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A study of the reactions and properties of petroleum sulfuric acid sludge and some of its derivatives

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A STUDY OF THE REACTIONS AND PROPERTIES OF PETROLEUM
SULFURIC ACID SLUDGE AND SOME OF ITS DERIYATBfES
A T h esis
P re se n te d to
t h e F a c u l t y o f t h e G ra d u a te S c h o o l
?Die U n i v e r s i t y o f S o u th e r n C a l i f o r n i a
In P a r tia l F u lfillm e n t
o f t h e R e q u ir e m e n ts f o r t h e D eg ree
M a s te r o f A r t s
by
C lau d e H en ry P e r i e r
A u g u st 1941
UMI Number: EP41538
All rights reserved
INFORMATION TO ALL USERS
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IJM I
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This thesis, w ri tt en by
CLAUDE..MNRX..PEMEH.................................
under the direction of h.Xs. F acu lty C o m m it te 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 be en
p res en te d to a n d a c c e p te d by the C oun ci l on
G rad u ate S t u d y and R ese arc h in part ial fulfill н
m e n t o f 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
MASTER OF ARTS
Secretary
D a te..
A ugU зt...l.9.41
F aculty C om m ittee
^
.
. г
?1^
^
?
Chairman
ACKNOWLEDGMENTS
The aim o f t h i s r e s e a r c h p r o j e c t was t o p re p a re , a n d
i n v e s t i g a t e d e r i v a t i v e s made fro m p e t r o le u m s u l f u r i c a c i d
slu d g e .
The p u r p o s e w as t o make a n d d e s c r i b e p r o d u c t s w h ich
w ould u s e a c i d s lu d g e a s a raw m a t e r i a l f o r m a n u f a c t u r i n g i n
o r d e r t o s a v e t h i s m a t e r i a l , w h ich i s d i s c a r d e d i n so many
oases.
I t was n e c e s s a r y t o o b t a i n p e t r o le u m s u l f u r i c a c i d
s lu d g e fro m v a r i o u s o i l co m p a n ie s a n d a p p r e c i a t i o n i s
e x p r e s s e d t o Mr. C. K. Hewes, C h i e f C h e m ist, R i c h f i e l d O i l
C o r p o r a t i o n ; Mr. E . P a lm e r, C h i e f C h e m is t, U nion O i l Company
o f C a l i f o r n i a ; Mr. F r e d e r i c k S c h e r f , W i l s h i r e O i l Company;
f o r a i d i n s e c u r i n g sa m p le s o f a c i d s lu d g e an d f o r d e s c r i p н
t i o n s o f t r e a t i n g p r o c e s s e s b y w h ich t h e r e s p e c t i v e sa m p le s
w ere fo rm e d .
TABLE OF CONTENTS
CHAPTER
I.
PAGE
THE PROBLEM AND DEFINITIONS. OF TERMS USED . . . .
D e f i n i t i o n an d t y p e s o f p e t r o le u m a c i d s l u d g e .
1
The p ro b le m
3
^
S ta te m e n t of t h e p ro b le m .
III.
V*
3
.
3
REVIEW OF LITERATURE AND HISTORICAL INFORMATION .
5
L i t e r a t u r e d e a l i n g w ith t h e e x a c t p ro b le m . . .
5
L i t e r a t u r e p e r t a i n i n g t o r e l a t e d p r o b le m s . . .
7
THE MATERIALS USED. . . . .
E q u ip m en t . . ........................
IV .
.
. . . . . . . . . .
Im p o rta n c e o f t h e s t u d y
II.
1
i . . . . . . . . .
.
11
. . . . . . . . . . .
11
C h e m ic a ls . . . . . . . . . . . . . . . . . . .
11
SPECIAL METHODS OF ANALYSIS.................................
13
PREPARATION AND GENERAL DESCRIPTION OF VARIOUS
DERIVATIVES............................. . . *. ......................................15
V I.
A COMPREHENSIVE INVESTIGATION OF THE
CHLORINATED DERIVATIVE. . . . . . . . . . . . .
V II.
SUMMARY AND CONCLUSIONS................................
Summary . . .
............................
C o n c l u s i o n ..........................................
33
40
40
41
BIBLIOGRAPHY.................................* .
-43
APPENDIX..........................................
44
L IST OF TABLES
TABLE
1.
PAGE
S o l u b i l i t y of t h e c h l o r i n a t e d r e s i d u e fro m
p e tro le u m a c id slu d g e
2.
25
A c o m p a ris o n of th e p r o p e r t i e s of T o r n e s i t
an d t h e c h l o r i n a t e d r e s i d u e from p e t r o le u m
a c i d s l u d g e .......................
45
L IS T OF FIGURES
FIGURE
1.
PAGE
F low s h e e t show ing t h e p r e p a r a t i o n o f
c h lo rin a te d m a te ria l
2.
22
The c o r r e l a t i o n b e tw e e n s l u d g e a c i d s t r e n g t h
and th e p e r c e n t o f c h lo rin e p r e s e n t i n th e
f i n a l p ro d u c t.
3.
...................................................
35
The c o r r e l a t i o n b e tw e e n t h e p e r c e n t of
c h lo r in e in th e f i n a l d e r i v a ti v e s and th e
a v e r a g e m o l e c u l a r w e ig h ts of t h e r e s p e c t i v e
p r o d u c t s .............................
. . . . . . .
56
CHAPTER I
THE PROBLEM AND DEFINITIONS OF TERMS USED
The f i n a n c i a l l o s s i n v o l v e d b y t h e f o r m a t i o n o f
p a r t i a l l y - s p e n t a c i d and th e a c t u a l d is p o s a l of p e tro le u m
s u l f u r i c a c i d s l u d g e have a lw a y s b e e n m a jo r p ro b le m s i n th e
o il in d u stry .
The p u r p o s e o f t h e i n v e s t i g a t o r h a s b e e n t o
c o l l e c t i n f o r m a t i o n an d d a t a w h ich may s u g g e s t some
co m m ercia l u s e o r a p p l i c a t i o n f o r t h i s m a t e r i a l .
I.
DEFINITION AND TYPES OF PETROLEUM ACID SLUDGE
D e fin itio n .
In th e p e tro le u m i n d u s t r y , p a r t i a l l y
r e f in e d p ro d u c ts a re o f te n t r e a t e d w ith s u l f u r i c a c id to
remove u n d e s i r a b l e i n g r e d i e n t s a n d t o im pro ve c o l o r .
In
g e n e ra l, th e p ro c e ss c o n s is ts of m e c h a n ic a lly a g i t a t i n g a
p e t r o l e u m d i s t i l l a t e w i t h a s m a ll q u a n t i t y
(u su a lly 1 to
10 po u n d s p e r 42 g a l l o n b a r r e l o f o i l ) o f s u l f u r i c a c i d .
