4
7/23/2019 kolom absorbsi http://slidepdf.com/reader/full/kolom-absorbsi 1/4 United States Patent [191 Eakman 4,250,160 Feb. 10, 1981 [11] [45] [54] [75] [731 PRODUCTION OF AMMONIUM SULFATE Inventor: James M. Eakman, Houston, Tex. Exxon Research Engineering Co., Florham Park, NJ. 824,456 Assignee: [21] [22] Appl. No.: Filed: Aug. 15, 1977 Related US. Application Data Continuation of Ser. No. 700,738, Jun. 29, 1976, aban doned. Int. Cl.3 ....................... . C01C 1/24; COlB 17/00 US. l. .................................. . 423/547; 423/ 45; 423/242; 423/237 Field of Search .............. 423/237, 242, 545, 547 [63] [51] [52] [5 8] [5 6] References Cited U.S. PATENT DOCUMENTS 9/1924 West t a1. ......................... . 423/547 1 0 / 1933 Hodsman et a1. .. 11/1933 Van Peske 1/ 1935 Fulton ...... .. l/1935 Sperr, Jr. ..... . 2/1935 Von Girsewald 0/ 1937 Muus ................................. . 423/547 1,508,736 1,931,408 1,934,573 1,986,889 1,986,899 1,992,681 2,095,074 WATE (may contain H2504) FOREIGN PATENT DOCUMENTS 377504 7/1932 United Kingdom .................. . 423/547 1031724 6/1966 United Kingdom .................. . 423/545 Primary Examiner—Herbert T. Carter Assistant Examiner—Gary P. Straub Attorney, Agent, or Firm—L. A. Proctor; Y. S. Finkle [57] ABSTRACT A rocess for the production of ammonium sulfate in a multistage contactor or column) inclusive of liquid cyclone recycle. A as, or gases, which contains sulfur dioxide, e. g., a ?ue gas, is contacted with ammonia in an oxygen and water environment in a column comprised of three sections (zones). Sulfur dioxide is contacted in vapor phase in a central section of the contactor with a stoichiometric excess of ammonia in the presence of oxygen and water vapor to produce ammonium ulfate. A crubbing section for the removal of ammonia from the effluent gas by countercurrent contact with water or acid solution is provided in the upper section of the contactor. Liquid cyclones are utilized in the lower section of the contactor where: product ammonium sulfate is removed as a slurry, crystalline ammonium sulfate is removed from the slurry, and liquid is returned as recycle to the contactor. 9 Claims, 1 Drawing Figure 14 CLEAN FLUE GAS /’9 ' ' AMMONIA sc‘nuame __ __. sscnou —— — —/|o REACTION SECTION II Z FLUE GAS AMMQN‘A _L_'—‘''|7 CONTAINING s02 )- ____/_ l6 muomssrmppme AND _____ CRYSTALLIZATION SECTION _ _____ 19 PRIMARILY SOLID AMMONIUM SULFATE CRYSTALS AMMONlUM SULFATE AND AMMONIA SOLUTION __ ___ _ : 23 AIR 1 SUPERHEATED STEAM

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United

S t a t e s Patent [ 1 9 1

Eakman

4 , 2 5 0 , 1 6 0

F e b .

1 0 , 1 9 8 1

[ 1 1 ]

[ 4 5 ]

[ 5 4 ]

[ 7 5 ]

[ 7 3 1

PRODUCTION OF AMMONIUM SULFATE

I n v e n t o r : J a m e s

M.

Eakman,

H o u s t o n ,

T e x .

E x x o n

R e s e a r c h E n g i n e e r i n g

C o . ,

F l o r h a m

P a r k , NJ.

8 2 4 , 4 5 6

A s s i g n e e :

[ 2 1 ]

[ 2 2 ]

A p p l . N o . :

F i l e d : A u g . 1 5 , 1 9 7 7

R e l a t e d

US. A p p l i c a t i o n

D a t a

C o n t i n u a ti o n o f S e r .

N o .

7 0 0 , 7 3 8 , J u n . 2 9 , 1 9 7 6 , a b a n

d o n e d .

I n t . C l . 3 . . . . . . . . . . . . . . . . . . . . . . . .

C01C

1/24; COlB 17/00

US. l .

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

.

