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The oxidation of hydrogen sulfide to sulfur

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THE OXIDATION OF
HYDROGEN SULFIDE TO SULFUR
A T h e sis
P re se n te d to
t h e D e p a rtm e n t o f C h e m is try
U n iv e rs ity of S o u th e rn C a lif o r n ia
In P a r tia l F u lfillm e n t
o f t h e R e q u ire m e n ts f o r t h e D eg ree
M a ste r o f S c ie n c e
by
C h a r l e s W. R o b i n s o n
Ju n e 1941
UMI Number; EP41530
All rights reserved
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This thesis, w ritten by
(2Ja*r.les.. W . ' K . l !n tTovt
under the direction of h
Fa culty C o m m i t t e e ,
a n d a p p r o v e d b y a l l its m e m b e r s , has been
p r es e nt e d to a n d a c c e p te d by the C ou nc il on
G ra du ate S t u d y an d Research in pa r ti al fulfill­
m e n t of t h e r e q u i r e m e n t s f o r th e d e g r e e o f
J ’c
D ean
Secretary
F aculty C om m ittee
-
Chairman
TABLE OF CONTENTS
CHAPTER
I.
II.
III.
PAGE
INTRODUCTION.....................................
1
....................
HISTORICAL BACKGROUND
PROBLEMS OF H2S IN PETROLEUM ANDTHEIR REMOVAL .
P ro p e rtie s
5
o f HgS ...................................................................
5
I r o n O x id e M e t h o d ...................................................................
5
F e l d P r o c e s s .................................................................................
6
L e a h y P r o c e s s ................................................................................
7
..............................................................
8
S eab o ard P ro c e s s
. .
S o d iu m P h e n o l a t e P r o c e s s .........................................
9
T r i p o t a s s i u m P h o s p h a t e P r o c e s s .... ....................................
IV .
2
DESCRIPTION OF THE PROCESS AND THE METHOD
. . .
10
11
V.
THE A P P A R A T U S ....................................................................................
13
V I.
EXPERIMENTAL W O R K ..........................................................................
16
E f f e c t o f T e m p e ra tu re
. . . . .
...............................
E f f e c t o f C a t a l y s t s .........................................
17
C a lc u la tio n of Y ie ld of S u lfu r. . . . . . . . .
20
R a t e o f F l o w ..............................................
21
R a t i o o f HgS t o A
23
i r ..............................................................
E f f e c t o f H y d ro c a rb o n s on t h e Y i e l d s
A n a l y s i s o f E x i t G as f o r HgS
V II.
16
. . . . .
24
..........................................
C O N C L U S IO N ....................................................
24
.
28
S u m m a tio n o f W o r k ...................................................................
28
C o m m e r c i a l I m p o r t a n c e .........................................................
29
S u g g e stio n s f o r F u rth e r I n v e s tig a tio n
29
. . . .
B IBLIO G RA PH Y.........................................................................................................
31
LIST OF GRAPHS
GRAPH
I.
PAGE
E f f e c t o f T e m p e ra tu re and C a t a l y s t s
Y ie ld o f S u lf u r
II.
III.
.
on th e
......................................................................... 1 8
E f f e c t o f R a t e .o f F lo w on t h e
E f f e c t o f T e m p e r a t u r e on
Y ie ld
of S u lfu r .
th e O x id a tio n
of
HgS .
22
27
LIST OF ILLUSTRATIONS
ILLUSTRATION
1.
D r a w i n g o f A p p a r a t u s .........................................................
PAGE
15
CHAPTER I
INTRODUCTION
The o x i d a t i o n o f h y d ro g e n s u l f i d e u n d e r o r d i n a r y con
d i ti o n s g iv e s s u l f u r d io x id e .
When a c o n t r o l l e d a m o u n t o f
oxygen o r i n s u f f i c i e n t su p p ly o f a i r i s u se d , th e p ro d u c ts
a r e s u l f u r and w a t e r .
gen s u l f i d e
r e a c t s w i t h a h a l f m o le o f o x y g e n , s u l f u r and
w a te r a re th e p ro d u c ts .
v a rio u s
T h e o r e t i c a l l y , w h e n o n e m o le o f h y d r o
The p r o c e s s
i s n o th in g new , b u t t h e
c o n d itio n s and f a c t o r s a f f e c t i n g th e r e a c tio n have
no t been d isc lo s e d
in g re a t d e ta il in th e l i t e r a t u r e .
The g r e a t am ount o f w a s te h y d ro g e n s u l f i d e a ro u n d
p e t r o l e u m r e f i n e r i e s w as t h e b a s i s f o r s e l e c t i n g t h i s
The e f f e c t o f t e m p e r a t u r e ,
r e a c tin g g a se s , and th e
c a ta ly sts,
ra te
o f flo w o f th e
e f f e c t o f s m a l l a m o u n ts o f h y d r o c a r ­
bons i n t h e h y d ro g e n s u l f i d e g as a r e t o be in c lu d e d
in v e s tig a tio n .
to p ic .
in th is
CHAPTER I I
HISTORICAL BACKGROUND
The f a c t t h a t h y d ro g e n s u l f i d e
s u l f u r b y a t m o s p h e r i c o x y g e n w as f i r s t
1777 d u r i n g tR e p h l o g i s t i c
th e f i r s t to
p e rio d .
c o u ld be o x id iz e d t o
n o te d by S c R e e le i n
B e r t R o l l e t i n 1 7 9 6 w as
r e a l i z e t h a t t h e g a s w as a n o x y g e n f r e e a c i d ,
a n d m ade a n a n a l y s i s o f i t s
c o n stitu e n ts
I t w as fo u n d t h a t s lo w , f l a m e l e s s
c o m b u s t i o n o f Hg S
was p o s s i b l e ,
and t h e p r o c e s s c o u ld be a c c e l e r a t e d by c o n t a c t
P
w i t h h e a te d s o l i d s su c h a s c h a r c o a l , i r o n o x id e , o r p u m ic e .
A c a ta ly tic
e ffe c t of th is
t y p e was a p p l i e d t o r e c o v e r y o f
s u l f u r fro m t h e a l k a l i w a s te s o f th e Le B la n c soda p r o c e s s .
I n t h i s m e t h o d , known a s t h e C h a n c e C l a u s p r o c e s s ,
t h e HgS
m ix e d w i t h a i r w a s p a s s e d t h r o u g h a h e a t e d m a s s o f i r o n o x i d e
(bog i r o n o r e ) ,
wasr t h e f i r s t
s u p p o rte d on fra g m e n ts o f f i r e b r i c k s . ^
c a s e i n w h ic h t h i s
W h ile t h e Le B la n c p r o c e s s
is
T h is
r e a c t i o n w as u s e d c o m m e r c i a l l y
o b so le te to d a y ,
one o f t h e m o s t fam o u s c h e m ic a l r e a c t i o n s
it
re p re se n ts
in th e e a r ly h is to r y
o f i n d u s t r i a l c h e m is try and e n g in e e rin g p r i n c i p l e s .
1 1
- J . W. M e l l o r , A C o m p r e h e n s i v e T r e a t i s e o n I n o r g a n i c
an d T h e o r e t i c a l C h e m istry "
L o n d o n : L o n g m a n s , G r e e n a n d co m -'
pany, 1950.
Pp. 1 1 4 -1 4 6 .
2
'
J . N e w to n F r i e n d , T e x t b o o k o f I n o r g a n i c C h e m i s t r y .- L o n
d o n : C h a r l e s G r i f f i h a n d Company L i m i t e d , 1 9 1 9 .
P p . 46-67.
3 L u n g e a n d C u m m in g s, S u l f u r i c A c i d a n d S u l f u r D i o x i d e .
London: G u rn ey and J a c k s o n , 193 1 .
Pp. 4 5 -4 5 .
TBe r e a c t i o n w a s a s
'2-NaCl +■ H2S 0 4 =
H a g S O ^ -t- 2 0
=
N agS + CaCOrj »
GaS
+
C0g -a HgO
fo llo w s:
N a 2tJ04 +■ 2HC1
N ag S +- 2C 0g
N a2 C03 +• CaS
=
CaCOg +- HgS
T he s o d a a s h was le a c J b h d ly s m t a n d r e c r y s t a l l i z e d
se p a ra te
i t fro m th e
gen s u lf id e
c a lc iu m s u l f i d e .
