e n t

a t a temperature of a t l e a s t about 70°

C

with an

anhy

d r o u s m i x t u r e o f l - I N O a

and

o l e u m . When h e t r i n i t r a

t i o n

r e a c t i o n

i s c o m p l e t e , t h e r e a c t i o n m i x t u r e i s

c o o l e d

t o p r e c i p i t a t e t h e TNT, which

i s s e p a r a t e d ,

a s

5

20

25

35

4 0

55

6 5

2

by

? l t r a t i o n and

washed

w i t h

w a t e r

t o remove a d h e r i n g

a c i d .

The c o n c e n t r a t e d n i t r i c a c i d - s u l f u r i c

a c i d mother

l i q u o r s h a v e a h i g h c a p a c i t y

f o r

r e t a i n i n g

i m p u r i t i e s i n

s o l u ti o n s o t h a t a TNT roduct

o f

e x c e l l e n t p u r i t y i s

t h u s o b t a i n e d d i r e c t l y .

I f

d e s i r e d ,

a

TNT r o d u c t o f

g r e a t e r p u r i t y

c a n

b e o b t a i n e d b y

w a s h i n g

t h e

TNT

c r y s t a l s , p r i o r

t o

w a s h i n g w i t h w a t e r , w i t h

c o n c e n t r a t e d

s u l f u r i c

a c i d a n d / o r n i t r i c

a c i d .

BRIEF DESCRIPTION

OF

THE DRAWING

The

drawing

shows

a

schematic f l o w

diagram

o f a

c o n t i n u o u s c l o s e d - l o o p p r o c e s s f o r

m a n u f a c t u r i n g

TNT rom t o l u e n e according

t o

t h i s

i n v e n t i o n .

o E s c R i R r I o N 0?

THE

PREFERRED

EMBODIMENTS

We o n s i d e r

t h a t

t h e h i g h r e a c t i v i t y o f t h e a n h y d r o u s

n i t r a t i n g m i x t u r e o f HNO3

nd

oleum i s

due

i n p a r t t o

t h e f o r m a t i o n o f n i t r o n i u m b i s u l f a t e

(NO2HSO4)

from

HNO3

a n d

S 0 3 1

The s t o i c h i o m e t r i c c o n v e r s i o n o f

HNO3

o t h i s n i t r o

nium s a l t p r o v i d e s a h i g h c o n c e n t r a t i o n

o f n i t r o n i u m

i o n ,

which i s r e c o g n i z e d a s t h e r e a c t i v e s p e c i e s i n

most

a r o m a t i c

n i t r a t i o n r e a c t i o n s .

The f a v o r a b l e

s o l v a t i o n

e f f e c t

p r o v i d e d

b y

a n h y d r o u s H2804

a l s o

c o n t r i b u t e s

t o

t h e h i g h r e a c t i v i t y

o f

t h e

s y s t e m .

U S .

P a t .

No. 2 9 3 4 5 7 1 d i s c l o s e s a pr ocess f o r pro

d u c i n g DNT

u b s t a n t i a l l y i n s t a n t a n e o u s l y a n d

i n

n e a r l y

q u a n t i t a t i v e y i e l d b y

c o n t a c t i n g t o l u e n e w i t h

a

m i x t u r e

of l - I N O a

and oleum a t

a

temperature between

—50° C

and

6 0 °

C .

However,

t h e

p r o c e s s o f

t h i s

p a t e n t i s

l i m

i t e d

t o

t h e

production o f DNT nd o t h e r aromatic com

pounds c o n t a i n i n g n o t more t h a n 2

n i t r o

g r o u p s .

We have

now

found t h a t TNT can

be obtained

i n

o v e r

9Q% y i e l d

a n d r a p i d

r e a c t i o n r a t e b y n i t r a t i n g

DNT ith

a

mixture of

HNO3

nd

oleum

a t a

tempera

t u r e

o f about

7 0 °

C

r h i g h e r . We

ave a l s o unexpect

e d l y

found

t h a t

t h e n i t r a t i o n

o f

t o l u e n e

i n

t h e

a f o r e s a i d

man n e r produces

a

DNT

o n t a i n i n g l e s s t h a n

2

o f

me t a i s o m e r s , which i s

only

h a l f a s much

s

i n t h e cur

r e n t TNT r o c e s s o f

m a n u f a c t u r e ;

and t h a t b y

n i t r a t i n g

t h e

DNT

u r t h e r w i t h a n i t r a t i n g

m i x t u r e o f

l - I N O 3 and

o l e u m , a

TNT r o d u c t

c a n

b e d i r e c t l y o b t a i n e d h a v i n g

a

p u r i t y s u f ? c i e n t

f o r m i l i t a r y u s e .

I n

c a r r y i n g o u t

t h e

n i t r a t i o n

o f t o l u e n e

t o

DNT

i t h

an anhydrous m i x t u r e o f HNO; nd

oleum a c c o r d i n g

t o

t h e p r e s e n t i n v e n t i o n , two moles

o f

l - I N O 3 a r e t h e o r e ti

c a l l y r e q u i r e d t o

i n t r o d u c e

two n i t r o

groups

i n t o each

mole o f

t o l u e n e ; h o w e v e r ,

i t i s p r e f e r a b l e

t o

employ

a

s m a l l molar e x c e s s of I - I N O 3 , e . g . about

5%,

over t h e

t h e o r e t i c a l a mou nt r e q u i r e d s o a s t o maximize t h e y i e l d

o f DNT r o d u c e d . C o n s i d e r a b l y h i g h e r m o l a r

r a t i o s

o f

HNOg o t o l u e n e ,

e . g .