423/547;

4 2 3 /

4 5 ;

4 2 3 / 2 4 2 ; 4 2 3 / 2 3 7

F i e l d

o f

Search

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

423/237,

2 4 2 , 5 4 5 ,

547

[ 6 3 ]

[ 5 1 ]

[ 5 2 ]

[ 5 8 ]

[ 5 6 ] R e f e r e n c e s C i t e d

U . S . PATENT

DOCUMENTS

9/ 19 2 4 West

t

a 1 .

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

. 4 2 3 / 5 4 7

1 0 / 19 3 3

Hodsman et a 1 .

. .

1 1 / 1 9 3 3

Van P e s k e

1 /

1 9 3 5

Fulton . . . . . .

. .

l / 1 9 3 5 Spe rr,

J r .

. . . . . .

2 / 1 9 3 5

Von Girsewald0/ 1937

Muus

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2 3 / 5 4 7

1 , 5 0 8 , 7 3 6

1 , 9 3 1 , 4 0 8

1 , 9 3 4 , 5 7 3

1 , 9 8 6 , 8 8 9

1 , 9 8 6 , 8 9 9

1 , 9 9 2 , 6 8 1

2 , 0 9 5 , 0 7 4

WATE

( m a y c o n t a i n H2504)

FOREIGN PATENT DOCUMENTS

37 7 50 4

7 /19 32 U n i t e d Kingdom

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

. 4 2 3 / 5 4 7

10 317 24 6/1966 U n i t e d

Kingdom . . . . . . . . . . . . . . . . . .

.

4 2 3 / 5 4 5

P r i m a r y Examiner—Herbert T . C a r t e r

A s s i s t a n t Examiner—Gary

P .

S t r a u b

A t t o r n e y , A g e n t ,

o r Firm—L. A .

P r o c t o r ; Y . S . F i n k l e

[ 5 7 ] ABSTRACT

A

r o c e s s

f o r t h e

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

ammonium s u l f a t e

i n

a

m u l t i s t a g e

c o n t a c t o r

o r c o l u m n )

i n c l u s i v e

o f

l i q u i d

c y c l o n e

r e c y c l e . A a s ,

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

d i o x i d e , e . g . , a

?ue

g a s , i s contact ed with ammon i a i n an

oxygen and

water

environment i n a column comprised

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

( z o n e s ) .

S u l f ur d i o x i d e i s c o n t a c t e d

i n

vapor p h a s e

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

w i t h

a

s t o i c h i o m e t r i c

e x c e s s o f ammoni a i n t h e p r e s e n c e of

oxygen and w a t e r vapor

t o

produce

ammonium

u l f a t e .

A c r u b b i n g s e c t i o n f o r t h e r e m o v a l o f

ammonia

f r o m

t h e

e f f l u e n t

g a s by c o u n t e r c u r r e n t c o n t a c t w i t h w a t e r

o r a c i d

s o l u t i o n i s

p r o v i d e d i n t h e

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

c o n t a c t o r . L i q u i d c y c l o n e s a r e u t i l i z e d i n t h e

l o w e r

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

c o n t a c t o r w h e r e :

p r o d u c t ammonium

s u l f a t e

i s removed

a s

a

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

ammonium

s u l f a t e i s removed f r o m

t h e

s l u r r y , a n d l i q u i d i s r e t u r n e d

a s r e c y c l e t o t h e c o n t a c t o r .

9

C l a i m s ,

1

D r a w i n g

F i g u r e

1 4

CLEAN FLUE

GAS

/’9

' ' AMMONIA

sc‘nuame

__ __.

sscnou

——— —/|o

REACTION

SECTION

II

Z

FLUE GAS

A M M Q N ‘ A

_L_'—‘''|7 C O N T A I N I N G s 0 2

)-

____/_

l 6 muomssrmppme AND

_____

CRYSTALLIZATION

SECTION

__

____

1 9

PRIMARILY

SOLID

AMMONIU M SU LFATE CRYSTALS

AMMONlUM SULFATE

AND AMMONIA SOLUTION

__ ___ _ :23

AIR

‘ 1 SU PERHEATED

STEAM

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US.

P a t e n t

WATE

( m a y

c o n t a i n H 2 3 0 4 )

PRIMARILY

SOLID

AMMONIUM

SULFATE

CRYSTALS

AMMONIUM SULFATE

AND

AMMONIA SOLUTION

4 , 2 5 0 , 1 6 0

e b .