The "b y -p ro d u ct h y d ro ­
g a s w as m i x e d w i t h t h e p r o p e r a m o u n t o f a i r a n d
t h i s m i x t u r e w as l e d i n t o t h e C l a u s k i l n
c o n siste d
in o rd er to
f o r c o m b u s tio n .
of a c y lin d r ic a l fu rn a c e f i l l e d w ith la y e rs
of iro n
o x id e p la c e d on g r a t i n g s o r beds o f b r o k e n f i r e - b r i c k s .
te m p e ra tu re
h e a t.
T h is
T he
o f t h e ‘w h o le m a s s w as m a i n t a i n e d a t a d u l l r e d
U nder th o s e c o n d itio n s , th e h ydrogen s u l f i d e
s u l f u r and w a te r,
and th e
b u rn t to
i r o n o x id e w as m a i n t a i n e d - a t a d u l l
r e d h e a t by t h e h e a t o f c o m b u stio n .
Y ie ld s of o v er e ig h ty
p e r c e n t w ere o b ta in e d by t h i s m e th o d .^
In
1 9 2 0 F . P r o ,1a im w o r k e d on a p r o c e s s w h i c h t h e y
c la im e d was b e t t e r t h a n t h e C h a n c e - C la u s .
fid e ,
a f t e r m i x in g 'w it h a i r ,
la y e r of b a u x ite
The h y d r o g e n s u l ­
i s p a s s e d d o w n w ard t h r o u g h a
i n a c u p o l a a t a b o u t 500° C e n t i g r a d e , t h e
t h i c k n e s s o f t h e c o n t a c t m a t e r i a l b e i n g a b o u t 30cm i n o r d e r
t o c o o l t h e g a s e s t o a m inim u m t e m p e r a t u r e o f a p p r o x i m a t e l y
200°C .
T h e m a i n r e a c t i o n 2 H g S +- 0 2 =
2H2 0
2S
p roceeds
4 L u n g e a n d C u m m in g s, S u l f u r i c A c i d a n d S u l f u r D i o x i d e .
L o n d o n : G-urney a n d J a c k s o n , 1 9 3 1 .
Pp. 4 3 -4 5 .
m ost f a v o r a b ly a t 300^0.
2HgS -+- SOg i s
o n ly f e e b l e a t 200°and i n t h e lo w e r l a y e r o f
th e c o n ta c t m a te ria l i s
2HgS
-h
SOg =
T h e i n j u r i o u s r e a c t i o n 2H2 0 ■+■ 3S
2H2 0 +- 3 S .
la r g e ly re p la c e d by th e r e a c tio n
T h is p r o c e s s h a s n e v e r r e c e iv e d
m uch i n d u s t r i a l u s e a g e , a n d l i t t l e
tu re .S
5 Ib id .
i s fo u n d i n 't h e
lite ra ­
CHAPTER I I I
PROBLEMS OF H2S IN PETROLEUM
AND THEIR REMOVAL
P e tro le u m
i s fo u n d to
c o n t a i n m any t y p e s
of su lfu r
com p o u n d s, d e p e n d in g on t h e e x a c t c ru d e o i l t h a t i s u n d e r i n ­
v e s tig a tio n .
su lfid e ,
I n p e tro le u m th e r e i s
su lfu ric
bon d i s u l f i d e s ,
fid e s,
a c id ,
fo u n d s u l f u r , h y d ro g en
a lk y l s u lf a te s ,
su lfo n ic a c id s,
a lk y l m e rc a p ta n s, a r y l m e re a p ta n s, a lk y l s u l ­
c y c lic s u l f i d e s and th e o p h e n e s.
The c o n c e rn o f t h i s p a p e r i s
and c h a r a c t e r i s t i c s
o n ly w i t h t h e p ro b le m s
of th e g a s , hydro gen s u l f i d e .
c o l o r l e s s w i t h a w e l l know n p u n g e n t o d o r .
a ir,
car­
It
h a v in g a s p e c i f i c g r a v i t y o f 1 .1 8 , and i s
The g a s i s
i s h e a v ie r th a n
so lu b le in
w a t e r t o t h e e x t e n t o f a b o u t 3 ml p e r ml o f w a t e r a t 20°C .
o r d e r t o be a b le t o c o n v e r t t h e h y d ro g e n s u l f i d e
to
t h e ' g a s h a s t o be rem o v ed fro m o t h e r g a s e s , so t h i s
im p o rta n t to th e to p ic
In
su lfu r,
phase is
o f t h is p a p e r..
T h e o l d e s t know n p r o c e s s f o r t h e r e m o v a l o f HgS i s t h e
i r o n o x id e m e th o d .^
It
c o n sists
of p a ssin g th e gas
o v e r wood
s h a v i n g s c o a t e d w i t h i r o n o x i d e , t h e HgS r e a c t i n g w i t h i r o n
o x id e fo rm in g i r o n s u l f i d e .
T he p r o c e s s i s
r e v e r s e d and th e
i r o n o x id e r e v i v i f i e d by b lo w in g i n a i r th r o u g h t h e s h a v in g s .
M ic h a e l J . L e a h y , " C le a n in g H ig h S u l p h u r G a s e s " . R e­
f i n e r a n d N a t u r a l G a s o l i n e M a n u f a c t u r e ^ 1 5 : 2 7 6 , d u l y , 1936*7”
T h is p ro c e s s i s n o t s u i t a b l e
(over
b e c a u s e t h e i n t e n s e h e a t b e tw e e n t h e i r o n o x id e
1% )
a n d t h e HgS i s l i a b l e
cost of th e
siv e .
f o r g a s e s w i t h h i g h HgS c o n t e n t
to c au se a sp o n ta n e o u s f i r e .
am o u n t o f t h e o x i d e n e c e s s a r y m a k e s i t
O th e r d i f f i c u l t i e s
a re th e
im p o s sib ility
The h ig h
to o ex pen-'
o f rem o v in g
th e s p e n t m a t e r i a l s from , and th e a d d in g o f f r e s h m a t e r i a l s
to , th e
sy s te m w ith o u t c o n ta m in a tin g t h e gas w ith a i r .
i s a lm o st im p o s s ib le t o
re a c tio n of th e p ro c e ss.
c o n tr o l th e te m p e ra tu re and r a t e
T h ere i s
s in g th e gas in o rd e r to fo rc e
is
tra tio n s
of
t h e added c o s t o f com pres­
i t th ro u g h th e s h a v in g s , and
th e e q u ip m e n t i s v e ry b u lk y an d e x p e n s i v e .
p ro cess
It
T h erefo re, th is
a b o u t o b s o l e t e a n d u s e d f o r o n l y v e r y lo w c o n c e n ­
o f hydrog en s u l f i d e g a s .
Some w o r k o n i r o n h y d r o x i d e s u s p e n s i o n s w a s t r i e d ,
but
w as n o t f o u n d t o b e v e r y s u c c e s s f u l o r p r a c t i c a l . 8
A n o t h e r m e th o d o f HgS r e m o v a l i s
I t c o n sists
th e F e ld p r o c e s s .
o f p a s s in g a gas th ro u g h a p o ly th io n a te s o lu tio n ,
and th e n t r e a t i n g th e s o lu tio n in a s e p a r a te c o n ta in e r w ith
s u lf u r d io x id e .
a th io s u lfa te
T h e HgS r e a c t s w i t h t h e p o l y t h i o n a t e t o f o r m
and p r e c i p i t a t e
out fre e
th e n r e a c t s w ith th e s u l f u r d io x id e to
th io n a te .
su lfu r.
The t h i o s u l f a t e
re g e n e ra te th e p o ly ­
The t h e o r y o f t h i s p r o c e s s seem s i d e a l ,
but under
a c t u a l w o r k i n g c o n d i t i o n s t h e r e w e r e m an y d i f f i c u l t i e s w h i c h
kept i t
fro m w o rk in g a s p la n n e d .
2
Ib ia .
3 Ib id .
T h e L e a h y p r o c e s s 4 c o n s i s t s o f a b s o r b i n g t h e HgS i n
w a te r, and th e n c o n ta c tin g t h i s w a te r s o lu tio n of h y d ro s u lfu rous a c id w ith s u l f u r d io x id e .
T h is fo rm s a w a te r s o l u t i o n o f
H_S a n d S 0 „ a n d a c o n s i d e r a b l e a m o u n t o f f r e e S i n s u s p e n s i o n .