3 t o 8 moles o f l - I N O a p e r

mole

o f t o l u e n e , c a n b e

employed t o

a c c o m p l i s h t h e

d i n i t r a

t i o n

r e a c t i o n

a t t h e

low t e m p e r a t u r e s

employed

i n

t h e

p r e s e n t p r o c e s s , b u t

p r o v i d e

no t e c h n i c a l

a d v a n t a g e .

F u r t h e r , i t

i s

p r e f e r a b l e

t o employ a s m a l l , e . g .

about

a

1 0 % molar e x c e s s o f

I - I N O Q

r e l a t i v e t o f r e e

S 0 3 , s i n c e

an

excess

of

SO;

over

HNO3

s

undesirable

due

t o

t h e

c o m p e t i n g s u l f o n a t i o n r e a c t i o n

w i t h

t o l u e n e . The r a t i o

o f f r e e 3 0 ; ,

t o H280, i n t h e

oleum employed i s r e l a

t i v e l y l e s s

i m p o r t a n t

and i s c o n v e n i e n t l y a b o u t I p a r t

b y w e i g h t p e r 4 p a r t s

H 2 8 0 4 .

The n i t r a t i o n o f t o l u e n e

t o DNT a n

be

c a r r i e d

out a t

minus 40°-50° C

r

lower;

but i t

i s preferably c a r r i e d

out a t a temperature not ex


4/6

3 , 7 9 9 , 9 9 3

3

c e e d i n g

about +l0°

C nd e s p e c i a l l y

a t between about

—l0°

C

and —20° C . At t h e s e p r e f e r r e d t e m p e r a t u r e s

t h e


i s

r a p i d

and

t h e p r o d u c t i o n o f

u n d e s i r e d

meta

i s o m e r s

i s

m i n i m i z e d .

R e a c t i o n

t e m p e r a t u r e s

above a b o u t 4 0 ° C .

a r e u n d e s i r a b l e ,

s i n c e t h e y promote

t h e formation

of undesired

meta i s o m e r s .

After

t h e


reaction

i s

complete,

the reac

t i o n

mixture

c o n t a i n i n g t h e DNT nd s p e n t a c i d l i q u o r

c a n b e c h a r g e d w i t h f r e s h HNO; and S 0 3 ,

a s

r e q u i r e d ,

and

t h e r e s u l t i n g

m i x t u r e

i s

h e a t e d t o a temperature

o f

about

7 0 °

C r h i g h e r ,

p r e f e r a b l y

between

7 0 °

and

1 0 0 °

C . , and e s p e c i a l l y about 9 0 ° C . , t o e f f e c t t h e n i t r a t i o n

of DNT o TNT. The amoun t

of

H N O _ - ,

i s s u f ? c i e n t t o

p r o v i d e

a t l e a s t

one

mole o f ljNOa p e r

mole

o f DNT,

a s

t h e o r e t i c a l l y

r e q u i r e d .

The amount o f S03 s p r e f e r a

b l y about

one m o l e , e . g .

from

0 . 9

t o 1 . 1

moles o f S 0 3 ,

p e r

mole

o f HNO3. The r a t i o o f SO3 t o H2504 employed

i n t h e

t r i n i t r a t i o n r e a c t i o n i s

n o t c r i t i c a l , s i n c e s u l f o n a

t i o n i s

n o t

a competing r e a c t i o n i n t h e

n i t r a t i o n

of

DNT;

i t

i s

c o n v e n i e n t l y

a b o u t

0 . 4 3

t o

l

b y

w e i g h t ,

w h i c h

c o r r e s p o n d s

t o

oleum c o n t a i n i n g a p p r o x i m a t e l y

30% f r e e S 0 3 .

To

ensure

a r a p i d and complete n i t r a t i o n of DNT o

TNT,

a n

e x c e s s o f

HNO3 nd

S03

s employed, p r e f e r a

b l y

from

about 3 t o about 5

moles

each o f l - l N O 3 and

5 0 ; , per

mole of

DNT.

The

u s e of e x c e s s r e a g e n t s i n

t h e

t r i n i t r a t i o n

s t e p

does n o t i m p a i r t h e economy o f t h e

t o t a l process f o r

TNT manufacture, s i n c e t h e e x c e s s

HNOB nd S03

c a n

b e employed i n t h e d i n i t r a t i o n s t e p

o f a c l o s e d - l o o p p r o c e s s . P r e f e r a b l y , i n a c l o s e d - l o o p

p r o c e s s t h e

amounts o f HNOQ and S03 adde d f o r

t h e

t r i n i t r a t i o n s t e p a r e such

t h a t

t h e a c i d

l i q u o r ,

recovered

by

f i l t r a t i o n o f

t h e t r i n i t r a t i o n r e a c t i o n

m i x t u r e

t o r e

move TNT,

h a s a p p r o x i m a t e l y

t h e

c o m p o s i t i o n o f

t h e

H N O , , - o l e u m n i t r a t i o n m i x t u r e r e q u i r e d f o r t h e d i n i t r a

t i o n s t e p .

I n

t h e

process of

t h e i n v e n t i o n

a d d i t i o n a l amounts of

s u l f u r i c

a c i d

a r e SO

by r e a c t i o n

o f f r e e S03 w i t h

t h e

w a t e r formed i n

t h e

n i t r a t i o n r e a c t i o n s . The p r o

d u c t i o n o f

such a d d i t i o n a l amounts

o f

s u l f u r i c

a c i d

r e s u l t s i n

a n i n c r e a s e i n

b o t h t h e

volume

and r a t i o

o f H50,

t o

03, w h i c h i s u n d e s i r a b l e i n c l o s e d

l o o p o p e r a t i o n . To p r e v e n t

s u c h

b u i l d - u p o f s u l f u r i c

a c i d i n a

c l o s e d - l o o p

p r o c e s s , a s u f f i c i e n t p o r t i o n

o f t h e r e a c t i o n

m i x t u r e

o b t a i n e d i n t h e


s t e p

i s

withdrawn and t h e

DNT o n t e n t i s s e p a r a t e d

t h e r e f r o m , e . g .

by

e x t r a c t i o n w i t h

a s u i t a b l e i n e r t

o r g a n i c

s o l v e n t , e . g .

m e t h y l e n e d i c h l o r i d e , w h i c h

i s t h e n

s e p a r a t e d

f r o m

t h e

DNT b y

d i s t i l l a t i o n .