1 0 , 1 9 8 1

Fl 6

u

R E

: 4

CLEAN FLUE

GAS

l 3

//9

_ / _ '

‘ AMMONIA SCRUBING

_____ SECTION

———--/|o

REACTION

SECTION

I I

I Z FLUE GAS

CONTAINING

S02

AMMONIA STRIPPING

AND

CRYSTALLIZATION

SECTION

_____

_

:23

AIR

I SUPERHEATED

STEAM

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1

PRODUCTION OF

AMMONIUM SULFATE

T h i s i s a c o n t i n u a t i o n , o f a p p l i c a t i o n S e r . N o .

7 0 0 , 7 3 8 , ? l e d J u n e 2 9 , 1 9 7 6 n ow a b a n d o n e d . 5

Gaseous e f ? u e n t s , w a s t e g a s e s , ?ue g a s e s a n d

t h e

l i k e

from

v a r i o u s

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

n e n t s

which

must b e r e m o v e d , e . g . ,

s u l f u r

o x i d e s ,

n o t a

b l y s u l f u r d i o x i d e . S u l f u r d i o x i d e , a v e r y h a r m f u l a i r

p o l l u t a n t , a n d

ammonia

o f t e n

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

o f t e n

i n

a d m i x t u r e w i t h o t h e r g a s e o u s c o m p o n e n t s .

C o a l

g a s i ?

c a t i o n p l a n t s

commonly

e m i t e f ? u e n t g a s s t r e a m s which

c o n t a i n

s u l f u r

d i o x i d e o r

ammonia. The

removal o f

t h e s e

c o m p o n e n t s

f r o m

g a s e s

t o s u p p r e s s

a i r

p o l l u t i o n

i s

h i g h l y

d e s i r a b l e ,

a n d g e n e r a l l y e s s e n t i a l .

P r o c e s s e s

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

o f

ammonium s u l f a t e

a r e

w e l l known.

Ammo nium

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

by

c o n t a c t

b e t w e e n s u l f u r - o x i d e

c o n t a i n i n g

?ue g a s e s a n d

a m m o n i a c a l

s o l u t i o n s , t h e ammonium s u l f a t e

b e i n g

f o r m e d

a s c r y s t a l s

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

f r o m

s o l u t i o n .

( S e e ,

e . g . ,

D e f e n s i v e

P u b l i c a t i o n No. T 9 0 9 , 0 l 7 t o J o r d a n e t

a l . ) O f t t i m e s

t h e

p r i m a r y p u r p o s e

i n t h e

o p e r a t i o n o f

s u c h p r o c e s s e s i s t o p r o d u c e ammonium a l t s , b u t

o f t e n

a l s o

t h e

p r i m a r y

p u r p o s e i s

t o

r e d u c e

a i r p o l l u t i o n

I n U . S . P a t . No. 3 , 1 8 6 , 8 0 2

t o

J . S . G e r r a r d , e . g . , a

p r o c e s s

i s

d i s c l o s e d f o r

t h e

r e m o v a l o f s u l f u r

o x i d e

from

w a s t e , o r ?ue

g a s ,

by c o n t a c t o f

t h e

g a s w i t h ammonia.

I n a r e a c t i o n v e s s e l ,

a n i n c o m i n g

a c i d i ? e d f e ed l i q u o r

i s

m i x e d w i t h

a

r e c i r c u l a t e d s u l f u r i c

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

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

a

r e a c t i o n i n which

ammonium

s u l ? t e

and a mm o n i um b i s u l ? t e a r e converted t o a mm o n i um

s u l f a t e and s u l f u r . S m a l l amounts o f s u l f u r i c a c i d a r e

u s e d t o

s c r u b

t r a c e

amounts

o f

ammoni a

from t h e ?ue

gas. _

I n

U . S . P a t . No.

3 , 8 4 3 , 7 8 9

t o

S p e c t o r e t

a l

a p r o c e s s

i s

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

o f

s u l f u r d i o x i d e f r o m

?ue

g a s by

c o n t a c t

o f t h e g a s

w i t h

a n ammonia

s o l u t i o n . The

f l u e

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

i n t o t h e l o w e r

p o r t i o n o f

a column

w h i l e t h e ammonia s o l u t i o n i s i n t r o d u c e d

i n t o

t h e u p p e r

p o r t i o n o f

t h e

c o l u m n ,

t h e ammonia r e a c t i n g

w i t h

t h e

s u l f u r

d i o x i d e t o produce ammonium

u l f i t e .