Cf
&
S u l f u r i n s u s p e n s io n can be f l o c c u l a t e d by a d d it i o n o f c e r ­
ta in so lu b le
ra te
e le c tro ly te s .
W h il e c e r t a i n
ty p es d e c re a s e th e
o f a b s o r p tio n o f HgS, o t h e r e l e c t r o l y t e s
w h ic h t h e r a t e
of a b so rp tio n is
g re a tly
a r e fo u n d by
in c re a se d .
f u r re c o v e re d from th e f o u l s o l u t io n f l o c c u l a t e s
t o th e b o tto m .
te ristic ,
th is
It
is
fin e ly
ty p e o f p ro c e ss
and s e t t l e s
d iv id e d and n e u t r a l in
b e in g u se d a s an i n s e c t i c i d e .
i s v e ry sim p le .
HgS w a s t r e a t e d a n d r e d u c e d t o
The s u l ­
ch arac­
T he a p p a r a t u s f o r
A n a t u r a l gas o f 9 .2 %
. 1 fo H g S .
The u n t r e a t e d g a s e s
e n t e r a t 3 0 p o u n d s p e r s q u a r e i n c h a n d l e a v e a t 21 p o u n d s
p e r s q u a r e i n c h . ' T he l o s s
in p ressu re
o f t h e v a p o r p r e s s u r e o f t h e H gS.
a t th e r a t e
f o r h e a t i n g an d no c o o l e r s needed*
The s u l f u r i s
th e s o lu tio n .
c irc u la te d
No s t e a m i s n e c e s s a r y
I f n o t o p e ra te d f o r s u l ­
c h e m ic a ls l a s t a lm o s t i n d e f i n i t e l y .
b u r n e d t o f o r m m o re s u l f u r d i o x i d e f o r m a k i n g
The t o t a l p o w e r n e c e s s a r y t o p r o c e s s t h r e e
m i l l i o n c u b ic f e e t o f g a s p e r day i s
above p ro c e s s i s
11 k i l o w a t t h o u r s .
The
o f n o u s e t o t h e r e c l a m a t i o n *o f HgS f o r o x i ­
d a tio n , because th e p ro d u ct i s s u lf u r ,
4 Ib id .
due t o t h e re m o v a l
The s o l u t i o n i s
o f 150 g a l l o n s p e r m in u te .
f u r as a b y -p ro d u c t, th e
is
a n d t h e HgS c a n n o t b e
re c la im e d f o r o x id a tio n .
The so d a a s h ,
tiv e
o r S eab o ard p r o c e s s ^ ,
one f o r lo w p e r c e n t a g e g a s e s .
is
The g a s i s s c ru b b e d
a b s o r p t i o n t o w e r b y a 5fo s o l u t i o n o f l\fagC03 .
w i t h t h e NagC03 , f o r m i n g HaHS.
tre a te d
an o ld b u t e f f e c ­
in an
T h e HgS r e a c t s
The f o u l s o l u t i o n
is th e n
i n a se c o n d to w e r o r a c t i f i e r w i t h l a r g e v o lu m e s o f
a i r and t h u s r e g e n e r a t e d .
HgS
Na2 C03 =■ NaHCOg + - NaHS
+
2NaHC0g
COg +• Hg 0 - f N ag C 0 3
The p r o c e s s c a u s e s a t e r r i b l e
odor fro m th e a c tif y in g p ro c e s s .
T h i s o d o r m ay b e r e m o v e d b y r e a c t i n g f e r r i c
NaHS i n t h e p r e s e n c e
o f HaHCOg.
3i\FaHS •+■ SNaHGOg
The f e r r i c
su lfid e
h y d ro x id e w ith
2 F e ( OH) 3 = F e 2S g i - 3 N a g C 0 g + 6 H g O .
i s th e n o x id iz e d t o
e le m e n ta l s u l f u r and
t h e F e (O H )g a g a i n f o r m e d .
2 F e g S g -t- 3 0 g +- 6HgO
=
4 F e ( 0 H ) 3 -h 6S
I n a c tu a l p r a c t ic e th e soda a sh p ro c e s s f o r g ases of h ig h
HgS c o n t e n t r e q u i r e s . t o o r a p i d a r a t e
of c ir c u la t io n 'o f th e
s o l u t i o n , an d th e am ount o f a i r r e q u i r e d t o r e g e n e r a t e t h e
fo u l so lu tio n is
e x c e ssiv e .
One d e s i r a b l e f e a t u r e
of t h is
p r o c e s s i s t h e f a c t t h a t t h e p a t e n t s h a v e r u n o u t a n d now c a n
be u se d by a n y o n e .
v ery good.
F o r lo w c o n c e n t r a t i o n s
A g a in , a s
5 Ib id .
o f HgS i t
is
still
i n t h e L e a h y p r o c e s s , t h e HgS c a n n o t b e
r e c la im e d from s o l u t i o n .
T h e re a r e tw o m o d ern m e th o d s o f r e m o v a l i n w h ic h t h e
HgS c a n he r e c l a i m e d , a n d t h u s a r e t h e m o s t i m p o r t a n t i n r e s ­
p e c t to th e s u b je c t o f t h i s
p ap er.
One o f t h e s e i s t h e
h o p p e r ’s so d iu m p h e n o l a t e p r o c e s s . 6
The H g S . l a d e n g a s e n t e r s
t h e b o tto m o f a n a b s o r p t i o n to w e r and p a s s e s up th r o u g h t h e
b u b b le cap t r a y s , m e e tin g t h e c o ld s o l u t i o n
c a u s t i c w h ich i s
c o m in g d o w n .
9 5 % t o 99.8 % o f i t s H gS .
c o lle c ts
in th e
The g a s i s
of phenol in
strip p e d
The s u l f i d e d p h e n o l a t e s o l u t i o n
b o tto m o f t h e a b s o r b e r , p a s s e s o u t i n t o a
h e a t exchanger and th e n to an a c t i f i e r .
It
f l o w s down o v e r
a c t i f i e r tr a y s th ro u g h s tr ip p in g - s te a m g e n e ra te d
b o i l e r w h i c h r e m o v e s t h e HgS f r o m t h e p h e n o l a t e .
la te
of fro m
on c o o lin g i s
in th e r e ­
The p h e n o ­
th e n read y f o r a re p e a t p ro c e s s .
l a d e n HgS l e a v e s t h e t o p o f t h e a c t i f i e r a n d p a s s e s
d e p h le g m a to rs.
The s te a m
i n t o tw o
The co n d en sed ste a m i s r e t u r n e d t o th e a c t i ­
f y i n g c o lu m n a n d t h e r e c o v e r e d HgS i s f o r c e d b y t h e a c t i f i e r
p re ssu re to th e a c id p la n t b u rn er o r,
o x id iz in g fu rn a c e .
e q u ip m e n t i s
T h is p r o c e s s
once i n s t a l l e d .
as
in our c a s e , to th e
i s v e ry e c o n o m ic a l a f t e r th e
T h e s o d iu m p h e n o l a t e s o l u t i o n
h a s a v e ry h ig h c a r r y in g c a p a c i t y and th u s
a s m a ll am ount o f
t h e s o l u t i o n w i l l h a n d l e a l a r g e v o lu m e o f t h e g a s .
6 R i e g e l , E m i l , I n d u s t r i a l C h e m i s t r y . New Y o r k :
R e i n h o l d P u b l i s h i n g C om pany, 1 9 5 7 . P p . 2 5 5 - 2 5 6 .
_________ , " T h e K o p p e r ’ s M e th o d o f HgS R e m o v a l , ” G as
and O il J o u r n a l . 3 6 :1 2 , A ugust 12, 1937.
The s e c o n d o f t h e s e n e w e r e f f i c i e n t m e th o d s i s
t r i p o t a s s i u m p h o s p h a te p ro c e ss .* ?
th o d o f o p e ra tio n
th e
T h e e q u i p m e n t u s e d a n d me­
is v e ry s im ila r to th e p h e n o la te p ro c e s s .
The g a s e n t e r s t h e b o tto m o f t h e a b s o r b e r and r i s e s th r o u g h
t h i r t y - s i x b u b b le p l a t e s c o u n te r c u r r e n t t o
c e n d in g a b s o r b e n t.