The DNT h u s recovered

i s

r e t u r n e d

t o s a i d

r e a c

t i o n m i x t u r e

f o r t h e

t r i n i t r a t i o n s t e p

and t h e a c i d

l i q u o r

remaining

a f t e r

removal of

i t s c o n t e n t o f DNT s

d i s

posed or u t i l i z e d i n s u i t a b l e manner.

We ave found t h a t

t h e

r e a c t i o n mass

obtained

i n t h e


s t e p

p o s s e s s e s

a

h i g h c a p a c i ty

f o r r e t a i n i n g

t h e

u n s y m m e t r i c a l TNT s o m e r s and o t h e r b y - p r o d u c t s

and

DNT n s o l u t i o n ,

w i t h t h e

r e s u l t t h a t

TNT

f e x c e l

l e n t p u r i t y

can

b e o b t a i n e d d i r e c t l y from t h e cooled r e

a c t i o n

m a s s b y

? l t r a t i o n

f o l l o w e d b y w a s h i n g w i t h

water

t o

re move

adherent a c i d . The

TNT

r y s t a l s r e

covered from

t h e r e a c t i o n

mass can

be

f u r t h e r

puri?ed

by

washing

w i t h s u l f u r i c a c i d o r n i t r i c a c i d of a concen

t r a t i o n

a t l e a s t about 50%, o r m i x t u r e s of such a c i d s .

The

f o l l o w i n g

e x a m p l e s p e c i ? c a l l y i l l u s t r a t e s t h e p r o

c e s s

of

t h i s i n v e n t i o n .

EXAMPLE

P a r t A . P r e p a r a t i o n o f D i n i t r o t o l u e n e

(DNT)

H)

2 0

25

30

50

55

6 0

65

4

A

i t r a t i n g m i x t u r e

o f

2 5 . 1 g ( 3 9 8 mmoles)

o f

a b s o

l u t e

n i t r i c

a c i d

and

1 4 3 . 9 g o f

2 0% oleum c o n s i s t i n g o f

2 9 . 6

g

(370

mmoles) f r e e 8 0 ; ,

and

I

1 4 . 3

g H280,

was

p l a c e d

i n a t w o - p i e c e g l a s s

r e a c t o r

p r o v i d e d w i t h a

thermometer

and a g l a s s

a g i t a t o r

s h a f t w i t h a Te?on

b l a d e . The bottom p a r t of the reactor was a 1 0 0

ml

?ask,

which was

joined

t o

t h e top

by

a

ground g l a s s

?ange

and was ? t t e d w i t h an i n t e r n a l g l a s s c o i l

f o r

h e a t

i n g t h e

c o n t e n t s w i t h

s t e a m

o r

c o o l i n g w i t h w a t e r ; and

t h e t o p

p a r t was ? t t e d w i t h a thermometer

p o r t and

t h r e e

o t h e r

ground g l a s s j o i n t s . l

7 .3

g ( 1 8 8 mmoles) o f

t o l u e n e ( r e ? n e d g r a d e )

w e r e

added d r o p w i s e d u r i n g

100 minutes t o t h e a g i t a t e d n i t r a t i n g m i x t u r e which was

maintained

a t

about — ~ 8 t o

- — l 0 ° C . , a f t e r

which

t h e

r e

a c t i o n mixture

was a g i t a t e d f o r

' 1 5 minutes a t — - 8 t o

—lO°

C. a n d then allowed t o warm

o room t e m p e r a

ture

A

a m p l e

( 1 8 . 2 g )

o f t h e

s o l u t i o n

t h u s o b t a i n e d was

removed, poured on i c e and

t h e DNT

as s e p a r a t e d . A

y i e l d

o f

99.4%

( b a s e d

on

t o l u e n e )

o f

DNT

a v i n g

t h e

f o l l o w i n g c o m p o s i t i o n ( ‘ b y g l c a n a l y s i s ) w a s o b t a i n e d :

2 . 6 - DNT 15.6%

2 , 3 -

and

2 , 5 - DNT 0.6%

2 , 4 -

DNT

82.6%

3 , 4 ~

DNT

1.2%

100.0%

Thetotal

meta i s o m e r s

i n

t h e

DNT

h u s obtained

was

1 . 8 % .

P a r t B . P r e p a r a t i o n

o f

TNT

The s o l u t i o n r e m a i n i n g i n

t h e

r e a c t o r a f t e r removal

o f t h e 1 8 . 2 g s a m p l e i n p a r t A a s f o r t i ? e d b y a d d i n g

6 0 . 1

g .

( 7 5 ]

mmoles)

o f

8 0 : ,

( a

s t a b i l i z e d

SO3

marketed

under t h e n a m e S u l f a n b y A l l i e d Chemical

C o r p . ) and 4 6 . 1 g . ( 7 3 l mmoles) o f a b s o l u t e

H N O _ - ,

i n

t h a t

o r d e r w i t h

i c e b a t h

c o o l i n g

f r o m d r o p p i n g

f u n n e l s

equipped

w i t h Te?on s t o p c o c k s .