A f t e r t h e m ix i n g , t h e fo rm e d a c i d s lu d g e w h ich i s a m i x t u r e
o f com p lex r e a c t i o n p r o d u c t s i s a l l o w e d t o s e t t l e t o t h e
b o tto m o f t h e t r e a t i n g t a n k , an d i s t h e n d e c a n te d f o r d i s p o s н
a l.
S in c e t h e d i s p o s a l o f a c i d s lu d g e c r e a t e s a n i m p o r t a n t
p ro b le m , t h i s r e s e a r c h w ork h a s b e e n done t o a i d i n s o l v i n g
th is o il re fin e ry d if fic u lty .
I n many p l a n t s a c i d r e c o v e r y
p r o c e s s e s h ave been' t r i e d and u s u a b l e s u l f u r i c a c i d h a s b e e n
r e g e n e r a t e d b y su c h m e th o d s a s e m p lo y in g s lu d g e t o p ro d u c e .
s u l f u r d i o x i d e fro m w hich t h e a c i d may be f o rm e d .
More
o f t e n , due t o t h e g r e a t e x p e n s e o f a c i d r e c o v e r y m e th o d s ,
t h e s p e n t s lu d g e h a s b e e n f e d t o r e f i n e r y b o i l e r h o u s e s a n d
b u r n e d m e r e ly t o sa v e i t s h e a t i n g v a l u e a s a f u e l .
B u rn in g
a c i d s lu d g e t o s o l v e t h e d i s p o s a l p ro b le m r e s u l t s i n a huge
l o s s b e c a u s e a l l o f t h e r e s i d u a l a c i d an d com plex o r g a n i c
compounds a r e d e s t r o y e d w i t h a r a t h e r i n s i g n i f i c a n t r e c o v e r y
of h e a t.
F o r t r e a t i n g , a c i d s o f v a r y i n g s t r e n g t h a r e em ploy ed,
d e p e n d in g on th e p u r p o s e o f th e a c i d t r e a t a n d .the m a t e r i a l
t o be t r e a t e d .
S om etim es a n a c i d w h ich h a s b e e n u s e d i n
some r e l a t e d p r o c e s s , f o r exam p le c a t a l y s i s i n p o l y m e r i z a н
t i o n , may h av e s u b s e q u e n t a p p l i c a t i o n i n t h e t r e a t i n g p l a n t
w hich a l t e r s t h e n a t u r e o f t h e r e s u l t i n g s p e n t a c i d ; b u t t h i s
a l s o i s a p r o d u c t o f t h e p e t r o le u m s lu d g e c l a s s ev en th o ug h
th e a c id has serv ed a tw o -fo ld p u rp o se.
T h i s l a t t e r ty p e o f .
s lu d g e was g iv e n a d d i t i o n a l c o n s i d e r a t i o n b e c a u s e i t h a s
r a p i d l y become v e r y p l e n t i f u l due t o im p ro v e d r e f i n i n g m e th o d s
a n d new p e t r o l e u m c h e m ic a l e n g i n e e r i n g p r o c e s s e s *
T ypes.
S lu d g e may be d i v i d e d i n t o t h e f o l l o w i n g
c la sse s:
1.
L i g h t l i q u i d s lu d g e r e s u l t i n g f ro m t h e
t r e a t m e n t o f " s t r a i g h t r u n " g a s o l i n e a n d k e r o s e n e w ith
s u lfu ric a c id .
2.
L i g h t l u b r i c a t i n g o i l s l u d g e w h ich i s b l a c k
3
and v is c o u s .
3.
Heavy l u b r i c a t i n g o i l s lu d g e w h ich i s
p r a c t i c a l l y s o l i d when c o ld *
'4 .
A l i g h t b l a c k o i l y a c i d s l u d g e o f lo w a c i d i t y
w hich i s p r o d u c e d b y c o l d a c i d t r e a t i n g c r a c k e d s t o c k s .
T h is
m a t e r i a l , w hich i s u s u a l l y b u r n e d , i s v e r y h i g h i n h y d r o н
c a r b o n c o n t e n t due t o t h e t y p e o f m a t e r i a l t r e a t e d .
The p e r
c e n t o f a c i d i n th e s lu d g e d e p e n d s on t h e t e m p e r a t u r e a t
w h ich t h e u n s a t u r a t e d h y d r o c a r b o n s a r e p u t i n c o n t a c t w i t h
th e a c id and th e e f f e c t i v e n e s s o f th e s e p a r a tin g p ro c e s s
e m p lo y e d .
II.
THE PBOBLEM
S t a t e m e n t o f th e p r o b le m .
The p ro b le m was d i v i d e d
i n t o t h e f o l l o w i n g two s t e p s :
A..
A th o r o u g h i n v e s t i g a t i o n of v a r i o u s r e a c t i o n s
o f p e tro le u m a c i d s lu d g e .
B.
An e x t e n s i v e s t u d y o f th e m o st i n t e r e s t i n g
a p p e a r i n g p r o d u c t a s p r e p a r e d b y one o f t h e r e a c t i o n s t r i e d
i n t h e p r e l i m i n a r y e x p e r i m e n t a l w ork.
I m p o rta n c e o f th e r e s e a r c h p r o . l e c t .
The econom ic
v a l u e o f a s o l u t i o n t o t h e p ro b le m i s s u g g e s t e d i n t h e
fo llo w in g q u o ta tio n :
"The u t i l i z a t i o n o f t h i s m a t e r i a l
^ p e tr o le u m a c i d s lu d g e j
in d u stry i t s e l f .
i s a s o l d a s th e p e t r o le u m r e f i n i n g
The v a l u e o f th e s u l f u r i c a c i d u s e d o n l y
I n t r e a t i n g l u b r i c a t i n g o i l s i n th e U n i t e d S t a t e s i n 1929
h a s b e e n e s t i m a t e d a t # 8 ,5 0 0 ,0 0 0 o f w hich 4 0 $ was i r r e v o c a b l y
lo s t." 1
N ot o n l y h a s t h e l o s s o f v a l u a b l e a c i d b e e n a n
econ om ic p ro b le m b u t t h e d i s p o s a l o f t h e r e s u l t i n g s lu d g e
c r e a t e s a n a d d i t i o n a l d i f f i c u l t y w hich h a s p r a c t i c a l l y
re m a in e d u n s o l v e d .
The t r o u b l e s o f d i s p o s a l h a v e b ee n
c o n f ir m e d b y i n v e s t i g a t i o n and o b s e r v a t i o n an d s u b s t a n t i a t e d
by R a th e r .2
O l i v e r , T. C. an d S p a n g l e r , S . F . , M i s c e l l a n e o u s
R e a c t i o n s o f H a lo g e n D e r i v a t i v e s o f P a r a f f i n s a n d C y o lo p a r a f f i n s . D u n s ta n , D r. il. S . , an d o t h e r s , e d i t o r s , The
S c ie n c e o f P e tr o le u m
(O x fo rd U n i v e r s i t y P r e s s , 19 3 8 ,
London, New Y ork, T o r o n t o ) , V o l . - 4 , p . 2764
2R a t h e r , J . B , , ,rA c id S lu d g e D i s p o s a l Rem ains
U n so lv e d P ro b le m t o R e f i n i n g P l a n t s , ? N a t i o n a l P e t r o l e u m .