T h e a b s o r b e n t c o n t a i n s tw o g ra m m o I s o f
TCgPO^ p e r k i l o g r a m o f s o l u t i o n .
o u t th e to p o f th e
a c t i f i e r w here i t
a stre a m o f d e s ­
The s t r i p p e d
g a s p a s s e s - , on
c o lu m n , w h i l e t h e f o u l s o l u t i o n ' g o e s t o t h e
i s r e g e n e r a t e d , a n d t h e HgS p a s s e s o u t t o
t h e b u r n e r o r o x i d i z i n g cham b er.
in te re s tin g fe a tu re
T h is p r o c e s s u t i l i z e s
o f t h e p h o s p h a te sy s te m .
s o lu tio n s a tu ra tio n ,
one
The e q u il i b r i u m
e x p r e s s e d a s mo I s HgS p e r m o l o f KgPQ^
c o r r e s p o n d i n g t o a g i v e n c o n c e n t r a t i o n o f HgS i n t h e h y d r o ­
carb o n ,
i s g r e a t e r f o r a d i l u t e s o l u t i o n t h a n f o r a m ore c o n ­
c e n tra te d one.
A d v a n tag e i s
ta k e n o f t h is
f a c t by d o in g t h e
b u lk of th e s t r i p p i n g w ith a c o n c e n tra te d s o l u t i o n
in th e
lo w e r s e c t i o n o f th e a b s o r b e r and u s in g a d i l u t e s o l u t i o n t o
re m o v e t h e l a s t t r a c e s
o f HgS i n t h e u p p e r s e c t i o n .
K3 P 0 4 i s
sa lt,
a v ery s ta b le
e f f e c t i v e and t h i s
u sed e x te n siv e ly
th is
S in c e
p ro c e ss h as p ro ved v e ry
o n e , a lo n g w ith th e p h e n o la te p r o c e s s ,
are
in th e p e tro le u m in d u s tr y .
*? I s o m , ' H A W . , "New R i c h f i e l d R e f i n e r y ” , G as a n d O i l
J o u r n a l , 5 7 :3 6 , M arch 2 , 1939.
M u l l e n , J . M. , " H y d r o g e n S u l p h i d e Removed b y U s i n g
T r i p o t a s s i u m P h o s p h a t e , " G as a n d O i l J o u r n a l , 3 7 : 3 7 , A p r i l 1 3 .
193.9.
R o se b a u g h , T . W . , " T h e P h o s p h a te P r o c e s s f o r Rem oval
o f HgS f r o m N a t u r a l G a s " , G as J o u r n a l , 2 4 , A u g u s t , 1 9 3 8 .
CHAPTER IV
DESCRIPTION OP THE PROCESS
'
AND THE METHOD
A s was- s t a t e d b e f o r e ,
i n o r d e r t o o b t a i n s u l f u r from
HgS, a n i n s u f f i c i e n t s u p p ly o f oxygen i s n e c e s s a r y .
tio n t h a t ex p resses tb e
re a c tio n is :
2IIgS -+- Og -
T be e q u a
2S -t- 2HgO.
T h u s f o r e v e r y m o le o f H g S , a h a l f m o l e o f o x y g e n i s
neces­
sary .
p ro cess,
A ir is th e o x id iz in g ag en t to
and, sin c e a i r is
o n e -fifth
be u se d in t h i s
o x y g en b y v o lu m e , i t w i l l be
n e c e s s a r y t o u s e tw o a n d o n e - h a l f v o l u m e s o f a i r f o r e a c h
v o lu m e o f HgS .
T h e r e q u i r e d a m o u n t s o f t h e HgS a n d a i r a r e m i x e d a n d
p a s s e d th r o u g h t h e o x i d i z i n g cham b er.
H ere th e r e a c t i o n
ta k e s p la c e and th e p r o d u c ts , s u l f u r and w a te r v a p o r ,
out th e
o th e r end.
th e s u lf u r ,
e x it
The s u l f u r and w a te r a r e c o l l e c t e d and
a f t e r s e p a r a t i o n from th e w a t e r ,
i s w e ig h e d .
T he
c o l l e c t i o n o f th e s u l f u r was p r o b a b ly th e - m o s t d i f f i c u l t p a r t
of th is
p ro cess.
T h e s u l f u r f r o m t h e r e a c t i o n c h a m b e r w as
la rg e ly c o llo id a l in n a tu re .
The p a r t i c l e s w e re s o s m a l l
t h a t m uch o f t h e s u l f u r w o u l d n o t c o n d e n s e o u t i n t h e f l a s k s ,
b u t s e e m e d t o p a s s o n o u t t h e e x i t t u b e w i t h som e o f t h e u n ­
condensed w a te r v a p o r.
The c o l l o i d a l n a t u r e
of th e p ro d u ct
w as p r o v e n b y t h e f a c t t h a t a b o t t l e w i t h som e o f t h i s
l e c t e d s u l f u r , w hen m i x e d w i t h w a t e r t o
sh o w ed v e r y l i t t l e
c o l­
form a s u s p e n s io n ,
e v i d e n c e a f t e r t h r e e m o n th s o f t h e s u l f u r
se ttlin g
o u t.
S in c e tlie w a t e r v a p o r seem ed .to a c t a s a c a r ­
r i e r f o r th e s e s m a ll p a r t i c l e s
of su lfu r,
th e
condense o u t a l l th e w a te r v a p o r p o s s ib le .
r e c e i v i n g f l a s k s w ere s u rr o u n d e d by an i c e
p r o b l e m w as t o
T h erefo re, th e
b a th .
S till a
l a r g e a m o u n t o f s u l f u r w as n o t d e p o s i t i n g o u t i n t h e f l a s k s .
P e r c h l o r e t h y l e n e , a n o n -in fla m m a b le l i q u i d w h ic h b o i l s a t 123°C ,
i s an e x c e lle n t so lv e n t f o r s u lf u r a t i t s
b o ilin g p o in t.
It
w as f o u n d t h a t b y p a s s i n g t h e e x i t g a s t h r o u g h p e r c h l o r e t h y ­
le n e in th e v a p o r p h ase, p r a c t i c a l l y a l l th e s u lf u r t h a t
n o t c o n d e n se o u t i n t h e f l a s k s w as d i s s o l v e d
so lv e n t.
The s u l f u r c r y s t a l l i z e d
d id
in th e re flu x in g
o u t o f t h e s o l u t i o n on
c o o lin g .,
The v a r i o u s c a t a l y s t s
u se d w ere p la c e d i n th e f u r n a c e
an d t h e i r e f f e c t on t h e r e a c t i o n was i n v e s t i g a t e d .
T he e x i t
g a s w as a n a l y z e d f o r HgS i n o r d e r t o d e t e r m i n e t h e a m o u n t o f
g a s g o in g th r o u g h u n r e a c t e d .
w as a l s o v a r i e d t o
The t e m p e r a t u r e o f t h e f u r n a c e
o b ta in th e d iffe re n c e s
a t th e s e te m p e ra tu re s.
in y ie ld
of su lfu r
CHAPTER V
THE APPARATUS .
The a p p a r a t u s c o n s i s t e d
su re th e -ra te
o f tw o v e n t u r i m e t e r s t o m e a ­
o f flo w o f th e g a s e s , an e l e c t r i c
a p o rc e la in tu b e,
c o n d en sin g f l a s k s ,
h y d ro g e n s u l f i d e was g e n e r a t e d
cam e f r o m t h e f i f t y
a n d a R e f l u x c o lu m n .
i n a K ip p g e n e r a t o r .
pound p r e s s u r e p ip e l i n e
E n g in e e rin g B u ild in g .
tu b e fu r n a c e ,
The
The a i r
su p p ly in g th e
B o t h t h e HgS a n d a i r w e r e p a s s e d t h r o u g h
s e p a r a t e h o m e-m ad e f l o w m e t e r s . w h i c h h a d b e e n c a l i b r a t e d f o r
t h e g as u se d by a w e t - t e s t m e te r .
c lu d e d in th e flo w l i n e
A t h i r d m an o m e te r w as i n ­
to a c t as a p ressu re
a ls o as a s a f e ty v a lv e .
A lin e
and a i r i n to one end o f th e tu b e
i n d i c a t o r and
t h e n l e d t h e m i x t u r e o f HgS
in th e f u r n a c e .