The e s s e n

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

t o

remove t h e s u l f u r d i o x

i d e

t o

r e d u c e a i r p o l l u t i o n .

The p r i m a r y o b j e c t i v e 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 new a n d i m p r o v e d p r o c e s s f o r t h e s e p a r a t i o n

and removal o f s u l f u r o x i d e s o r

ammonia,

o r b o t h ,

from

g a s e o u s s t r e a m s

f o r

t h e s u p p r e s s i o n o f i r p o l l u t i o n o r t o

p r o d u c e u s e f u l

b y - p r o d u c t s ,

o r b o t h .

A ore

p a r t i c u l a r o b j e c t

o f t h i s

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 wherein s u l f u r d i o x i d e

c a n

b e s e p a r a t e d

from

waste

g a s ,

o r

?ue

g a s

s t r e a m s

by

c o n t a c t

w i t h

ammonia

i n a m u l t i p l e s t a g e l i q u i d - v a p o r c o n t a c t o r ,

column

o r r e a c t o r .

A n o t h e r a n d

more

s p e c i ? c o b j e c t o f

t h i s

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 t h e more

e f f e c t i v e

s e p a r a t i o n o f 5 5

s u l f u r

d i o x i d e

f r o m

? u e g a s

s t r e a m s ,

n o t a b l y

b y

c o n t a c t

w i t h ammonia i n a

m u lt i p l e s t a g e l i q u i d - v a p o r

c o n t a c t

column, c o n t a c t o r o r r e a c t o r .

These o b j e c t s a n d

o t h e r s

a r e

a c h i e v e d

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

w i t h

t h e

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

a

p r o c e s s

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

o f s u l f u r d i o x i d e from

a

g a s e o u s

s t r e a m ,

n o t a b l y

a

w a s t e g a s

o r ?ue

g a s

s t r e a m , by

c o n t a c t

o f t h e

g a s e o u s s t r e a m

w i t h ammonia,

which

c a n

a l s o b e

a w a s t e

g a s s t r e a m ,

i n

t h e

p r e s e n c e o f oxygen

and

w a t e r ,

i n

a

m u l ti p l e s t a g e l i q u i d - v a p o r c o n t a c t o r ,

o r

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

c o m p r i s e d

o f a t l e a s t

t h r e e

s e c t i o n s

( o r

z o n e s ) .

I n t h e

c o n t a c t o r ,

i n

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

s u l f u r

d i o x i d e i s c o n t a c t e d

i n vapor p h a s e w i t h a n

e x c e s s o f

1 5

2 5

3 0

6 5

4 , 2 5 0 ,

l

60

2

ammon i a i n t h e p r e s e n c e o f oxygen

and

water

vapor

t o

produce ammoni a s u l f a t e . I n a n

upper

s e c t i o n

o f

t h e

c o n t a c t o r ,

e x c e s s

ammoni a s

s c r u b b e d

from

t h e e f ? u e n t

g a s by c o u n t e r c u r r e n t c o n t a c t with wate r o r a c i d

s o l u

t i o n .

L i q u i d c y c l o n e s a r e u t i l i z e d i n t h e

l o w e r s e c t i o n

o f

t h e c o n t a c t o r , p r o d u c t

ammonium s u l f a t e i n c r y s t a l l i n e

form being r e m o v e d from t h e lower

s e c t i o n

o f

t h e c o n

t a c t o r .

A

l u r r y

o f

ammonium

s u l f a t e

i s removed

f r o m

t h e b o t t o m s t a g e s

o f

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

c r y s t a l l i n e

amm o

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

m o t h e r

l i q u o r

i s

r e c y c l e d t o t h e

c o n t a c t o r .