2 0 : 7 5 - 8 , F e b r u a r y 2 2 , 1938
CHAPTER I I
REVIEW OF THE LITERATURE AND HISTORICAL INFORMATION
I.
LITERATURE DEALING WITH THE EXACT PROBLEM
A v e r y l i m i t e d am ount o f i n f o r m a t i o n w hich d e s c r i b e s
t h e u s e o f , a c i d s lu d g e a s a w hole f o r s y n t h e t i c p u r p o s e s i s
a v a ila b le .
More o f t e n th e m a t e r i a l , I f n o t s u b j e c t e d t o
a c i d r e c o v e r y p r o c e s s e s , h a s b e e n u s e d a s a c r u d e raw s o u r c e
fro m w hich one c h e m ic a l h a s b e e n i s o l a t e d o r h a s b e e n
s y n t h e s i z e d a s a com ponent p a r t .
G a m e r 1 s t a t e s , nThe u s u a l l a r g e p a t e n t l i s t a p p e a r s
c o v e r i n g a v a r i e t y o f m eth o d s f o r u t i l i z i n g a c i d s l u d g e .
I n m o st c a s e s th e o b j e c t i n v ie w i s t h e r e c o v e r y o f s u l f u r i c
a c id ."
E l l i s d e s c r i b e s th e i s o l a t i o n o f s u l p h o n i c a c i d s , 2
s u l f a t e d com po un ds,5 a n d t h e s y n t h e s i s o f a l c o h o l s from
p e tro le u m a c id s lu d g e .^
^ G a r n e r , F . H ,, P e tr o le u m T e c h n o lo g y i n 1958 (The .
I n s t i t u t e o f P e tr o le u m , V o l . 4 , , London: The A d e l p h i ,
1 9 3 9 ) , p . 511
2E l l i s , C a r l e t o n , C h e m is tr y o f P e tr o le u m D e r i v a t i v e s
(V o l. 2 . New Y ork: C h e m ic al C a t a l o g Company, 1 9 3 4 ) , p . 3 5 3
3I b i d . , p p . 1 0 1 3 -1 6
4 I b i d . , p . 1023
Beardо d i s c u s s e s th e r e a c t i o n o f v a r i o u s h y d r o c a r b o n s
w ith s u l f u r i c a c i d b u t does n o t in c lu d e any a p p l i c a t i o n f o r
th e r e s u l t i n g p r o d u c ts .
B i r d 6 a d d e d w ater- t o a c i d s lu d g e a n d by e f f e c t i n g a
r e a c t i o n b e tw e e n t h e h y d r o l y z e d p r o d u c t an d a h a l o g e n a t i n g
a g e n t he fo rm e d a r e s i n o u s p r o d u c t s u i t a b l e f o r a c o a t i n g
m a te ria l.
H i l l 7 c o n t r i b u t e s v a l u a b l e i n f o r m a t i o n by e l a b o r a t i n g
on
t h e c o m p o s iti o n o f a c i d s l u d g e .
He s t a t e s , ??A cid s lu d g e
is
a p o t e n t i a l so u rce o f h y d rocarbon su lp h o n ic a c i d s . "
T h is
i n f o r m a t i o n t e n d s t o s u g g e s t t y p e s o f r e a c t i o n s w hich s h o u ld
be c h a r a c t e r i s t i c o f p e t r o l e u m a c i d s l u d g e ,
Holzman an d S u k n a ro w s k i8 s u b s t a n t i a t e t h e f i n d i n g s
o f H i l l an d g iv e t h e f o l l o w i n g a n a l y s e s o f a c i d s lu d g e w i t h
a c o m p le te d e s c r i p t i o n of. t h e m eth o d s of a n a l y s i s :
оBeard, L. C . , " G e n e r a l L a b o r a t o r i e s , o f S t a n d a r d O il
Company o f Hew Y o r k ," O i l and Gas J o u r n a l . Y o l. 2 8 , No. 4 2 ,
March 6 , 1930 ( T u l s a , Oklahom a: P e tr o le u m P u b l i s h i n g Company)
6B i r d , J . C . , U n i t e d S t a t e s P a t e n t 1 . 9 1 7 . 8 6 9 . J u l y
1 1 , 1 9 3 3 , t o S t a n d a r d O i l Company, C h e m ic al A b s t r a c t s . 19 33,
No. 2 7 , Column 4 6 6 6 .
7H i l l , J . B e n n e t t , "W aste P ro b le m s i n th e P e tr o le u m
I n d u s t r y , ? I n d u s t r i a l a n d E n g i n e e r i n g C h e m i s t r y . Y o l. 3 1 ,
P a r t 2 , No. 2 , p . 1 3 6 1 , November, 1939
h o l z m a n , E . a n d S u k n a r o w s k i, S t e f a n , " A n a l y s i s o f
A c id S lu d g e s fro m M in e r a l O i l T r e a t m e n t s , " I n d u s t r i a l a n d
E n g i n e e r i n g C h e m is tr y ?A n a l y t i c a l - E d i t i o n . 7 :3 7 8 - 3 8 0 , 1 9 3 5 .
S lu d g e Sample
A.
B.
C.
M in e r a l O i l
1 5 .4 $
4 . 7 fa
5 9 .2 $
S u l p h o n ic A c id s
3 7 .0 $
6 3 .2 $
1 7 .9 $
F r e e S u l f u r i c A c id
4 5 .5 $
2 9 .3 $
2 0 .8 $
In s o lu b le M a tte r
o * i$
0 .0 9 $
1*6$
(S u lfu ro u s a n h y d rid e n e g l e c t e d . )
The p r e s e n c e o f l a r g e q u a n t i t i e s o f s u l p h o n i c a c i d s
. a s d e t e r m i n e d by t h e s e two i n v e s t i g a t o r s l i k e w i s e shows why
t h e p r o p e r t i e s o f a c i d s lu d g e s h o u l d re s e m b le t h o s e o f
su lp h o n ic a c id s .
II.
LITERATURE PERTAINING TO RELATED PROBLEMS
H a lo g e n a te d r u b b e r , w h ich i s c o m m e r c ia lly r e f e r r e d
t o a s T o r n e s i t , i s now m a n u f a c tu r e d i n th e U n i t e d S t a t e s . 9
Ellis**-0 t h o r o u g h l y d e s c r i b e s th e p r e p a r a t i o n , p r o p e r t i e s ,
a n d u s e o f t h i s p r o d u c t w h ic h , fro m th e d e s c r i p t i o n g i v e n ,
a p p e a r s t o b e a r a r e m a r k a b le s i m i l a r i t y t o th e p r o d u c t fo rm e d
b y t h e c h l o r i n a t i o n o f p e t r o le u m a c i d s l u d g e .