The f u r n a c e w as h e a t e d b e f o r e t h i s
v o lta g e by a V a ria c t r a n s f o r m e r .
by c o n t r o l l i n g t h e
When t h e d e s i r e d t e m p e r a t u r e
w as r e a c h e d and re m a in e d .c o n s ta n t a s m ea su re d by a th e rm o ­
c o u p l e a n d p y r o m e t e r , t h e t h e r m o c o u p l e w as re m o v e d f r o m t h e
t u b e a n d a p o r c e l a i n b o a t c o n t a i n i n g t h e c a t a l y s t was p l a c e d
a t th e
c e n te r o f th e fu rn a c e ,
had been m easu red .
se rie s
a t w h ic h p o i n t t h e
te m p e ra tu re
A t th e e x i t end o f th e fu rn a c e tu b e a
o f f i v e 250 cc E r lim n e y e r f l a s k s ,
i c e b a t h , w ere c o n n e c te d .
T he l a s t
su rro u n d e d by an
f l a s k c o n ta in e d ab o u t
75 c c o f b o i l i n g p e r e h l o r e t h y l e n e w h i c h r e f l u x e d u p i n t o a
w a t e r c o o le d c o n d e n s e r a t t a c h e d t o
strip p e d of p r a c tic a lly a l l
its
th e f l a s k s .
The e x i t g a s ,
s u l f u r and c o n s i s t i n g of
14
n i t r o g e n a n d som e u n r e a c t e d HgS a n d o x y g e n a n d w a t e r v a p o r ,
p a sse d o u t t h e to p o f th e c o n d e n se r and on o u t i n to a hood.
When a n a n a l y s i s
o f th e e x i t
g a s w as m ade f o r u n r e a c t e d
H _ S , t h e g a s w as a b s o r b e d i n a s t a n d a r d i z e d s o l u t i o n
(Zi
a n d t h e e x c e s s i o d i n e w as t i t r a t e d
d iu m a r s e n i t e s o l u t i o n .
of io d in e ,
a g a in st sta n d a rd iz e d so­
T h e a m o u n t o f HgS p a s s i n g o u t t h e
e x i t tu b e f o r a c e r t a i n p e r io d o f tim e c o u ld be c a l c u l a t e d by
th e am ount o f i o d in e r e d u c e d .
I n o rd e r to re c o v e r th e s u l f u r t h a t had d e p o s ite d o u t
w ith th e
c o n d en se d w a t e r i n t h e f l a s k s , t h e f l a s k s w ere h e a t e d
a t a te m p e r a tu re o f a ro u n d 110°C f o r a b o u t t h i r t y m in u te s so
as to
get rid
of a l l th e w a te r.
T h e s u l f u r w as t h e n d i s s o l v e d
by th e p e rc h lo re th y le n e th a t re f lu x e d
in th e f i f t h
fla sk .
T h e s u l f u r c r y s t a l l i z e d o u t on c o o l i n g t h e s o l v e n t , a n d t h e n
t h e r e m a i n i n g s u l f u r i n s o l u t i o n a t ro o m t e m p e r a t u r e w as
c ry s ta lliz e d
5 cc.
out by d i s t i l l i n g
o ff th e
The s u l f u r w as a llo w e d t o
s ta n d f o r tw e n ty - f o u r h o u rs
so a s t o a llo w a n y s o lv e n t c o n ta in e d
e v a p o ra te .
l i q u i d down t o a b o u t
in th e .c ry s ta ls to
Then i t w as w e ig h e d s o a s t o d e te r m i n e t h e y i e l d
o f s u l f u r from th e
known v o lu m e o f H0S u s e d .
- Cl
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C . V<-/i / Jtri / A c / c r f o r A ? S
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/A c tt-r
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f o r
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i
CHAPTER TEE
EXPERIMENTAL WORK
I.
The e f f e c t
EFFECT OF TEMPERATURE
o f te m p e ra tu re and th e ty p e of c a t a l y s t
u s e d a r e tw o o f t h e
first.
im p o r ta n t p o i n t s w h ic h w e re i n v e s t i g a t e d
T h e r e a c t i o n o f o x y g e n w i t h HgS r e q u i r e s a m o d e r a t e l y
h ig h te m p e ra tu re in o r d e r to s t a r t t h e r e a c t i o n , a lth o u g h
o x i d a t i o n w i l l go o n s l o w l y a t ro o m t e m p e r a t u r e .
The tem ­
p e r a t u r e u s e d a c c o r d i n g t o t h e l i t e r a t u r e w as a b o u t a d u l l
r e d h e a t , w h ic h i s v e r y i n d e f i n i t e .
E a rly p u b lic a tio n s ^
gave a te m p e r a tu re o f aro u n d 5 50°F .
A lth o u g h t h i s r e a c t i o n
needs c o n sid e ra b le h e a t in o rd e r t o
its e lf
is
d e c id e d ly e x o th e rm ic .
sta rt it,
th e o x id a tio n
The th e r m o c h e m is tr y o f t h e
re a c tio n is :
BE2 S
°2
=
5 ,£ 6 0 c a l .
5 7 ,8 2 6 -
5 ,2 6 0
2HE ° +
BS
5 7 ,8 2 6 c a l .
=
5 2 ,5 6 6 c a l .
The l a r g e am ount o f h e a t on t h e
r i g h t hand s id e o f th e equa­
t i o n sh o w s t h a t t h i s r e a c t i o n i s
e x o th e rm a l and a l a r g e
am ount o f h e a t w i l l b e g iv e n o f f .
1 F r i e n d , I . N e w to n , T e x t b o o k o f I n o r g a n i c C h e m i s t r y .
L o n d o n : C h a r l e s G r i f f i n a n d Company L i m i t e d , 19 19 . P p . 4 6 - 6 7 .
M e l l o r , J . W ., A C o m p re h e n siv e T r e a t i s e on I n o r g a n i c
C h e m i s t r y . L o n d o n : L o n g m a n s , G r e e n a n d C om pany, 1 9 5 0 •
Pp. 1 1 4 -1 4 6 ..
17
The t e m p e r a t u r e s i n v e s t i g a t e d i n t h i s w o rk ra n g e d from
500° t o
1400°F.
I t w as f o u n d ( s e e G ra p h # 1 ) t h a t b e lo w 500°
th e y i e l d o f s u l f u r dropped o f f r a p i d l y s in c e t h e te m p e ra tu re
i s t o o lo w f o r r a p i d o x i d a t i o n .
The d r o p i n y i e l d ab o v e 1000°F
p r o b a b l y is . d u e t o t h e h i g h e r l o s s e s o f s u l f u r a t h i g h t e m p e r ­
a tu r e r a t h e r th a n th e
is th e
f a i l u r e o f t h e HgS t o b e o x i d i z e d , a s
c a s e a t lo w t e m p e r a t u r e s .
The d a t a show s t h e r e
i s no s h a rp b re a k o r te m p e ra tu re
f o r w h ic h t h e r e a c t i o n
is
t h e a cc o m p a n y in g g r a p h
( s e e G raph # 1 )
is
a t to p e ffic ie n c y .
A c co rd in g t o
a n a v e r a g e maximum y i e l d
o b t a i n e d a t t e m p e r a t u r e s b e tw e e n 9 5 0 °an d 1 0 5 0 °F .
sa y t h a t th e te m p e ra tu re i s n o t c r i t i c a l a s lo n g a s
One m i g h t
it
is
o v er 850.
II.
EFFECT OF CATALYSTS
T he c a t a l y s t u s e d d o e s n o t seem t o h a v e a g r e a t i n f l u ­
e n ce on t h e r e a c t i o n .
W o rk w as d o n e i n a p o r c e l a i n t u b e
u s i n g i r o n o x i d e ( F e g 03 ) , c o p p e r g a u z e , v a n a d i u m o x i d e a n d
no c a t a l y s t a t a l l .
The r e s u l t s show t h a t a p l a i n p o r c e l a i n
tu b e seem ed t o g i v e t h e b e s t r e s u l t s , w i t h c o p p e r g a u z e b e t t e r
th a n th e
i r o n o x id e c a t a l y s t .
T he i r o n o x i d e c a t a l y s t ,
es­
p e c i a l l y a t l o w e r t e m p e r a t u r e s , f o r m e d a s u l f i d e w h i c h w as
p ro v e n by th e e v o lu tio n o f s m a ll q u a n t i t i e s
a d d itio n of d ilu te h y d ro c h lo ric a c id .
o f HgS o n t h e
At h ig h te m p e ra tu re s
t h i s w as n o t n o t i c e d .