I n

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

i s c o m p r i s e d

o f

t h r e e f u n c t i o n a l s e c t i o n s ( o r z o n e s ) . The f e e d

s t r e a m s

t o

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

a r e comprised o f

ammonia; a ?ue g a s

c o n t a i n i n g s u l f u r d i o x i d e which may l s o c o n t a i n n i t r o

g e n , c a r b o n d i o x i d e , o x y g e n , a n d

o x i d e s

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

a i r s t r e a m t o s u p p l y any n e e d e d . e x c e s s oxygen r e q u i r e

m e n t s ;

a water

stream

which

may c o n t a i n

a s m a l l

amount

o f s u l f u r i c

a c i d t o

scrub t r a c e

amounts

o f am

monia

from

t h e ?ue g a s ; and s u p e r h e a t e d s t r e a m

t o

v a p o r i z e w a t e r a n d c o n c e n t r a t e

t h e

ammonium s u l f a t e

s o l u t i o n . The

s e v e r a l

f u n c t i o n s

which

t a k e p l a c e w i t h i n

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

a r e

g e n e r a l l y a s f o l l o w s :

The p r i m a r y p u r p o s e o f

t h e

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

i s

t o p r o v i d e

v a p o r p h a s e c o n t a c t between t h e s u l f u r

d i o x i d e

a n d

ammonia, t h e s u l f u r d i o x i d e

b e i n g

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

c e s s c o n c e n t r a t i o n of ammon i a n t h e p r e s e n c e o f

e x c e s s

oxygen and

w a t e r

v a p o r

t o produce

ammonium

u l f a t e .

Temperature and p r e s s u r e a r e n o t

c r i t i c a l .

The o v e r a l l

s t o i c h i o m e t r y o f

t h e

v e r y

r a p i d

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

i n v o l v e d i n s u c h

r e a c t i o n

i s r e p r e s e n t e d by t h e

f o l l o w

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

The

ammonium

s u l f a t e

f o r m s i m m e d i a t e l y

a n d

c r y s t a l

l i z e s

a s

a s o l i d .

I n o r d e r t o o b t a i n an e s s e n t i a l l y s t o i c h i o m e t r i c

con

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

ammonium

s u l f a t e

w i t h o u t

t h e

p r o d u c t i o n

o f b y - p r o d u c t s

s u c h a s ammonium u l f a

m a t e a

h e r b i c i d e ) , t h e

m o l a r r a t i o o f a m m o n i a z s u l f u r

d i o x i d e s h o u l d b e a p p r o x i m a t e l y 2 . 3 : 1 , o r

g r e a t e r .

P r e f

e r a b l y , t h e

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

t h e

c e n t r a l

s e c t i o n i s m a i n t a i n e d by

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

c a r r i e d

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

o f

t h e

c o l u m n .

The p r i m a r y f u n c t i o n

o f

t h e u p p e r

ammonia

s c r u b

b i n g

s e c t i o n

i s t h e r e m o v a l o f ammonia

f r o m

t h e

?ue

g a s e f ? u e n t .

A m a l l amount o f s u l f u r i c a c i d can b e

added t o w a t e r which s f e d t o t h e t o p o f t h e s c r u b b i n g

s e c t i o n t o n e u t r a l i z e

and r em o v e

t h e r e s i d u a l

amounts

o f ammon i a

s o

t h a t an e s s e n t i a l l y ammonia-free s t r e a m

l e a v e s t h e

t o p o f t h e s c r u b b e r .

The p r i m a r y

f u n c t i o n o f t h e l o w e r s e c t i o n

o f

t h e

c o n t a c t o r

i s

t o

s t r i p

t h e

ammonia f r o m t h e l i q u i d , t o

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

a n d t o

s e p a r a t e t h e

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

ammonium

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

lower s e c t i o n o f

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

can be o p e r a t e d i n

v a r i

o u s

modes which i n c l u d e : a ) r e m o v a l

o f

p r i m a r i l y

s o l i d

ammonium s u l f a t e

c r y s t a l s t r e a m s ,

b ) r e m o v a l o f a n

amm o n i um

s u l f a t e

s o l u t i o n

which a l s o

c o n t a i n s

ammo

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

o f

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

f e r r e d

m od e o f o p e r a t i o n , and ( 1 c )

removal

o f t h e p r i

m a r i l y

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

s t r e a m s

w i t h

no

s i g n i ? c a n t

l i q u i d

p h a s e

r e m o v a l .