The t o t a l

amounts o f

S03

and

HNO3

i n t h e

r e s u l t i n g

s o l u t i o n

were 7 5 ]

mmoles

e a c h , a l l o w i n g f o r

t h e

HNO3 r e m a i n i n g

a f t e r

t h e


s t e p and a l s o t h e amount removed i n t h e

1 8 . 2

g .

a l i q u o t ; and t h e

amount o f DNT e m a i n i n g

i n

the reactor

was

171

mmoles.

T r i n i t r a t i o n

was

effected

b y h e a t i n g t h e r e s u l t i n g s o l u t i o n a t 7 0 ° C . f o r 3 0

min

u t e s , t h e n a t

8 0 ° C .

f o r

1 5 minutes

and

? n a l l y a t

9 0 ° C .

f o r 1 5 m i n u t e s . T h i s was

accomplished by p l a c i n g an

o i l

b a t h

p r e h e a t e d t o

7 0 °

C . around t h e

?ask and i n t r o d u c ~

i n g

steam

through

t h e

r e a c t o r

c o i l

t o

h e a t

t h e s o l u t i o n

t o

7 0 °

C i t h i n

1 m i n u t e , and m a i n t a i n i n g

t h e tempera

t u r e

w i t h i n

i

°

C . by i n t e r m i t t e n t f l o w of a s m a l l

amoun t of

c o o l i n g w a t e r .

The temperature

was r a i s e d

t o 8 0 ° C . i n

4 0

seconds

and

? n a l l y

from

8 0 ° t o 90° C .

i n 4 5

s e c o n d s .

The

h o t

r e a c t i o n

m i x t u r e

was poured

i n t o an Erlenmeyer ?ask and'cooled t o 0 °

C .

and

t h e

TNT r y s t a l s t h u s o b t a i n e d

were s e p a r a t e d

b y ? l t r a t i o n

on

a

c o a r s e ,

s i n t e r e d g l a s s f u n n e l . The mother l i q u o r

was c h i l l e d t o —l0°

C.

a n d ?ltered t o obtain

a

second

c r o p

o f TNT r y s t a l s on a s e p a r a t e

? l t e r . The

c r y s t a l

crops

were combined, washed w i t h

water u n t i l

a c i d f r e e

and d r i e d .

The

d r i e d c r y s t a l s had a s e t t i n g p o i n t

o f

802°

C . and weighed 36

g r a m s , c o r r e s p o n d i n g

t o a

y i e l d

o f

9 4 %

o f t h e o r y

b a s e d

on

t h e t o l u e n e

s t a r t i n g

m a t e r i a l . (A p r o d u c t o f s o m e w h a t h i g h e r s e t t i n g

p o i n t

was o b t a i n e d b y w a s h i n g t h e f i l t e r c a k e

w i t h

7 0 %

H2804

p r i o r t o w a s h i n g w i t h w a t e r

a s

d e s c r i b e d b el o w ) .

About

5

f t h e

DNT

as o x i d i z e d and t h e remain

i n g

95

as c o n v e r t e d

t o

TNT.

About

1 %

o f t h e

TNT

was

s u b s e q u e n t l y o x i d i z e d , r e s u l t i n g i n

a n e t

y i e l d o f

about

94%. The p r o d u c t s of t h e DNT x i d a t i o n

were


5/6

3 , 7 9 9 , 9 9 3

5

CO2,

CO, N20

and

H 2 0

w h i l e t h e

TNT as

c o n v e r t e d ,

a t l e a s t

i n

p a r t ,

t o s e v e r a l b y - p r o d u c t s ,

m a i n l y 2 , 4 , 6

t r i n i t r o b e n z o i c a c i d .

RECYCLE CLOSED~LOOP OPERATION

The

a c i d ? l t r a t e ,

o b t a i n e d b y r e m o v i n g

t h e TNT

c r y s t a l s

from t h e r e a c t o r mass i n P a r t

B

above

had

v e r y

n e a r l y t h e d e s i r e d

c o m p o s i t i o n

f o r t h e d i n i t r a t i o n r e a c

t i o n , a s d e s c r i b e d i n p a r t A b o v e , and i t s composition

was a d j u s t e d , a s r e q u i r e d , by a d d i t i o n

of

a

s m a l l

a m o u n t

o f

l - l N O a or§O3 t o

p r o v i d e t h e

a f o r e s a i d

r a g o

o f 3 9 8 m m o l e s

HNOQW'

m o l e s 8 ? }

p e r

‘ 1 8 8

mmoles t o l u e n e

a s employed i n p a r t A

a b o v e .

The

c y c l e w a s t h e n r e p e a t e d b y a d d i n g 17 .3 g . ( 1 8 8

mmoles) o f

t o l u e n e

and c o n d u c t i n g

t h e


and


r e a c t i o n s

a s d e s c r i b e d i n

p a r t

A

nd

p a r t

B

a b o v e , r e s p e c t i v e l y . For f o r t i ? c a t i o n o f t h e

r e a c t i o n

mass r e s u l t i n g from t h e d i n i t r a t i o n

r e a c t i o n ,

t h e

amount

o f

DNT formed, t h e

amount

o f

HNOS

r e m a i n i n g a n d t h e amount

o f

H2SO4 p r o d u c e d w e r e

c a l c u l a t e d o n t h e a s s u m p t i o n o f a

l ' 0 0 > ' y i e l d

o f ljNT

a c c o r d i n g

t o

t h e e q u a t i o n :

and a d d i n g t h e n e c e s s a r y amounts o f

S03

and

HNO3 o

a d j u s t

t h e

a c i d s f o r

t r i n i t r a t i o n a s d e s c r i b e d i n p a r t 8 .

Nine

c y c l e s

were

c a r r i e d out

i n

t h e

f o r e g o i n g

man

n e r .