The p r o p e r t i e s
o f T o r n e s i t a s g iv e n by Hodgman-*-**- a r e co m pared w i t h t h o s e
9E l l i s , C a r l e t o n , C h e m is tr y o f S y n t h e t i c R e s i n s . T o l ,
2 (New Y ork: R e i n h o l d t P u b l i s h i n g C o r p o r a t i o n , 1 9 5 5 ) , p . 1117
10I b i d . , p p . 1 1 0 5 -28
"^Hodgman, 0 . D . , C h em ical .T a b l e s fro m th e Handbook o f
C h e m is try a n d P h y s i c s ( C l e v e l a n d , O h io : C hem ical R ubber
P u b l i s h i n g Company, 1938) p p . 573-58 9
8
o f c h l o r i n a t e d a c i d s l u d g e i n t h e A p p e n d ix .
Berger-*-** u t i l i z e d s l u d g e d e r i v e d fro m r e f i n i n g
h y d r o c a r b o n s w ith an a c t i v e m e t a l h a l i d e such a s alum inum
t r i o h l o r i d e to s y n th e s iz e a p l a s t i c
re sin .
To a c c o m p l is h t h i s ,
B e r g e r c o n d e n s e d th e s l u d g e w i t h r e l a t e d a l k y l h a l i d e s .
H is
p r o d u c t, a c c o rd in g to th e p r o p e r t i e s g iv e n , i s s i m i l a r to a
p r o d u c t fo rm e d b y c h l o r i n a t i n g p e t r o l e u m a c i d s l u d g e .
Biroh-1-^ i n h i s e x t e n s i v e r e p o r t , " A p p l i c a t i o n o f
H y p o c h l o r i t e P r o c e s s , " e x p l a i n s w hat may t a k e p l a c e d u r i n g
h y p o c h lo rite t r e a t s i f th e a g i t a t e d m a te r ia ls a re n o t k ep t
out of c o n ta c t w ith a c id .
He e x p l a i n s , " . . . . h y p o c h l o r i t e
s o lu tio n s a re p a r t i c u l a r l y s u ita b le f o r t r e a t i n g cracked
d i s t i l l a t e s b e c a u s e t h e low c o n c e n t r a t i o n o f h y p o c h l o r o u s
a c i d due t o t h e p r e s e n c e o f e x c e s s o f a l k a l i i s a s a f e g u a r d
a g a in s t th e danger of
*c
h lo rin a tio n .*
The te r m c h l o r i n a t i o n
i s s t r i c t l y s p e a k in g i n c o r r e c t s i n c e i t a p p e a r s u n l i k e l y t h a t
any d i r e c t s u b s t i t u t i o n o c c u rs ; th e a c t i o n p ro b a b ly o o n s is ts
m a i n l y i n th e a d d i t i o n o f h y p o c h l o r o u s a c i d t o u n s a t u r a t e d
compounds w ith th e f o r m a t i o n o f c h l o r h y d r i n s . "
The r e p o r t
d o e s n o t g i v e a n y m ore i n f o r m a t i o n c o n c e r n in g - t h e p r o d u c t o r
^ B e r g e r , H, G ., U n i t e d S t a t e s P a t e n t 2 . 0 4 5 . 8 2 4 . June
9 , 1 9 3 6 , t o Socony Vacumn O i l Company. C h e m ic a l A b s t r a c t s .
1 9 3 6 , No. 3 0 , Column 5 3 2 7 .
T%
B irc h , S. F . , " A p p lic a tio n of H y p o c h lo rite P r o c e s s ,"
O il a n d Gas J o u r n a l . V o l. 2 8 , May 2 3, 1 9 2 9 .
( T u l s a , Oklahoma:
P e tr o le u m P u b l i s h i n g Company, 1930) p . 174
o h l o r h y d r i n s fo rm e d b u t , b e c a u s e of t h e d e s c r i b e d r e a c t i o n ,
compounds o f t h e c h l o r h y d r i n c l a s s a r e p r o b a b l y f o rm e d i n
l a r g e q u a n t i t i e s when sodium h y p o c h l o r i t e i s a d d e d t o a c i d
slu d g e .
M o r r e l l , B a r r y , a n d L an g to n
T4
w r i t e of t h e v a l u e o f
c h l o r i n a t e d n a p h t h a l e n e s , "The m e l t i n g a n d b o i l i n g p o i n t s o f
c h l o r i n a t e d n a p h t h a l e n e s i n c r e a s e w i t h th e number o f c h l o r i n e
ato m s i n t h e m o le c u le and t h e m e l t i n g r a n g e of t h e c o m m e rc ia l
p r o d u c t s i s 6 0 ░ - 1 25░C .
They a r e im p e r v io u s t o m o i s t u r e a n d
do n o t b u r n . "
Carmody^-5 h a s p a t e n t e d t h e p r e p a r a t i o n o f a r e s i n w i t h
a c i d s lu d g e f r o m a n o t h e r s o u r c e , " a b r i g h t , g l o s s y , d a r k
brown r e s i n i s o b t a i n e d a s a r e s i d u e i n d i s t i l l i n g m i x t u r e s
o f a c i d s lu d g e a n d p u r e s t i l l
re sid u e s r e s u ltin g r e s p e c tiv e ly
fro m a c i d wash and f r a c t i o n a t i o n o f l i g h t o i l s p r o d u c e d i n
b y - p r o d u c t c o k in g o f c o a l , . . . . . "
H ass-^ i n d i r e c t l y p o in ts o u t th e la c k of in fo rm a tio n
l ^ M o r r e l l , R. A . , B a r r y , T. H e d le y , L a n g to n , H. M .,
S y n t h e t i c R e s in s and A l l i e d P l a s t i c s (London, E n g la n d :
O x fo rd U n i v e r s i t y P r e s s , 1 9 3 7 ) , p* 224
?^?^Carmody, W. H . , U n i t e d S t a t e s P a t e n t 2 . 1 4 9 . 2 7 5 . J u l y
3 , 1 9 3 9 . A b s t r a c t s . V o l. 2 5 , 19 3 9 , J o u r n a l o f I n s t i t u t e o f
P e tr o le u m T e c h n o l o g i s t s
( E d g b a s to n , B irm ingham , E n g la n d :
I n s t i t u t e o f P e t r o l e u m , 1939)
^ % a s s , H. B . , a n d o t h e r s , The C h l o r i n a t i o n o f M ethane
an d I t s H om ologues. D u n s ta n d , D r. A. E . , a n d o t h e r s , e d i t o r s ,
The S c i e n c e o f P e tr o le u m
(London, E n g la n d : O x fo rd U n i v e r s i t y
P r e s s , 1 9 3 8 ) , p p . 2 7 8 7 -93
10
on h i g h m o l e c u l a r w e i g h t c h l o r i n a t e d h y d r o c a r b o n s w h ich
c o u l d e a s i l y be p r o d u c e d i n m i x t u r e s from a c i d s l u d g e s from
d if fe re n t sou rces.