The

r e m o v a l

o f

t h e

w a t e r

from t h e

p r o d u c t

t o

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

a c c o m p l i s h e d b y

m e a n s o f v a p o r i z a t i o n ,

s u p e r h e a t e d

s t e a m ,

o r u n s a t u r a t e d g a s , e . g . , h e a t e d

a i r ,

o r

b o t h ,

b e i n g

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4 , 2 5 0 , 1 6 0

3

f e d t o t h e bottom

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

t o s t r i p

o u t

t h e w a t e r

v a p o r .

T h e

p r o c e s s

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

v a p o r - l i q u i d c o n t a c t i n g

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

c o m p o n e n t s . T h e s e

a n d o t h e r f e a t u r e s

o f t h e p r e s e n t

p r o c e s s

w i l l

b e

i l l u s

t r a t e d , a n d c o n s e q u e n t l y b e t t e r u n d e r s t o o d ,

b y r e f e r

e n c e t o t h e a t t a c h e d

d r a w i n g ,

t h e f o l l o w i n g d e s c r i p t i o n ,

a n d

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

T h e FIGURE

d e p i c t s

v a p o r - l i q u i d

c o n t a c t i n g

a p p a

r a t u s

i n s c h e m a t i c

f o r m , a n d

a n

a r r a n g e m e n t o f t h e

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

c o m p o n e n t s

a d a p t e d t o

c a r r y

o u t t h e p r e s e n t

p r o c e s s .

R e f e r r i n g t o t h e FIGURE, t h e r e i s

shown

a c o n t a c t

c o l u m n , o r

Column

1 0 , o f t h e v a p o r - l i q u i d c o n t a c t t y p e

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

o f

a n o u t e r

m e t a l s h e l l w i t h i n

which c a n b e

p r o v i d e d a p l u r a l i t y

o f

v e r t i c a l l y s e p a

r a t e d

t r a y s 9 .

The c o n t a c t o r

1 0

i s

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

o f an upper ammonia

s c r u b b i n g s e c t i o n ,

a

c e n t r a l r e a c

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

a

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

l i z a t i o n s e c t i o n . G a s e o u s

f e e d s ,

a ? r s t c o n t a i n i n g s u l f u r

d i o x i d e ,

e . g . , a

f l u e

g a s , i s i n t r o d u c e d v i a l i n e 1 1

i n t o

t h e

c e n t e r

o f

t h e

c o n t a c t o r

1 0 ,

o r

i n t o

t h e

r e a c t o r

s e c t i o n .

A

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

s t r e a m i s

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

v i a l i n e 1 2

i n t o

a b o u t

t h e c e n

t e r o f Column

1 0 . I n t h e e n s u i n g

v a p o r p h a s e r e a c t i o n ,

w h e r e i n

ammonia

i s p r e s e n t i n s t o i c h i o m e t r i c e x c e s s

r e l a t i v e t o

t h e s u l f u r

d i o x i d e ,

s u i t a b l y

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

NH3:SO2 o f 2 . 3 : 1 , o r g r e a t e r , ammonium u l f a t e i s p r o

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

e q u a t i o n :

A m m o n i a

a s

a s c e n d s

w i t h i n

t h e column,

and an ammo

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

lower

s e c t i o n

t o

t h e

bottom

o f

t h e

c o l u m n .

I n a n y g i v e n

s t a g e , l i q u i d

a n d

v a p o r

p h a s e s

a r e

p r e s

e n t .

A

o l i d p h a s e i s

a l s o p r e s e n t

i n t h e l o w e r

s e c t i o n

o f

t h e

c o l u m n . Each o f

t h e

s e v e r a l s t a g e s a t

t h e

lower

p o r t i o n o f

Column

1 0 , i t

w i l l b e

o b s e r v e d , i s p r o v i d e d

w i t h l i q u i d c y c l o n e s o r

h y d r o c l o n e

s e p a r a t o r s 1 5 . The

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

Column

1 0 i s t o

s t r i p ammonia

from t h e

l i q u i d ,

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

a m m o

nium u l f a t e a n d t o s e p a r a t e t h e c r y s t a l l i z e d ammonium

s u l f a t e

from

s o l u t i o n .

I n

o p e r a t i o n ,

h e a t e d

a i r

o r s u p e r

h e a t e d s t e a m ,

o r

b o t h , a r e i n j e c t e d i n t o t h e

bottom

o f

Column

1 0 v i a

l i n e s 2 3 , 2 4 , ‘ r e s p e c t i v e l y .