The

c o m p o s i t i o n o f

t h e

a c i d p h a s e s u s e d f o r t h e

d i n i t r a t i o n and t r i n i t r a t i o n r e a c t i o n s i n t h r e e o f t h e

cy

c l e s

i s

shown

i n t h e f o l l o w i n g t a b l e :

ACID

PHASE COMPOSITION

D i n i t r a t i o n T r i n i t r a ti o n

C y c l e C o m p o n e n t

( ‘ 7 )

( ‘ 7 1 : ’ ) ( % )

( ‘ 7 c ’ )

1

H250,

6 7 . 6 6 7 . 6 4 9 . 7

560

S 0 : ‘

1 7 . 5

1 7 . 5

2 1 . 8 2 4 . 6

HNO;

1 4 . 9

1 4 . 9 1 7 . 2 1 9 . 4

NOHSO,

0 0 0 O

Organics 0 0

1 1 . 3

0

100.0 1 0 0 . 0 100 0 1 0 0 . 0

6 H250, 58.2 6 1 . 4 45.9 5 3 . 1

5 0 ; ,

1 5 . 0 1 5 . 8 1 9 . 8 2 2 . 9

H 1 5 1 0 ; I 1 2 . 8 1 3 . 5 1 5 . 5

1 7 . 9

NOHSO, 8 . 8 9 . 3 5 . 3

6 . 1

O r g a n i c s

5 . 2 O 1 3 . 5

0

100.0 100.0

100.0 100.0

9

H150.

58.0

6 1 . 1 4 5 . 7 5 2 . 6

5 0 , 1

1 4 . 7 1 5 . 4 1 9 . 7 2 2 . 7

HNOn 1 2 . 4 1 3 . 0 1 5 . 5 1 7 . 8

NC’HSO4 1 0 . 0 1 0 . 5 6 . 0 6 . 9

O r g a n i c s 4 . 9 0 1 3 . 1 0

100.0 100

0 1 0 0 . 0 1 0 0 . 0

The d i n i t r a t i o n

r e a c t i o n i n t h e

? r s t c y c l e was

c a r r i e d

out w i t h f r e s h a c i d s s o t h a t

n e i t h e r

n i t r o s y l s u l f u r i c a c i d

(NOHSOJ n o r

d i s s o l v e d

o r g a n i c s were p r e s e n t .

NOHSO, as formed d u r i n g

each

o f

t h e


r e

a c t i o n s

due t o t h e competing o x i d a t i o n r e a c t i o n . How

e v e r ,

t h e b u i l d u p

o f NOHSO, was compensa ted by r e

moving a p o r t i o n o f

t h e

f i l t r a t e a f t e r e a c h


r e a c t i o n f o r a n a l y s i s .

The NOHSO, o n c e n t r a t i o n was

l o w e r i n

t h e

t r i n i t r a

t i o n

s t e p t h a n

i n t h e d i n i t r a t i o n

s t e p

due t o d i l u t i o n by

t h e

S03 a n d HNO3

added t o f o r t i f y

t h e a c i d p h a s e . The

d i s s o l v e d

o r g a n i c s p r e se n t i n t h e a c i d

phase

a t

t h e

s t a r t

o f

t h e


r e a c t i o n

were

t h e

i m p u r i t i e s

and

TNT

t h a t had

n o t c r y s t a l l i z e d o u t f o l l o w i n g t h e

p r e v i o u s

t r i n i t r a t i o n r e a c t i o n ; t h e s e

m a t e r i a l s p l u s

DNT o n s t i

t u t e c l

t h e o r g a n i c s

d i s s o l v e d

i n

t h e a c i d

p h a s e a t t h e

s t a r t o f

t h e

t r i n i t r a t i o n r e a c t i o n . The columns

headed

5

25

30

35

45

50

55

6

b y % ’ g i v e t h e r e l a t i v e

w e i g h t pe r c e n t a g e c o m p o s i t i o n

o f t h e

a c i d s e x c l u s i v e

o f

t h e d i s s o l v e d

o r g a n i c s .

The average y i e l d o f TNT aed on t o l u e n e

was 93

o f t h e o r y

f o r

t h e n i n e

c y c l e s .

T h i s f i g u r e i n c l u d e d t h e

TNT

h a t

c r y s t a l l i z e d

o u t o f

t h e a c i d p h a s e , t o g e t h e r

w i t h

t h e i m p u r e

TNT

h a t r e m a i n e d

i n

s o l u t i o n , ( 2 , 4 , 6

TNT as t h e major component

o f

t h e o r g a n i c m a t e r i a l s

i n

t h e a c i d

p h a s e

a f t e r c r y s t a l l i z a t i o n

o f

t h e

TNT;

t h e

t o t a l amount o f d i s s o l v e d o r g a n i c s

was

r e g a r d e d s i m p l y

a s

impure

TNT). The

method

o f o p e r a t i o n d i d n o t

a l l o w d e t e r m i n a t i o n o f a v a l u e f o r t h e

y i e l d

of

c r y s t a l

l i z e d

TNT

ue

t o

l o s s o f a p o r t i o n o f

t h e

d i s s o l v e d

TNT

i n

t h e

b y - p r o d u c t a c i d . The q u a l i t y o f

t h e

TNT ob

t a i n e d i n

t h e

n i n e

c y c l e s

o f o p e r a t i o n was c o n s i s t e n t l y

g o o d , i n d i c a t i n g

t h a t

t h e a c i d p h a s e p o s s e s s e d a

h i g h

c a p a c i t y

f o r

r e t a i n i n g

t h e

u n s y m m e t r i c a l TNT i s o m e r s

and

o t h e r b y - p r o d u c t s .

PURIFYING TNT

The wet ? l t e r c a k e o f TNT

r y s t a l s

o b t a i n e d b y s e p a ~

r a t i n g t h e c r y s t a l s f r o m t h e n i t r a t i o n

m i x t u r e

i n

t h e l a s t

c y c l e ,

was

s l u r r i e d

i n

about an

e q u a l

w e i g h t

o f

7 0 %

H2804 ( c o r r e s p o n d i n g t o

about 1 . 5 g .

o f

7 0% HZSO4

per g ram

of

TNT o l i d s )

a t r o o m

temperature.