"The m e th a n e h om ologues h i g h e r t h a n th e
p e n t a n e s a r e d i f f i c u l t t o o b t a i n i n th e p u r e f o im a n d t h e i r
c h lo r in a tio n has been r e l a t i v e l y l i t t l e
s tu d ie d w ith th e
e x c e p t i o n o f a c o n s i d e r a b l e amount of work on p a r a f f i n w a x ."
W ith h i s d i s c u s s i o n on "The C h l o r i n a t i o n o f M ethane a n d I t s
H o m o lo g u e s," he i n c l u d e s a l o n g t a b l e o f d a t a on o h l o r o compounds w h ich c o n t a i n s v a l u a b l e i n f o r m a t i o n by w hich
d e f i n i t e c h lo ro -c o m p o u n d s ca n be com pared w i t h c h l o r i n a t e d
s lu d g e p r o d u c t s .
CHAPTER I I I
THE MATERIALS USED
I.
EQUIPMENT
No s p e c i a l e q u ip m e n t was n e c e s s a r y f o r t h e I n v e s t i g a н
tio n .
H ow ever, f o r a more e x t e n s i v e s t u d y , p l a s t i c p r e s s e s
an d p l a s t i c t e s t i n g a p p a r a t u s would a i d much i n o b t a i n i n g
v a l u a b l e d a t a on s y n t h e s i z e d p l a s t i c s .
A m e c h a n i c a l m ix e r
and some l a r g e o r d i n a r y e q u ip m e n t, two l i t e r
b eak ers,
la rg e
B u c h n er f u n n e l , a n d s e v e r a l two l i t e r g r a d u a t e d c y l i n d e r s
w ere u s e d d u i i n g much of t h e r e s e a r c h .
An a n a l y t i c a l b a l a n c e
a n d " m o l e c u l a r w e ig h t d e t e r m i n a t i o n " a p p a r a t u s w ere n e c e s s a r y
e q u ip m e n t.
A t h e r m o s t a t i c a l l y c o n t r o l l e d c o n s ta n t te m p e ra tu re
oven was a v a i l a b l e an d s e r v e d t o g r e a t a d v a n ta g e when t e s t i n g
th e s t a b i l i t y of v a r io u s p ro d u c ts .
II.
CHEMICALS
I n a d d i t i o n t o t h e u s u a l c h e m ic a ls f o u n d i n an
a n a l y t i c a l l a b o r a t o r y , th e o n ly c h e m ic a ls r e q u i r e d w ere a
l a r g e s u p p ly o f sodium h y p o c h l o r i t e a n d c h l o r i n a t e d l i m e .
P e tr o le u m s u l f u r i c a c i d s lu d g e w as s u p p l i e d by l o c a l o i l
r e f i n i n g c o m p a n ie s .^
^S ee ack no w led gm en t s h e e t
CHAPTER I T
SPECIAL METHODS OF ANALYSIS
F o r t h e d e t e r m i n a t i o n o f m o l e c u l a r w e i g h t s by t h e
f r e e z i n g an d b o i l i n g p o i n t m e th o d s , a o e to p h e n o n e and a c e t o n e
were u s e d r e s p e c t i v e l y a s s o l v e n t s e x c e p t f o r a few p a r t i н
c u l a r c a s e s when t h e h a l o g e n c o n t e n t o f th e m a t e r i a l was
o b v i o u s l y s m a ll a n d b en zen e was u s e d f o r a s o l v e n t .
For
c a l c u l a t i o n s 5 6 .5 d e g r e e s C e n t i g r a d e p e r 100 gram s o f
s o l v e n t was u s e d a s th e c r y o s c o p i c c o n s t a n t f o r a o e t o p h e n o n e ,1
a n d 2 2 .2 d e g r e e s C e n t i g r a d e p e r 100 c c , of s o l v e n t a t b o i l н
in g te m p e ra tu re as th e b o i l i n g p o in t c o n s ta n t f o r a c e t o n e , 2
an d 3 2 . 0 d e g r e e s C e n t i g r a d e p e r 100 c c . o f s o l v e n t a t t h e
b o ili n g p o in t f o r b e n z e n e .^
(In a l l c a se s th e av erag e
m o l e c u l a r w e ig h t o f e a c h p r o d u c t m s d e t e r m i n e d b e c a u s e th e
d e r i v a t i v e s t e s t e d w ere m i x t u r e s of com plex compounds
d e r i v e d from a c i d s l u d g e . )
To d e t e r m in e s u l f u r c o n t e n t , a d i g e s t i o n o f s a m p le s
w ith fu m in g n i t r i c a c i d a n d p o ta s s iu m c h l o r a t e was c a r r i e d
^W ashburn, Edward W . , e d i t o r , I n t e r n a t i o n a l C r i t i c a l
T ab le s
( P u b l i s h e d f o r t h e N a t i o n a l R e s e a r c h C o u n c il of t h e
U n ite d S t a t e s , T o l . 4 . New Y ork: M cG raw -H ill Book Company,
1 9 2 8 ) , p . 183
2Hodgman, C. D . , C h em ical T a b le s fro m th e Handbook of
C h e m is try and P h y s i c s
( C l e v e l a n d , O hio: C h e m ic a l R ubber
P u b l i s h i n g Company, 1 9 3 8 ) , p . 1043
%
Loc . c i t .
15
on.
When th e s o l u t i o n was c l e a r ,
t h e s u l f u r was p r e c i p i t a н
t e d i n th e form o f b a riu m s u l p h a t e .
A c a r b o n - h y d r o g e n c o n t e n t was d e t e r m in e d i n one
p a r t i c u l a r c a s e and th e m eth o d o f Cohen^ was f o l l o w e d .
T h is
p a r t i c u l a r m ethod m o d i f i e s th e r e g u l a r c o m b u s tio n m e th o d b y
th e u s e of f u s e d l e a d ohrom ate i n th e b u r n in g tu b e i n o r d e r
to a v o id e r r o r due to th e p re se n c e o f h alo g en s o r s u l f u r .
To d e t e r m in e th e p e r c e n t a g e of c h l o x i n e i n d a r k
p r o d u c t s th e s i l v e r - t h i o c y a n a t e ? f e r r i c alum m ethod was
used.
S m a ll s a m p le s ( 0 , 1 t o .0 5 g ram s) w ere d i g e s t e d i n
a c e t o n e a n d m e t a l l i c so dium was a d d e d s l o w l y .
th i s s p e c ia l m o d ific a tio n ,
F o llo w in g
th e m etho d a s e x p l a i n e d b y S c o t t 5
was c a r r i e d t o c o m p l e t i o n .
To t i t r a t e
t h e m i n e r a l a c i d p r e s e n t i n s lu d g e th e
m ethod em ployed b y th e U nion O i l Company o f C a l i f o r n i a was
a p p lie d .
T h is m ethod c a l l s f o r t h e u s e o f a s m a ll sam ple
t o w hich a s m a ll q u a n t i t y o f c a r b o n t e t r a c h l o r i d e i s a d d e d .