The c o n d it i o n o f t h e c a t a l y s t a f t e r a ru n v a r i e d g r e a t l y
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19
w ith th e te m p e ra tu re and th e le n g th o f th e ru n in tim e .
The
i r o n o x id e a t lo w t e m p e r a t u r e s t e n d s t o t u r n b l a c k due t o
r e a c t i o n w ith th e HgS, w h ile a t h i g h e r te m p e r a t u r e s ,
th e
1000° F
and o v e r , t h e c a t a l y s t w as u n c h a n g e d a n d c o u ld b e u s e d o v e r
a g a in .
T h e c o p p e r a t a l l t e m p e r a t u r e s cam e o u t a b l a c k b r i t t l e
m ass w h ic h w o u ld p o w d e r b y m e r e ly t o u c h i n g
a g a in be u s e d .
it,
and c o u ld not
The f a c t t h a t t h e r e a c t i o n g o es a s w e l l ,
n o t b e t t e r , w i t h n o c a t a l y s t , m ade i t
if
h a rd t o d e te rm in e th e
e f f i c i e n c y o f t h e c a t a l y s t on s u c c e s s iv e r u n s .
T h erefo re,
th e c a ta ly s t
re a c tio n .
i s n o t an im p o rta n t f a c t o r i n t h i s
The f o l lo w in g i s a t a b l e g i v i n g t h e t e m p e r a t u r e and
th e y ie ld s u sin g th e d i f f e r e n t c a t a l y s t s .
T hese v a l u e s r e ­
p r e s e n t th e h ig h e s t y ie ld s o b ta in e d f o r each o f th e
u s e d a f t e r s i x m o n th s r e s e a r c h .
Low y i e l d s
c a ta ly sts
o b ta in e d on th e
f i r s t w o rk was due t o p o o r m e th o d s o f s u l f u r r e c o v e r y .
CATALYST
°F
T e m p e ra tu re
5 3 0 ° - 550*
750*
835°
94 0 °
1060
1200*
1400°
The r a t e s
I r o n O x id e
3 9 .8 $
5 1 .8 $
7 2 .2 $
7 8 .3 $
7 8 .5 $ 7 5 .1 $
7 1 .8 $
o f f lo w o f t h e g a s e s w ere
N one
— __
------ --
7 2 .4 $
8 2 .5 $
8 4 .5 $
8 2 .0 $
8 0 .1 $
C o p p e r G auze
————
7 8 .2 $
8 2 . 5$
7 9 .7 $
7 9 .1 $
7 0 .7 $
. 0 1 c u b i c f o o t o f HgS p e r
m i n u t e a n d . 0 2 5 c u b i c f o o t o f a i r p e r m i n u t e <o n a l l t h e a b o v e
ru n s.
The d u r a t i o n o f t h e r u n s v a r i e d fro m f o r t y - f i v e m in u te s
to an h o u r.
The g rap h
( s e e G raph #1)
sh o w s t h a t u s i n g n o c a t a l y s t
and u s in g co p p er gauze g iv e s r e s u l t s t h a t ru n t r u e
to fo rm .
T h e maximum y i e l d s a r e b e t w e e n 9 5 0 " a n d 1 1 0 0 " a n d t h e
drop o f f fro m t h a t p o i n t .
cu rv es
I r o n o x id e g iv e s a v e ry good c u rv e ,
ex ce p t t h a t th e y i e l d o f s u l f u r i s n o t a s h ig h a s th o s e w ith
c o p p e r g a u z e an d no c a t a l y s t a t a l l .
III.
CALCULATION OF YIELD OF SULFUR
T y p ic a l s e t o f d a ta .
C a ta ly s t — copper gauze
V o lu m e o f HgS p e r m i n u t e
.0 1 c u b ic f e e t
V o lu m e o f a i r p e r m i n u t e
.0 2 5 c u b ic f e e t
T e m p e ra tu re
960° F
T im e o f r u n
51 m i n u t e s
E x p e rim e n ta l y i e l d — s u l f u r
1 7 . 2 5 0 0 g m s.
T h e o re tic a l y ie ld — s u lf u r
2 0 . 9 8 7 0 g m s.
P e rc e n ta g e y ie ld
8 2 .5 $
C a lc u la tio n s.
HgS + 4 / 2 Ng 1
4- ° 2 j
1 v o l . HgS +
2jg
a ir
=
v o l.
S Hh Hg 0
a ir
=
2Ng
S + Hg 0 + 2 v o l . Ng
1 c u b i c f o o t =■ . 2 8 , 3 1 5 l i t e r s
D e n s i t y o f HgS =
1 . 5 3 9 2 gm s. p e r l i t e r a t 2 0 ° C
.0 1 c u b ic f o o t —
.2 8 3 0 l i t e r s
W e i g h t o f HgS =
.2 8 3 0 x 1 .5 3 9 2
=
. 4 3 5 6 g m s.
21
T h e o r e tic a l w e ig h t o f s u l f u r fro m
m in u te :
. 0 1 c u b i c f o o t o f HgS p e r
.4 5 5 6 _ W t . o f S
34 “
32
T h e o r e t i c a l w e i g h t o f s u l f u r p e r m i n u t e = . 4 1 1 5 g m s.
T h e o r e t i c a l w e i g h t o f s u l f u r f o r 51 m i n u t e s — 2 0 . 9 8 7 0 g m s.
E x p e rim e n ta l y ie ld :
W eig h t o f
d ish
W eig h t o f
d ish
4 4 .1 0 0 7
W eig h t o f
su lfu r
1 7 .2 4 9 8
P e rc e n ta g e y ie ld :
■+■s
RATI OF FLOW
The e f f e c t o f r a t e
u sin g
re a c tio n .
6 1 .3 5 0 5
1 7 . 2 4 9 8 =. 8 2 . 5 $
2 0 .9 8 7 0
IV .
in th is
u lfu r
o f flo w is
a v ery d e c id in g f a c t o r
M o s t o f t h e d a t a g a t h e r e d was o b t a i n e d b y
.0 1 c u b ic f o o t o f h y d ro g e n s u l f i d e p e r m in u te .
T h is
w a s a b o u t t h e l a r g e s t v o lu m e t h e K i p p g e n e r a t o r w o u l d p u t
o u t o v e r a p e r i o d o f 50 - 60 m i n u t e s .
T h e l a r g e v o lu m e w a s
u s e d b e c a u s e a g r e a t e r y i e l d o f s u l f u r w as o b t a i n e d , a n d t h e
l o s s e s o f s u l f u r d ue t o
m in im iz e d .
its
r e c o v e r y and o t h e r c a u s e s w e re
T hese l o s s e s w ere a b o u t c o n s t a n t ,
an d t h e y w o u ld
a f f e c t . t h e f i n a l y i e l d m uch m o r e w h e n s m a l l v o l u m e s o f g a s
w ere u s e d and c o n s e q u e n tly s m a lle r y i e l d s o f s u l f u r .
S in c e th e sp eed of r e a c tio n in
im p o rta n t,
d a t a w as g a t h e r e d u s i n g b o t h l a r g e r and s m a l l e r
v o lu m e s t h a n
V o lu m e s o f
v o lu m es a n d
th e cham ber w as v e ry
.0 1 o f a c u b ic f o o t p e r m in u te ( s e e G rap h # 2 ) .
.0 2 0 an d .0 1 6 c u b ic f e e t w e re u s e d f o r g r e a t e r
.0 0 6 o f a c u b ic f o o t u s e d a s t h e s m a l l e s t v o lu m e .
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I t w as f o u n d t h a t t h e
s m a l l e r t h e v o lu m e p e r m in u te t h e h i g h e r
th e y ie ld
T he h i g h e r v o l u m e s o f g a s p a s s e d t h r o u g h
th e tu b e
of su lfu r.
of th e fu rn ac e to o f a s t to
c o m p le te ly r e a c t ,
and
t h u s m uch o f t h e h y d r o g e n s u l f i d e g o e s t h r o u g h u n r e a c t e d .
t h e d a t a i n t h e t a b l e b e lo x v , i t
o b ta in e d i n th e f i r s t
ta b le
can be seen t h a t t h e y i e l d s
c o u ld a l l
be r a i s e d a b o u t f i v e
o r s i x p e r c e n t i f a s m a l l e r v o lu m e l i k e
been used r a th e r th a n
F ro m
.0 0 6 c u b i c f o o t h a d
*’ s
.0 1 c u b ic f o o t o f h y d ro g e n s u l f i d e .