A

i x e d , p r i

m a r i l y l i q u i d a n d s o l i d p h a s e i s withdrawn from one o r

more o f a p l u r a l i t y

o f

t r a y s

9

a t t h e lower s e c t i o n o f

Column 1 0 v i a l i n e s 1 6 , a n d

f e d i n t o l i q u i d c y c l o n e s ,

o r

h y d r o c l o n e s , 1 5 w h e r e i n s e p a r a t i o n o f t h e l i q u i d

a n d

s o l i d

p h a s e s

i s e f f e c t e d . A r i m a r i l y l i q u i d s t r e a m i s

r e t u r n e d t o t h e Column 1 0 v i a a

l i n e 1 7 , and t o

a t r a y 9

f r o m

which t was

w i t h d r a w n .

Very

s m a l l

s o l i d p a r t i

c l e s , which g e n e r a l l y r a n g e below a b o u t 2 0 m i c r o n s i n

d i a m e t e r , a r e r e c y c l e d with t h e l i q u i d

and

s e r v e a s nu

c l e a t i o n

s i t e s

f o r f u r t h e r c r y s t a l

g r o w t h . The

l a r g e r

s o l i d

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

p r i m a r i l y s o l i d ammonium

s u l f a t e c r y s t a l s , on s u b s e q u e n t p a s s a g e , a r e s e p a r a t e d

from t h e l i q u i d a n d p a s s e d v i a

l i n e

1 8 t o a n

a p p r o p r i a t e

m a n i f o l d 1 9 . The o l i d p h a s e i n

t h e

m a n i f o l d 1 9 i s p a s s e d

t o

l i n e

2 0 and

removed from t h e

p r o c e s s . Ammonium

s u l f a t e and ammoni a s o l u t i o n

a r e re mov e d v i a

l i n e s

2 1 , 2 2 from t h e

bottom s t a g e o f

t h e c o l u m n .

W i t h i n

t h e

ammonia

s c r u b b i n g

s e c t i o n ,

which

may

c o n s i s t o f p a c k i n g o r t r a y s 9 , w a t e r o r

d i l u t e s u l f u r i c

a c i d

s o l u t i o n

i s added

t o

t h e

t o p

o f Column

1 0

v i a l i n e

1 3

t o

re mov e o r

n e u t r a l i z e t h e

ammonia. An

s s e n t i a l l y

ammonia- and s u l f u r

d i o x i d e - f r e e , o r

c l e a n ,

f l u e g a s

3 0

3 5

6 0

6 5

4

s t r e a m i s

t a k e n

f r o m t h e t o p o f t h e Column 1 0

v i a

l i n e

1 4 .

I t

i s

a p p a r e n t t h a t v a r i o u s

m o d i ? c a t i o n s a n d c h a n g e s

c a n b e

made

w i t h o u t d e p a r t i n g

t h e

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

o f

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

H a v i n g d e s c r i b e d t h e i n v e n t i o n , w h a t

i s

c l a i m e d i s :

1 .

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

nium

s u l f a t e

a n d

r e m o v i n g

s u l f u r

d i o x i d e

f r o m

a

s u l f u r

d i o x i d e - c o n t a i n i n g

g a s

i n a d i s t i l l a t i o n column c om

p r i s e d

o f a n u p p e r

ammonia

s c r u b b i n g z o n e , a c e n t r a l

r e a c ti o n z o n e , a n d a

l o w e r

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

z o n e

t h a t

c o n t a i n s a t l e a s t one v a p o r - l i q u i d c o n t a c t t r a y

w h i c h

c o m p r i s e s :

a ) i n t r o d u c i n g

a s u l f u r

d i o x i d e - c o n t a i n i n g g a s

a n d

a m

m o n i a

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

d i o x i d e , ammonia,

water a n d o x y g e n r e a c t t o

form

a n

ammonium s u l f a t e - c o n t a i n i n g s o l u t i o n w h i c h f l o w s

downward

i n t o s a i d

l o w e r s t r i p p i n g

a n d

c r y s t a l l i z a

t i o n

z o n e ;

b )

i n t r o d u c i n g

w a t e r i n t o

t h e

u p p e r ammonia

s c r u b

b i n g

z o n e

o f -

s a i d

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

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

s c r u b b i n g t h e

a s c e n d i n g

g a s e s

a s

i t

?ows do wnward

i n t o s a i d

c e n t r a l r e a c t i o n z o n e ;