To t h i s s o l u t i o n a b o u t 50 c c . o f s a t u r a t e d c a l c i u m c h l o r i d e ,
n e u t r a l t o bro m o ph eno l b l u e , i s a d d e d an d t h e a c i d i s t i t r a t e d
t o th e b lu e e n d p o i n t o f t h e i n d i c a t o r w i t h a s t a n d a r d
4C ohen, J . B . , P r a c t i c a l O rg a n ic C h e m is try (London,
E n g la n d : M a c m illa n a n d Company,? 1 9 2 8 7 7 p . 15
^ S e o t t , W i l f r e d W,, S t a n d a r d M ethods of C hem ical
A n a l y s i s (New Y ork: D. Van N o s t r a n d , 1 9 3 5 ) , p . 149
p o t a s s i u m h y d r o x id e s o l u t i o n .
V i o l e n t s h a k in g m u st be
r e s o r t e d to d u rin g th e t i t r a t i o n .
Many m eth o d s f o r t h e a n a l y s i s of p e t r o l e u m a c i d
s lu d g e have b ee n s u g g e s t e d i n t h e w r i t i n g s o f v a r i o u s
e x p e r i m e n t e r s , b u t th e m eth od o f Holzman a n d S u k n aro w sk i,о
w h ich i d e n t i f i e s o n l y g ro u p s r a t h e r t h a n p a r t i c u l a r com pounds,
was f o u n d m o st s u i t a b l e .
h o l z m a n , E . a n d S u k n a r o w s k i, S t e f a n , " A n a l y s i s o f
A c id S lu d g e s fro m M i n e r a l O i l T r e a t m e n t s , " I n d u s t r i a l a n d ,
E n g i n e e r i n g C h e m is t r y ?A n a l y t i c a l E d i t i o n . 7 .;3 7 8 -3 8 0 , 1935
CHAPTER V
PREPARATION AND DESCRIPTION OF VARIOUS DERIVATIVES
B ecause o f t h e h i g h p e r c e n t a g e o f s u l p h o n i c a c i d s
p r e s e n t i n a c i d s l u d g e , some r e a c t i o n s s u g g e s t e d by Camming^
w ere a p p l i e d .
The a c i d s lu d g e u s e d f o r th e f o l l o w i n g t e s t s
c o n t a i n e d 81$ s u l f u r i c a c i d .
E x p e rim e n t 1^.
A sam ple o f s lu d g e was v i g o r o u s l y r e f l u x e d w i t h
g la c ia l a c e tic a c id .
The p r o c e s s fo rm e d a b r i g h t p u r p l e -
c o l o r e d v i s c o u s s o l u t i o n w h ich d e f i e d a l l a t t e m p t s t o g i v e
u p t h e p u r p l e com ponent b y s e l e c t i v e s o l u b i l i t y .
E v id e n tly
t h e dye o r p u r p l e c o n s t i t u e n t was v e r y s u s c e p t i b l e t o
h y d r o l y s i s b e c a u s e t h e a d d i t i o n o f a s m a ll q u a n t i t y o f
w a te r d e s tro y e d th e c o lo r .
E t h y l a l c o h o l , a c e t o n e , an d
e t h y l e t h e r a l s o d e s t r o y e d t h e c o l o r w hich i n d i c a t e d t h e
im p o s s ib il ity of u sin g th e s e s o lv e n ts f o r e x t r a c t i o n p u rн
poses.
A d d itio n a l a c e t i c a c i d m e re ly a c te d a s a d i l u e n t
w h ile c a r b o n t e t r a c h l o r i d e a n d k e r o s e n e w ere v e r y l i g h t l y
t i n t e d by a g i t a t i o n w i t h th e s o l u t i o n .
E th y l a c e ta te
seem ed t o p o s s e s s t h e g r e a t e s t po w er o f s e l e c t i v e s o l u b i l н
i t y and t u r n e d i n t e n s e l y c o l o r e d when a g i t a t e d w ith a s m a ll
q u a n tity of th e p ro d u c t.
A tte m p ts t o r e c o v e r th e p u r p l e
^"Gumming, W i llia m , S y s t e m a t i c O rg a n ic C h e m is tr y
(New Y ork: D. Van N o s t r a n d , 1 9 3 1 ) , p. 324
m a t e r i a l from th e e t h y l a c e t a t e f a i l e d .
Expe r i m e n t 2^.
A q u a n t i t y of s l u d g e was t r e a t e d w i t h sodium
n i t r a t e u n t i l no more h e a t was g e n e r a t e d .
The am ount o f
s a l t r e q u i r e d was a p p r o x i m a t e l y t h e b a s i c e q u i v a l e n t of t h e
a c id p re se n t.
A s o l i d m a t e r i a l was fo rm e d w h ich was r e a d i l y
rem oved by f i l t r a t i o n a n d d r i e d ,
Q u a l i t a t i v e t e s t s proved
t h a t t h e pow dered p r o d u c t , l i g h t brown i n c o l o r , c o n s i s t e d
o f o rg a n ic n i t r a t e s .
B oth s t r o n g p o ta s s iu m h y d r o x id e s o l u н
t i o n an d e t h y l a l c o h o l a c t e d a s good s o l v e n t s f o r th e unknown
m a t e r i a l , b u t t h e p r o d u c t w o uld n o t u n d e r g o c r y s t a l l i z a t i o n .
A s m a l l sam ple was e n c l o s e d i n t i n f o i l a n d s u b j e c t e d t o a
v i o l e n t blow b u t i t d i d n o t e x h i b i t t h e e x p l o s i v e p r o p e r t y
c h a r a c t e r i s t i c o f some o t h e r n i t r a t e d o r g a n i c com pounds.
E x p e rim e n t 3 ,
N i t r i c a c i d was s l o w l y a d d e d t o f i f t y gram s o f
a c id slu d g e .
The r e a c t i o n was e x c e e d i n g l y v i o l e n t , an d
b e c a u s e o f t h i s t h e v e s s e l was e n c l o s e d i n p a c k e d i c e .
The
p r o d u c t fo rm e d was r e c o v e r e d a s i n E x p e r im e n t 1 , b u t i t s
c o l o r was more of a g o ld e n brown..
T h is p r o d u c t a p p e a r e d
e x c e e d i n g l y s t a b l e when s u b m i t t e d t o num erous t e s t s c h a r a c t e r н
is tic
o f " n i t r o " com pounds.
E x p e rim e n t 4 .
A l l a t t e m p t s t o e f f e c t n i t r a t i o n b y th e u s e of
th e n i t r a t e s o f ca d iu m , z i n c , i r o n , c o p p e r , c o b a l t , m agnesium ,
17
an d m an g an ese gave v i o l e n t r e a c t i o n s r e q u i r i n g c o o l i n g .