The

s l u r r y

was

? l t e r e d

and t h e f i l t e r cake was washed a c i d

f r e e

w i t h

w a t e r and d r i e d .

The p u r i ? e d

TNT r y s t a l s

t h u s

o b t a i n e d

had a

s e t t i n g

p o i n t o f 803°

C . , which

i s

s a t i s f a c t o r y f o r

t y p e

I

m i l i t a r y e x p l o s i v e - g r a d e

TNT.

The f o r e g o i n g d e m o n s t r a t e s

t h a t t h e

n o v e l p r o c e s s i s

c a p a b l e

o f

p r o d u c i n g TNT

f

a c c e p t a b l e

m i l i t a r y e x

p l o s i v e

grade w i t h o u t

t h e u s e

o f

t h e

c o n v e n t i o n a l s e l l i t e

p u r i ? c a t i o n

p r o c e s s .

The p r e s e n t p r o c e s s can

be r e a d i l y adapted f o r

con

t i n u o u s

manufacture

o f

TNT.

The

drawing

shows a

s c h e m a t i c f l o w

d i a g r a m o f a

c o n t i n u o u s c l o s e d - l o o p

p r o c e s s f o r p r o d u c t i o n o f TNT r o m t o l u e n e a c c o r d i n g

t o t h e p r o c e s s

of

t h e p r e s e n t

i n v e n t i o n .

Metered

s t r e a m s o f t o l u e n e and

f r e s h

o r r e c y c l e d n i t r a t i n g ac i d ,

i n t h e r a t i o o f

2 . 1 m o l e s

o f HNO3,

2 m o l e s

ofSO3 a n d

about 3-4 moles of H2SO4 p e r mole o f

t o l u e n e , a r e f e d

c o n t i n u o u s l y

t o t h e d i n i t r a t o r which i s o p e r a t e d a t

a b o u t —l0° C . F r e s h n i t r a t i n g a c i d i s u s e d f o r s t a r t u p ;

t h e r e a f t e r r e c y c l e d n i t r a t i n g

a c i d f r o m t h e t r i n i t r a t o r i s

employed ( s e e b e l o w ) . The

d i n i t r a t o r

can b e

a

s t a i n l e s s

s t e e l t a n k

p r o v i d e d

w i t h a n a g i t a t o r , c o o l i n g

c o i l s ,

b o t

tom f e e d p o r t s and t o p

o u t l e t

f o r e f f l u e n t r e a c t i o n mix

t u r e .

The average r e s i d e n c e

time

of t h e r e a c t a n t s i n t h e

d i n i t r a t o r i s

about 30

m i n u t e s , which a s noted above i s

s u b s t a n t i a l l y

l o n g e r

t h a n

t h e

t i m e

r e q u i r e d

t o

c o m p l e t e

t h e

n i t r a t i o n of t o l u e n e t o DNT nder

t h e s e

c o n d i t i o n s .

The

e f f l u e n t f r o m t h e

n i t r a t o r

c o n t a i i n g t h e

DNT n

H2SO4 and l i t t l e i f any

l - l N O S

o r NO2HSO4, i s

d i v i d e d

s u c h

t h a t ,

f o r

e x a m p l e ,

80%

t h e r e o f ?ows

d i r e c t l y

t o

t h e t r i n i t r a t o r

a n d

20 f l o w s

t o a

s o l v e n t e x t r a c t i o n

u n i t ,

such

a s

a S c h e i b e l

e x t r a c t o r , wherein

t h e DNT s

c o n t i n u o u s l y

e x t r a c t e d

from

t h e

a c i d

l i q u o r

w i t h

a

s u i t

a b l e

s o l v e n t ,

e . g . m e t h y l e n e c h l o r i d e . The

s u r p l u s

a c i d

from

t h e

e x t r a c t o r i s p u m p e d t o s t o r a g e f o r recovery o r

s a l e and t h e DNT

x t r a c t

f l o w s

t o a s t i l l ( n o t

shown),

where t h e s o l v e n t i s

s e p a r a t e d b y

d i s t i l l a t i o n , a n d t h e

DNT h u s o b t a i n e d

i s f e d

t o

t h e t r i n i t r a t o r .

A d d i t i o n a l

l - l N O a

and

S03 a r e c o n t i n u o u s l y f e d i n t o t h e

t r i n i t r a t o r

a l o n g w i t h

t h e h e f t l u e n t

from

t h e

d i n i t r a t o r

s o

a s

t o

p r o

v i d e a p p r ' o x i m a t e l y

‘

m o l e s o f

NO2HSO4

3 m o l e s e a c h

o f

l - l N O s and

S 0 3 ) p e r

mole

o f DNT. The t r i n i t r a t o r ,

which

can be

a v e s s e l s i m i l a r t o t h e d i n i t r a t o r

but

pro

v i d e d w i t h h e a t i n g

c o i l s ,

i s o p e r a t e d a t a b o u t 9 0 ° C .


6/6

3 , 7 9 9 , 9 9 3

7

with

an average residence

time of r e a c t a n t s of

about 1

h o u r , which

i s

s u f f i c i e n t t o complete t h e c o n v e r s i o n

o f

DNT

o

TNT

nder t h e s e

c o n d i t i o n s .

I n s t e a d

ofa

s i n g l e


v e s s e l ,

t h e r e a c t i o n m i x t u r e can be f e d , f o r

e x a m p l e , t h r o u g h

a

s e r i e s o f t h r e e t r i n i t r a t o r s ,

w h e r e i n

the

? r s t i s maintained a t

70°

C . ,

the

second a t

80° C.

a n d

the t h i r d a t 90° C. a n d the residence time i n each

i s

s u i t a b l y a d j u s t e d ,

a s

i l l u s t r a t e d i n t h e

f o r e g o i n g

e x

a m p l e .