0 )

w i t h d r a w i n g

a

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

ammonia

a n d s u l f u r

d i o x i d e - f r e e g a s

o v e r h e a d

f r o m s a i d

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

c o l

umn;

d )

i n t r o d u c i n g

a n o x y g e n - c o n t a i n i n g

g a s

i n t o t h e

b o t

tom

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

s a i d d i s t i l l a t i o n c o l u m n ;

e ) s u p p l y i n g h e a t

t o

s a i d

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

c o l u m n ;

f )

w i t h d r a w i n g a s l u r r y

s t r e a m

o f l i q u i d a n d

a m m o

nium s u l f a t e s o l i d s f r o m e a c h v a p o r - l i q u i d c o n t a c t

t r a y on which

s u c h a s l u r r y e x i s t s i n

s a i d

l o w e r s t r i p

p i n g

a n d

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

g ) s e p a r a ti n g a s u b s t a n t i a l

p o r t i o n

o f

s a i d

ammonium

s u l f a t e s o l i d s

f r o m e a c h

s l u r r y s t r e a m

w i t h d r a w n

from

e a c h

v a p o r - l i q u i d

c o n t a c t

t r a y t o

produce

a

l i q u i d s t r e a m

d e p l e t e d

i n ammonium s u l f a t e s o l i d s ;

and

h ) r e t u r n i n g

e a c h l i q u i d -

s t r e a m

p r o d u c e d f r o m e a c h

s l u r r y s t r e a m

i n

s t e p g ) t o t h e v a p o r - l i q u i d

c o n t a c t

t r a y

f r o m

which

t h e

s l u r r y s t r e a m was

o r i g i n a l l y

w i t h d r a w n .

2 .

A

r o c e s s a s

de?ned by

c l a i m

1 wherein

t h e water

i n t r o d u c e d i n t o s a i d upper ammoni a

s c r u b b i n g

zone

c o n t a i n s

s u l f u r i c a c i d .

3 . A r o c e s s a s de?ned by c l a i m 1

wherein

a s u f ? c i e n t

amount o f ammoni a

s i n t r o d u c e d

i n t o

s a i d

c e n t r a l r e a c

t i o n

zone t o provide a molar r a t i o of

ammoni a

t o

s u l f u r

d i o x i d e

o f

a t

l e a s t a b o u t 2 3 : 1 .

4 .

A

r o c e s s

a s

de?ned by

c l a i m

1

wherein

s a i d

am

monia i n t r o d u c e d i n t o s a i d c e n t r a l

r e a c t i o n

zone s c o n

t a i n e d

i n a

waste

gas s t r e a m .

5 .

A r o c e s s a s de?ned by c l a i m 1

w h e r e i n

s a i d s u l f u r

d i o x i d e - c o n t a i n i n g

g a s

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

a c t i o n zone comprises a ?ue g a s .

6 . A r o c e s s a s ‘ d e ? n e d by

c l a i m

1 wherein s a i d oxy

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

g a s

i n t r o d u c e d i n t o

t h e

bottom o f s a i d

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

c o m p r i s e s

a i r .

7 .

A r o c e s s

a s de?ned

by c l a i m

1 wherein

a

hydro

c l o n e

i s u t i l i z e d

t o s e p a r a t e

s a i d

ammonium

s u l f a t e

s o l i d s f r o m e a c h s l u r r y

s t r e a m w i t h d r a w n

i n s t e p ( t ) .

8 .

A r o c e s s a s de?ned by

c l a i m

1 wherein s a i d h e a t

i s s u p p l i e d t o

s a i d

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

i n

s a i d oxygen

c o n t a i n i n g g a s .

9 .

A

r o c e s s

a s

de?ned

b y

c l a i m

1

wherein

s a i d

h e a t

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

c o l u m n

b y i n t r o d u c i n g

s u p e r h e a t e d

s t e a m i n t o t h e b o t t o m o f

s a i d

s t r i p p i n g

a n d

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

z o n e .

‘ I

i t

i t ‘

10