T h is c a n be e x p l a i n e d by t h e f a c t t h a t , u n l i k e t h e sodium s a l t ,
t h e s e compounds c o n t a i n fro m two t o s i x m o l e c u l e s o f w a t e r o f
c r y s t a l l i z a t i o n w h ich a c t u a l l y c a u s e t h e e q u i v a l e n t of a
la rg e h e a t of d ilu tio n .
As f a r a s c o u l d be d e t e r m in e d , t h e
p r o d u c t fo rm e d i n e a c h c a s e c o r r e s p o n d e d t o t h o s e fa rm e d i n
E x p e r im e n ts 1 a n d 3 ,
B e ca u se of t h e h i g h c o s t of f i x e d n i t r o g e n and t h e
v i o l e n c e of th e r e a c t i o n s o f p r a c t i c a l l y a l l f i x e d n i t r o g e n
compounds w i t h a c i d s lu d g e , i t a p p e a r e d w is e t o a t t e m p t
o t h e r r e a c t i o n s w h ich m ig h t b e more e a s i l y b r o u g h t a b o u t
on a c o m m e rc ia l s c a l e .
T h i s was a l s o s u g g e s t e d on a c c o u n t
o f t h e g r e a t s t a b i l i t y o f th e n i t r a t e d p r o d u c t .
E x p e r im e n t j5.
An e x c e s s o f c o n c e n t r a t e d sodium c h l o r i d e
s o l u t i o n was a d d e d t o a q u a n t i t y o f a c i d s lu d g e a n d a
h e a v y b l a c k r e s i d u e was r e c o v e r e d b y f i l t r a t i o n .
A ll
a t t e m p t s t o u s e th e r e s i d u e f o r t h e p r o d u c t i o n o f p l a s t i c н
lik e n a te ria ls fa ile d .
The r e s i d u e , when d r i e d , a p p e a r e d
v e r y carb o n aceo u s and u n r e a c t i v e .
E x p e r im e n t 6>.
To t e s t t h e s u s c e p t i b i l i t y o f a c i d s l u d g e t o
f r e e h a l o g e n s , a E50 gram sam ple was s l o w l y d i s t i l l e d w h ile
c h l o r i n e g a s was b u b b le d th r o u g h t h e h e a t e d m s s .
Much
c h l o r i n e g a s p a s s e d o v e r b u t d e f i n i t e t r a c e s of b e n z y l
18
c h l o r i d e were d e t e c t e d .
P u n g e n t f u m e s , which, c a u s e d th e
e y e s t o w a t e r an d w h ich s m e l l e d e x a c t l y l i k e t h e b e n z y l
compound, w ere so p l e n t i f u l t h a t e x t r a c a u t i o n h a d t o be
ta k e n .
A tte m p ts to i d e n t i f y t r a c e s o f m a t e r i a l s c o r r e s p o n d н
in g to c h lo ro fo rm o r ca rb o n t e t r a c h l o r i d e f a i l e d .
E x p e rim e n t 7 .
F i f t y gram s o f d r y sodium c h l o r i d e w ere a d d e d
to f i f t y gram s o f a c i d s lu d g e and t h e m a t e r i a l was h e a t e d
i n a gas g e n e r a to r .
G r e a t v o lu m e s o f h y d r o g e n c h l o r i d e
g a s w ere p ro d u c e d a n d no t r a c e o f o r g a n i c compounds c o u l d
be d e t e c t e d i n t h e " o v e r - h e a d . "
E x p e r im e n t 8 .
S u s p e c t i n g the p o s s i b i l i t y o f f o r m i n g c a r b o n
d i s u l f i d e w i t h a c i d s l u d g e , a q u a n t i t y of t h e w a ste m a t e r н
i a l m s a d d e d to s u l f u r .
C h l o r i n e was p a s s e d i n t o t h e r e t o r t
w h i l e t h e m i x t u r e was h e a t e d , and a few gram s o f i o d i n e w ere
added f o r c a t a l y t i c p u rp o se s.
I f a n y c a r b o n d i s u l f i d e w as
f o rm e d , th e o b j e c t was to h a v e i t r e a c t w i t h f r e e c h l o r i n e
i n t h e p r e s e n c e o f t h e i o d i n e c a t a l y s t t o p ro d u c e c a rb o n
te tra c h lo rid e .-
No t r a c e s o f th e c a rb o n t e t r a c h l o r i d e c o u ld
be d e te c te d in th e d i s t i l l a t e , b u t t e s t s i n d i c a t e d th e
p r e s e n c e o f a good y i e l d of s u l f u r m o n o c h l o r i d e .
E x p e r im e n t j3.
S u l f u r an d a c i d s l u d g e s were r e f l u x e d t o g e t h e r
f o r one h o u r w ith th e hope o f fo rm in g a c h e a p , i n t e r e s t i n g
19
p r o d u c t b u t no d e f i n i t e r e a c t i o n a p p e a r e d to t a k e p l a c e .
A f t e r t h e m a t e r i a l was c o o l t h e f r e e
s u l f u r , i n th e p l a s t i c
a l l o t r o p i c f o r m , c o u ld be r e c o v e r e d b y w a t e r w a s h in g .
E x p e r im e n t 1 0 .
One h u n d r e d gram s o f a c i d s lu d g e were n e u t r a l i z e d
w ith m ilk of lim e .
The p r e c i p i t a t e was e x c e e d i n g l y w h i t e
a n d c o n t a i n e d lim e o r g a n i c s a l t s i n a d d i t i o n t o q u a n t i t i e s
o f c a lc i u m s u l f a t e .
By f i l t r a t i o n , when t h e m i x t u r e was h o t ,
s m a l l q u a n t i t i e s o f c a lc i u m s a l t s o f s u l p h o n i c a c i d s c o u l d
be r e c o v e r e d ; b u t g e n e r a l o b s e r v a t i o n l e d t o th e c o n c l u s i o n
t h a t no com m ercial p r o c e s s c o u ld r e s u l t fro m su c h a n i n н
e f f i c i e n t means f o r s e p a r a t i o n .
Expe r im e n t 1 1 .
C h l o r i d e o f lim e was n e x t a d d e d t o a l a r g e
sample o f s lu d g e a n d t h e p r e c i p i t a t e was i n t e n s e l y y e l l o w .
The y e l l o w c o m p o n e n t, w hich l a t e r p r o v e d t o be a l k y l h a l i d e s ,
was r e a d i l y s o l u b l e i n h o t a l c o h o l .
By means o f s o x h l e t
e x t r a c t i o n t h e o r g a n i c h a l i d e s w ere r e c o v e r e d , a n d d u r i n g
t h e p r o c e s s t h e y c o a g u l a t e d i n t h e h o t a l c o h o l a n d form ed
s o f t brown d r o p l e t s w i t h a h i g h s p e c i f i c g r a v i t y .
On
re m o v a l fro m th e h o t a l c o h o l , t h e s e d r o p l e t s w ou ld c o n g e a l
t o form h a r d b r i t t l e m a s s e s o f o r g a n i c h a l i d e s .