The

r e a c t i o n

m i x t u r e

from

t h e

t r i n i t r a t o r

?ows

t o a workup i n s t a l l a t i o n , where i t i s

cooled

t o about

—lO° C . t o c r y s t a l l i z e t h e TNT,

and

t h e TNT r y s t a l s

a r e ? l t e r e d o f f

and p u r i ? e d ,

i f

n e c e s s a r y , by s u i t a b l e

means,

. g . washing w i t h 70

2804,

t h e n washed

w i t h

w a t e r

and

d r i e d .

The mother l i q u o r s s e p a r a t e d from t h e

c r y s t a l l i z e d

TNT

r e o f e s s e n t i a l l y t h e r e q u i r e d concen

t r a t i o n t o

convert

the toluene fee d t o DNT

n d

are r e

c y c l e d t o t h e d i n i t r a t o r ,

t o g e t h e r

w i t h

a d d i t i o n a l

HNOs

a n d

S 0 3 , i f

r e q u i r e d .

I t i s t h u s

e v i d e n t t h a t t h e

p r o c e s s o f t h i s i n v e n t i o n

p r o v i d e s

an

i m p o r t a n t

advance i n t h e

manufacture o f

TNT, i n c l u d i n g t h e f o l l o w i n g s p e c i ? c a d v a n t a g e s :

1 . I t p r o v i d e s r a p i d n i t r a t i o n r e a c t i o n r a t e s and h i g h

y i e l d s

o f TNT.

2 .

I t

p r o d u c e s

TNT f

m i l i t a r y s p e c i ? c a t i o n g r a d e

d i

r e c t l y b y c r y s t a l l i z a t i o n from t h e t r i n i t r a t i o n r e a c t i o n

m i x t u r e f o l l o w e d b y

washing

w i t h

w a t e r .

I f

n e c e s s a r y ,

t h e

TNT

an

b e f u r t h e r

puri?ed by washing w i t h

c o n c .

H 2 8 0 4 .

3 . I t o b v i a t e s t h e s e l l i t e process c u r r e n t l y used t o p u

r i f y

c r u d e

TNT

nd e l i m i n a t e s t h e “ r e d water”

d i s p o s a l

problem

a s s o c i a t e d

t h e r e w i t h , which

i s a

m a j o r p o l l u

t i o n problem

t h a t p l a g u e s t h e

c u r r e n t

method f o r

TNT

manufacture.

4 . I t does

n o t

produce N02 fumes a s

b y - p r o d u c t s

be

cause both NOZHSO4 nd NOT-{S04 a r e t h e r m a l l y s t a

b l e

i n

t h e

anhydrous

HNOQ

oleum

system

used

i n

both

t h e d i - a n d


r e a c t i o n s , t h e r e b y

e l i m i n a t i n g

t h e a t m o s p h e r i c p o l l u t i o n due t o

N02

fumes

e v o l v e d

i n

t h e

current process

f o r

TNT.

We wish i t t o be understood

t h a t

we d o not d e s i r e t o

be l i m i t e d t o t h e exact method a n d d e t a i l of constr uc

t i o n

described

f o r obvious

modi?cation w l l occur t o

persons s k i l l e d i n t h e a r t .

What

s claimed i s :

l . A p r o c e s s

f o r producing

TNT which

c o m p r i s e s

c o n t a c t i n g t o l u e n e w i t h a n

a n h y d r o u s n i t r a t i n g

m i x t u r e

of HNO3 and

oleum

a t

a

temperature below 40° C o

produce DNT, h e a t i n g t h e DNT n s i t u

a t

a

tempera

t u r e o f a t l e a s t about 7 0 ° C

i t h

an anhydrous n i t r a t i n g

m i x t u r e o f

HNO3

nd

oleum

t o

produce

TNT,

and

r e

c o v e r i n g t h e

TNT

rom

t h e r e a c t i o n

m i x t u r e ,

w h e r e i n

t h e

amoun t of

HNOS

s a t

l e a s t

2 moles

per

mole of t o l

uene and

t h e

a m o u n t of f r e e S03 i n

t h e

oleum does not

exceed

1

mole

p e r

mole of

HNOa n t h e n i t r a t i o n

o f

o l

uene t o DNT, and t h e

a mount

of HNO3 s between 1

and

5 moles

p e r

mole

o f DNT

n

t h e

n i t r a t i o n

o f DNT

t o

TNT.

2 .

The p r o c e s s according

t o

c l a i m l l , wherein t h e t o l

uene i s

n i t r a t e d a t

a tempera tu re

between about

— 2 0 °

C . a n d +1 0 ° C . and t h e DNT s n i t r a t e d

a t a

tempera

t u r e between

about

7 0 °

C.

and 1 0 0 ° C .

3 .

The p r o c e s s according t o c l a i m 1 , wherein t h e

amoun t of HNO3

s between

about 3 and

5

moles per

mole

o f

DNT nd

t h e

a mount

of

f r e e

S O ; , i n

t h e

oleum

i s about 1

mole per

mole o f HNOQ

n

t h e n i t r a t i o n

of

DNT.

2 0

30

35

4 0

45

5 0

55

60

65

8

4 . The p r o c e s s

a c c o r d i n g t o

c l a i m 3 ,

w h e r e i n

t h e

amount

o f HNO; s between about

2 . l

and 2 . 2 moles

per

mole

of t o l u e n e .