T h e v a l u e s i n t h e t a b l e b e l o w w e r e o b t a i n e d b y u s i n g no
c a ta ly st a t a ll,
o f HgS t o
a t e m p e r a t u r e o f 960P F , a t h e o r e t i c a l r a t i o
. a i r , an d t h e d u r a t i o n o f t h e r e a c t i o n was f i f t y
m in u te s" t o an h o u r.
V o lu m e o f H0S
.0 2 0 0 c u b i c f o o t
.0 1 6 6
"
"
.0 1 0 0
"
"
.0 0 6 0
"
"
V.
Y ie ld of S u lfu r
5 4 .1 #
7 2 .1 #
8 2 .5 #
8 7 .5 #
RATIO OF HgS TO A IR
W o rk w a s d o n e , u s i n g b o t h a n e x c e s s o f a i r a n d o f
hy d ro g en s u l f i d e , to s e e
y i e l d m ig h t be o b ta in e d .
i f by th e la w o f m ass a c t i o n a g r e a t e r
W hen a n e x c e s s o f a i r w a s u s e d , t h e
o x i d a t i o n t e n d e d t o go p a s t t h e d e s i r e d - p o i n t s o t h a t m uch
s u l f u r d i o x i d e w as b e i n g f o r m e d .
An e x c e s s o f h y d r o g e n s u l ­
f i d e g a v e n o b e t t e r y i e l d s a s m uch p a s s e d t h r o u g h u n r e a c t e d .
24
From t h e r e s u l t s
o b ta in e d , th e b e s t y i e l d s a r e o b ta in e d from
t h e t h e o r e t i c a l am o u n ts o f t h e g a s e s p a s s i n g th r o u g h t h e r e a c t ­
in g cham ber a t a slo w r a t e .
V I.
EFFECT OF HYDROCARBONS ON THE YIELDS
I n o r d e r t o m o re n e a r l y a p p r o a c h t h e c o n d i t i o n s t h a t
w o u ld b e f o u n d i n w a s te h y d r o g e n s u l f i d e
s tills
of a r e f in e ry ,
g a s from t h e ; c r a c k i n g
a s m a l l a m o u n t ' o f n a t u r a l g a s w a s m ix e d
w i t h t h e HgS b e f o r e o x i d a t i o n .
A c o rre sp o n d in g ly g r e a t e r
v o lu m e o f a i r w a s u s e d t o t a k e c a r e o f o x i d a t i o n o f t h e h y d r o ­
carb o n .
A b o u t o n e - f o u r t h a s m uch h y d r o c a r b o n a s h y d r o g e n
s u l f i d e w as u s e d .
T h is w o u ld r u n a g r e a t am ount h i g h e r i n
p e r c e n t o f h y d ro c a rb o n s th a n fo u n d i n a c t u a l c o n d i t i o n s , b u t
s m a l l e r v o lu m e s o f n a t u r a l g a s c o u ld n o t b e m ea su re d w i t h an y
d e g re e o f a c c u ra c y on t h e ty p e o f t h e m e te r in g d e v ic e u s e d .
On t w o d i f f e r e n t r u n s u s i n g t h e a b o v e m i x t u r e o f g a s e s
a t 9 6 0 °F a n d u s i n g n o c a t a l y s t , y i e l d s
w ere o b t a i n e d .
T h is
is
o f 6 1 .1 $ and 6 2 .$ $
a r e d u c tio n in y i e l d o f a b o u t tw e n ty
p e r c e n t , b u t u n d e r a c t u a l c o n d i t i o n s , w here h y d ro c a rb o n co n ­
t e n t w o u ld b e m uch s m a l l e r , t h e r e s h o u l d b e n o a p p r e c i a b l e
d ro p in th e y i e l d .
V II.
ANALYSIS OF EX IT GAS FOR HgS
I n o r d e r t o d e t e r m i n e how t h e y i e l d
o f s u l f u r com pares
w ith t h e am ount o f u n r e a c te d h y d ro g en s u l f i d e u n d e r d i f f e r e n t
c o n d itio n s,
su lfid e .
s o lu tio n
t h e e x i t g a s was a n a l y z e d f o r u n r e a c t e d h y d r o g e n
The e x i t g a s w as p a s s e d t h r o u g h a s t a n d a r d i z e d
o f io d in e f o r a d e f i n i t e p e rio d
of tim e .
The e x c e ss
i o d i n e t h a t w as n o t r e d u c e d b y t h e HgS %vas t i t r a t e d
a s t a n d a r d s o l u t i o n o f so d iu m a r s e n i t e .
a g a in st
By c a l c u l a t i n g t h e
a m o u n t o f i o d i n e t h a t h a d b e e n r e d u c e d , t h e a m o u n t o f HgS
p a s s in g o u t w ith e x it gas o v e r a c e r t a i n d u r a tio n c o u ld be
found.
I t w as f o u n d i n g e n e r a l t h a t t h e h i g h e r t h e
te m p e ra ­
t u r e , t h e s m a l l e r t h e a m o u n t o f HgS i n t h e e x i t g a s .
Thus i t
i s to be co n clu d ed t h a t a t t h e h ig h e r te m p e ra tu re s t h e
in y ie ld
o f s u l f u r i s due n o t o n ly t o u n r e a c te d H gS, b u t t o
m e c h a n ic a l lo s s e s
tu re s .
lo ss
o f s u l f u r w h ic h i n c r e a s e a t h i g h e r te m p e ra ­
F rom t h e d a t a i n t h e t a b l e a n d by o b s e r v i n g t h e
a c c o m p a n y in g g r a p h ( s e e G ra p h # 3 ) ,
it
is
seen th a t th e p e r­
c e n t o f r e a c t e d HgS p l u s t h e p e r c e n t o f u n r e a c t e d HgS d o e s
n o t a d d u p t o 100%, b u t o n t h e a v e r a g e o f 9£% t o
m e a n s t h a t a r o u n d 5% t o
m e d n a 1; ,
of th e y ie ld
is
95%.
lo s t by o th e r
T h is can be a t t r i b u t e d t o m e c h a n ic a l lo s s
reco v ery of th e s u lf u r in th e p ro c e ss.
in th e
The e x i t t u b e s , d e s ­
p i t e a l l p r e c a u t i o n s , w e re a lw a y s c o a t e d w i t h a t h i n
condensed s u l f u r a f t e r each ru n .
t h i s m e c h a n ic a l l o s s ,
h un dred p e r c e n t.
ly st,
T h is
So ta lc in g i n t o
film
of
c o n sid e ra tio n
th e t o t a l y i e l d a d d s up t o n e a r l y a
M o s t o f t h i s w orlc w a s d o n e u s i n g n o c a t a ­
b u t so m e w o r k u s i n g c o p p e r a s t h e
c a t a l y s t show ed t h a t
26
t h e p e r c e n t o f HgS i n t h e e x i t g a s r a n r o u g h l y a r o u n d 1% m o r e .
Temp e r a t u r e ° F
A verage v a lu e o f %
HpS i n e x i t g a s
1400° F
1200 °
1100 *
96 0*
840*
700*
1 2 .1 4 %
1 3 .7 9 %
1 4 .8 0 %
1 4 .1 8 %
1 5 .3 8 %
3 1 .1 2 %
T h e v a l u e f o r 960* F i s
have as th e o th e rs
do.
c o rre sp o n d in g v a lu e s .
p e rc e n t,
it
th e o n ly one t h a t does n o t b e ­
F o u r r u n s w e r e m ad e a n d a l l g a v e
S in c e th e
change i s
o n ly ab o u t h a lf a
seem s u n im p o r ta n t an d p r o b a b ly i s
m e n ta l e r r o r .
due t o e x p e r i ­
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CHAPTER V I I
CONCLUSION
The w o rk done on t h i s
p r o c e s s d e f i n i t e l y show s t h a t
w i l l go a lm o s t q u a n t i t a t i v e l y .
The s u l f u r o b t a i n e d i s
it
in a
v e r y d e s i r a b l e f o r m a n d w o u l d m ak e a n e x c e l l e n t i n s e c t i c i d e
due t o
its
sm a ll p a r t i c l e
siz e .