S . The p r o c e s s a c c o r d i n g t o c l a i m 1 ,

wherein

t h e

r e

a c t i o n mixture from

which t h e

TNT s

recovered i s

r e

cycled f o r use i n t h e n i t r a t i o n of t o l u e n e .

6 . The process

according

t o claim 5 , wherein a

por

t i o n

o f t h e r e a c ti o n m i x t u r e o b t a i n e d b y n i t r a t i n g t o l u

ene

t o DNT, i s

contacted

w i t h an i n e r t , i m m i s c i b l e

l i q

u i d o r g a n i c s o l v e n t f o r DNT,

t h e

r e s u l t i n g s o l v e n t s o l u

t i o n

of DNT

s

s e p a r a t e d

from t h e a c i d l i q u o r , and t h e

DNT

s recovered from t h e s o l v e n t s o l u t i o n and

sub

m i t t e d a l o n g w i t h t h e remainder

o f

t h e r e a c ti o n mix

t u r e t o t h e n i t r a t i o n

of DNT

o

TNT.

7 . The

process

according

t o claim

6 , wherein t h e o r

g a n i c

s o l v e n t

i s

m e t h y l e n e c h l o r i d e .

8 . The p r o c e s s a c c o r d i n g

t o

c l a i m 1 , w h e r e i n t h e

TNT e p a r a t e d from t h e r e a c t i o n m i x t u r e i s washed

w i t h

an

a c i d o f

t h e group c o n s i s t i n g

o f

5 0 - 1 0 0 %

H250,

and 5 0 - 1 0 0% HNO3 nd m i x t u r e s t h e r e o f .

9 . A

o n t i n u o u s

p r o c e s s f o r p r o d u c i n g TNT, which

c o m p r i s e s f e e d i n g

i n t o

a

? r s t

r e a c t i o n

v e s s e l

t o l u e n e

and a n

anhydrous n i t r a t i n g

m i x t u r e o f

HNOQ nd oleum

wherein

t h e a mou nt of l - I N O 3

i s a t l e a s t

2

moles

per

mole

o f

toluene and t h e a mou nt of f r e e 5 0 ; , i n t h e

oleum

does

not exceed 1 mole p e r mole o f HNOS,

maintaining

t h e

r e a c t a n t s i n

s a i d v e s s e l

a t a

t e m p e r a

t u r e below

4 0 ° C .

t o product DNT,

p a s si n g t h e r e a c ti o n

mixture from s a i d ? r s t reaction v e s s e l i n t o

a

second r e

a c t i o n v e s s e l

t o g e t h e r w i t h

s u f ? c i e n t a n h y d r o u s n i t r a t

i n g m i x t u r e o f

HNO3

and oleum t o p r o v i d e a

r a t i o

o f

between 1

and

5

moles

o f HNO3

p e r

mole o f DNT,

maintaining s a i d mixture

i n

t h e second v e s s e l a t a t e m

p e r a t u r e o f

a t l e a s t about 7 0 ° C . t o product TNT,

s e p a

r a t i n g t h e TNT from t h e r e a c ti o n m i x t u r e , and r e c y

c l i n g

t h e recovered

r e a c t i o n

mixture

t o t h e

f i r s t r e a c

t i o n v e s s e l .

1 0 . The p r o c e s s according t o c l a i m 9 , wherein

a

por

t i o n of t h e r e a c t i o n mixture from t h e ? r s t r e a c t i o n v e s

s e l i s c o n t a c t e d w i t h a n i n e r t ,

i m m i s c i b l e

l i q u i d o r g a n i c

s o l v e n t f o r t h e DNT, t h e

r e s u l t i n g

s o l v e n t s o l u t i o n

o f

DNT s

s e p a r a t e d

from

s a i d r e a c t i o n m i x t u r e ,

and

t h e

DNT s recovered from

s a i d s o l v e n t s o l u t i o n

and i n t r o

duced

a l o n g w i t h t h e

remainder

o f t h e r e a c ti o n

m i x t u r e

t o t h e second r e a c t i o n v e s s e l .

1 1 . The

p r o c e s s

a c c o r d i n g

t o c l a i m

1 0 , wherein

t h e

o r g a n i c s o l v e n t i s

m e t h y l e n e c h l o r i d e .

1 2 . The p r o c e s s a c c o r d i n g t o c l a i m 1 0 , w h e r e i n t h e

amoun t

of

HNOa

s

between

about

2 . 1

and

2 . 2

moles

p e r mole o f t o l u e n e and t h e

amoun t

o f

f r e e 5 0 ; , i n

t h e

oleum

i s l e s s

t h a n 1 mole p e r mole

o f

HNOB

n

t h e f i r s t

r e a c t i o n

v e s s e l ,

and t h e amount o f HNOa s between

about

3 and 5 moles

per mole

of DNT nd t h e

amoun t

o f

f r e e

8 0 ; , i n t h e

oleum i s

about

1 mole p e r mole o f

HNO3

n

t h e second r e a c t i o n

v e s s e l .

1 3 . The p r o c e s s a c c o r d i n g

t o

c l a i m 1 2 ,

w h e r e i n

t h e

oleum i n t h e ? r s t r e a c t i o n

v e s s e l

c o n t a i n s

about 2 0 %

b y

w e i g h t

o f

f r e e 03

and

t h e oleum

n

t h e second r e a c t i o n

v e s s e l

c o n t a i n s

a b o u t

30% b y w e i g h t o f f r e e $ 0 3 .

1 4 . The p r o c e s s a c c o r d i n g t o c l a i m 1 2 , wherein

t h e

? r s t r e a c t i o n

v e s s e l i s operated a t

a

temperature be

tween

about

— 2 0 ° C . a n d +1 0 ° C .

and

t h e

second

r e a c

t i o n

v e s s e l

i s

operated

a t

a

temperature between about

7 0 ° C . and 1 0 0 ° C .

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