The r e a c t i o n
is not c r i t i ­
c a l l y a f f e c t e d by te m p e r a tu r e o v e r a w id e r a n g e , and c a t a ­
l y s t s do n o t s e e m n e c e s s a r y t o
im p o rta n t f a c t o r i s th e r a t e
r e a c t i n g ch am b er.
th e y ie ld
is
o b ta in good y i e l d s .
The m o st
of flo w of th e g a se s th ro u g h th e
B y l o o k i n g a t ’G r a p h
$Z ,
it
i s found t h a t
a v ery d e f in ite fu n c tio n o f th e r a te
o f flo w .
T h e re w as a d ro p i n y i e l d w hen h y d r o c a r b o n s w ere a d d e d , b u t
i f th e y had been added to th e e x te n t th e y a re p r e s e n t in
w a s t e HgS g a s a r o u n d r e f i n e r i e s ,
if
any d e crea se
in th e y ie ld .
t h e r e w o u ld h a v e b e e n l i t t l e
The d i f f i c u l t y
o f m e a su rin g
a n y am ount s m a l l e r t h a n t h a t u s e d h e r e l e d t o t h e l a r g e v o l ­
ume o f h y d r o c a r b o n s u s e d i n p r o p o r t i o n t o t h e
am ount o f HgS.
M o s t r e f i n e r i e s h a v e e n o u g h w a s t e HgS t o m ake t o n s o f
s u l f u r a y e a r by t h i s
p ro cess.
T he r e a s o n t h a t t h e r e h a s
b e e n p r a c t i c a l l y no w ork done c o m m e rc ia lly on t h i s
lo c a l re fin e rie s
is
n e c e s s a r y e q u ip m e n t.
p ro c e ss in
due t o th e h ig h c o s t of i n s t a l l a t i o n
of
S i n c e s u l f u r i s o r d i n a r i l y m in e d i n
T e x a s an d L o u i s i a n a , t h e c o s t o n t h e m a r k e t i s v e r y lo w a s
com pared t o w h a t s u l f u r w o u ld h a v e t o
s e l l f o r in o rd er to
pay o f f th e o r i g i n a l in v e stm e n t in t h i s p r o c e s s .
When t h e
29
i n i t i a l e x p e n s e o f e q u i p m e n t w as p a i d f o r ,
c o u l d p r o b a b l y u n d e r s e l l m in e d s u l f u r ,
re fin e ry s u lfu r
s i n c e t h e c h i e f raw
m a t e r i a l was p r e v i o u s l y a w a s t e p r o d u c t .
By s p r e a d i n g t h e
o r i g i n a l in v e s tm e n t o v e r a lo n g tim e p e r i o d , t h e c o s t o f
s u l f u r m ad e f r o m HgS s h o u l d c o m p a r e v e r y f a v o r a b l e w i t h t h e
s u l f u r on th e m arket to d a y .
B efo re t h i s p ro c e ss
i s used c o m m e rc ia lly ,
be ta k e n th ro u g h th e p i l o t p la n t s t a g e .
be c a r r ie d
it
sh o u ld
E x p e rim e n ts s h o u ld
o u t u s i n g m uch l a r g e r v o l u m e s o f g a s e s a s w e l l a s
a l a r g e r o x i d i z i n g cham ber.
T he e f f e c t
o f te m p e ra tu re and
t h e v a r i o u s c a t a l y s t s u s e d s h o u ld be com p ared u n d e r t h e s e
c o n d itio n s w i t h th o s e f a c t s fo u n d i n t h e s m a lle r s c g l e
tio n .
The p r o d u c t s o t h e r t h a n s u l f u r ,
o p era­
such a s th io n ic a c id s
and p o l y t h i o n a t e s t h a t p r o b a b ly fo rm ed i n s m a ll a m o u n t, c o u ld
be c a r e f u l l y d e te rm in e d .
T h ere i s u n d o u b te d ly a f u t u r e
o il re fin e rie s.
T h is f u t u r e
of th e p e tro le u m
n o t o n ly i n t h e m ak in g o f g a s o l in e .,
lik e ,
in th is
fie ld
f o r th e
in d u stry l i e s
lu b r ic a tin g o i l and th e
b u t e v e n t o a m u ch g r e a t e r e x t e n t i n b y - p r o d u c t s a n d
sy n th e tic
o r g a n ic com pounds.
b e e n m uch r e s e a r c h c a r r i e d
fo re i t
lo o k s' as i f
In th e
on i n t h i s
l a s t few y e a r s t h e r e h as
lin e
th e p ro cess d isc u sse d
som e m o d i f i c a t i o n o f i t ,
of en d eav o r.
T h ere­
in t h is p a p e r, o r
w i l l s o o n 'becom e c o m m e r c i a l l y a c c e p ­
ta b le by th e o i l in d u s try .
BIBLIOGRAPEX
BIBLIOGRAPHY
A.
BOOKS
E n g e l d e r , C a r l , E l e m e n t a r y Q u a n i t a t i v e A n a l y s i s .J o hn Y / i l e y a n d S o n s , 1 9 3 7 .
P p . 1 4 6 -1 5 9 .
New Y o r k :
F r i e n d , J . N e w to n , T e x tb o o k o f I n o r g a n i c C h e m i s t r y . L ondon:
C h a r l e s G r i f f i n a n d Com pany L i m i t e d , 1 9 1 9 .
P p. 4 6-67.
L u n g e a a n d C u m m in g s, S u l f u r i c A c i d a n d S u l f u r D i o x i d e .
G urney and J a c k s o n , 193 1 .
Pp. 43-45.
London
M e l l o r , J . W . , A C o m p r e h e n s i r e T r e a t i s e on I n o r g a n i c a n d
T h e o r e t i c a l C h e m i s t r y . L o n d o n : L o n g m a n s , G r e e n a n d Com­
pany, 1930.
P p . 114-146.
R i e g e l , E m i l , I n d u s t r i a l C h e m i s t r y . New Y o r k : R e i n h o l d P u b ­
l i s h i n g Com pany, 1 9 3 7 . P p . 2 5 5 - 2 5 6 .
S c o t t , S t a n d a r d M e t h o d s o f C h e m i c a l A n a l y s i s . New Y o r k :
D . V an N o s t r a n d Com pany I n c o r p o r a t e d , 1 9 3 9 .
Pp. 12561264.
B.
PERIODICAL ARTICLES
F u l t o n , W. F . , " C o m p l e t e A n a l y s i s o f N a t u r a l G a s , " G as a n d
O i l J o u r n a l . 3 6 : 6 0 , May 2 0 , 1 9 3 $ .
I s o m , E . W. , "New R i c h f i e l d R e f i n e r y , ” G as a n d O i l J o u r n a l ,
5 7 :3 6 , M arch 2 , 1 9 3 9 .
L e a h y , M ic h a e l J . , " C le a n in g H ig h S u lp h u r G a s e s ," R e f i n e r
and N a tu r a l G a s o lin e M a n u fa c tu re r, 1 5 :2 7 6 , J u l y , 1936.
L i l l y , R . M . , . " D e t e r m i n i n g HgS C o n t e n t o f G as i n F i e l d , "
G as a n d O i l J o u r n a l , 3 6 : 5 2 , A u g u s t 1 9 , 1 9 3 7 .
M u l l e n , J . M. , " H y d r o g e n S u l p h i d e R em oved b y U s i n g T r i p o ­
t a s s i u m P h o s p h a t e " , G as and O i l J o u r n a l , 3 7 : 3 7 , A p r i l 1 3 ,
1939.
R o s e b a u g h , T . V /., " T h e P h o s p h a t e P r o c e s s f o r t h e R e m o v a l o f
HgS f r o m N a t u r a l G a s " , G as J o u r n a l , ‘ : 2 4 , A u g u s t , 1 9 3 8 .
32
T u t w i l e r , C . C . , ‘' Q u a n t i t a t i v e E s t i m a t i o n o f E gS i n I l l u m i n a ­
t i n g G a s " , J o u r n a l o f A m e ric a n G h e m ic a l S o c i e t y , 2 3 :1 7 3 ,
1901.
______ , " T h e K o p p e r ' s M e t h o d ‘o f HoS R e m o v a l " , G a s a n d O i l
J o u rn a l., 3 6 :1 2 , A ugust 1 2 , 1937.
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