E x p e rim e n t 1 3 .
To e l i m i n a t e th e n e e d f o r e x t r a c t i o n i n E x p e r i н
m ent 1 1 , a q u a n t i t y of a c i d s lu d g e was n e u t r a l i z e d w i t h
sodium h y p o c h l o r i t e , an d a f t e r s t a n d i n g t w e n t y - f o u r h o u r s
g r e a t q u a n t i t i e s of y e l lo w o r g a n i c h a l i d e s w ere d e p o s i t e d .
T h ese c o u ld r e a d i l y be r e c o v e r e d by f i l t r a t i o n * a n d when
d r y t h e p r o d u c t seemed so i n t e r e s t i n g t h a t an e x t e n s i v e
s t u d y o f t h e m a t e r i a l was m ade.
C h a p t e r s i x d i s c u s s e s th e p r o p e r t i e s o f t h e p r o d u c t s
fo rm e d from v a r i o u s s l u d g e s by t h i s m e th o d .
The e c o n o m ic s
f o r c o m m ercia l a p p l i c a t i o n an d v a r i o u s m o d i f i c a t i o n s u s e d
f o r p r e p a r i n g t h e p r o d u c t a r e a l s o c o n s id e r e d *
CHAPTER VI
T h is c h a p t e r c o n t a i n s a s t u d y o f t h e " O h lo ro "
d e r i v a t i v e fro m a g i v e n p e t r o le u m a c i d s l u d g e a n d i n c l u d e s
a c o m p a ris o n o f t h e c h l o r i n a t e d m a t e r i a l s fro m v a r i o u s
s a m p le s o f s l u d g e ,
I.
PREPARATION AND STUDY <F THE "CHLORO" DERIVATIVE
P re p a ra tio n
To 1000 gram s o f 8 1 $ a l k y l a t e a c i d s lu d g e
w h ich h a d b e e n u s e d f o r g a s o l i n e t r e a t i n g , 1500 gram s o f
d i s t i l l e d w a t e r c o n t a i n i n g 200 grams o f d i s s o l v e d sodium
c h l o r i d e w ere s l o w l y a d d e d .
The m i x t u r e was a l l o w e d t o
s t a n d s e v e r a l h o u r s a f t e r w h ic h tim e a muddy b r o w n - b la c k
p r e c i p i t a t e was f i l t e r e d o f f w ith t h e a i d o f a B u c h n er
fu n n e l,
W ith o u t w a s h in g o r d r y i n g t h e p r e c i p i t a t e , t h e
e n t i r e y i e l d was p l a c e d i n a tw o l i t e r b e a k e r a n d 1000 c c ,
o f 1 6 $ sodium h y p o c h l o r i t e was a d d e d .
The r e a c t i o n was
v i o l e n t due t o t h e p r e s e n c e o f a c i d b u t th e above q u a n t i t y
o f NaGlO r e p r e s e n t e d a n e x c e s s , and t h e r e f o r e some re m a in e d
u n re a c te d upon.
The ab o v e m i x t u r e was a l l o w e d t o s t a n d
t w e n t y - f o u r h o u r s a f te r* - s to ic h p e r i o d of t i m e t h e t a n
p r e c i p i t a t e , w hich h a d s e t t l e d t o th e b o tto m , was f i l t e r e d
o f f w ith a B u chn er f u n n e l a n d w ashed s e v e r a l t i m e s w i t h
d i s t i l l e d w a te r.
a p p r o x i m a t e l y 10$#
The p r o d u c t was t h e n d r i e d .
See F i g u r e I .
Y ie ld ?
IX .7 .iClZ) CTPIHGTH
. -J
s c d i u i .: h
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23
C ost of P re p a r a tio n
A ci d S l u d g e . . . . . . . . . . .
R e g a rd e d n i l
Sodium c h l o r i d e . . . . . . .
0.010
Sodium h y p o c h l o r i t e . . .
0 .0 7 - 2 5 0 p e r g a l l o n
T o ta l. . .
0 ,0 8 г p e r 100 gram s
o r 350 p e r pound
A s s a y of M a t e r i a l
P h y sic a l P r o p e r tie s
C o l o r Tan
Odor M usty
S p e c if ic G ra v ity 1 .0 p lu s
D ry am orphous pow der
C ry sta lliz a tio n te s ts fa ile d
N ot T h e r m o p l a s t i c (Decomposes when h e a t e d )
Not T h e r m o s e t t i n g (
?
w
" j
2 . 0 $ l o s s of w e i g h t on s t a n d i n g a t 1 0 0 ░F .
f o r two w eeks
T ery g r a d u a lly darkens w ith t r a c e s o f
c h lo r in e h ein g l o s t
M o l e c u l a r w e ig h t ? w i t h a c e to p h e n o n e
- - w i t h a c e to n e
345
330
322
S u l f u r on f i n i s h e d m a t e r i a l
A v erag e 2^00$
S u l f u r r e c o v e r e d fro m w a t e r a f t e r f i v e
gram s o f m a t e r i a l s t o o d i n c o l d
w a te r tw e n ty -fo u r h o u rs
0 .0 5 $
In so lu b le fix e d s u lfu r
C h lo rin e on f i n i s h e d m a te r ia l
H alo g e n c o n t e n t l o s t by 5 gram s
sta n d in g in w a te r
R e sid u a l f ix e d c h lo r in e
1 .9 5 $
23$
.$
1 0
22$
C a rb o n -H y d rc g e n r a t i o ;
b y c o m b u s tio n .
F u s e d l e a d ch ro m a te was u s e d i n c o m b u s tio n
t u b e b e c a u s e of th e h a l o g e n an d s u l f u r c o n t e n t ;
C a rb o n ..................... ..
7 3 .3 $
H y d ro g en .
...................................... T ra o e
24
Summary o f I n d i o a t e d R e s u l t s
A v erag e m o l e c u l a r w e i g h t
352
C h lo rin e
2 2 .0 $
S u lfu r
1 .9 5 $
C arbon
7 3 .3 $
H y d ro g en
T ra c e
Oxygen
By d i f f e r e n c e 2 .7 5 $
The r e s i s t a n c e to s o l v e n t s o f t h e c h l o r o d e r i v a t i v e
a p p e a r s t o be a v a l u a b l e p r o p e r t y of th e p r o d u c t .
T h erefo re,
i n T a b le 1 a c o m p le te l i s t o f t h e e f f e c t s o f v a r i o u s s o l н
v e n ts i s d e s c rib e d .
A s o l v e n t d e r i v e d fro m a h a l o g e n seem s t o y i e l d
p a r t i a l s o l u b i l i t y w h ile a s o lv e n t c o n ta in in g a c a rb o n y l
g ro u p seem s t o y i e l d t o t a l s o l u b i l i t y i n many e a s e s .
C hem ioal N a tu r e and R e a c t i o n s
An i m p o r t a n t r e a c t i o n o f c h l o r o d e r i v a t i v e s
s u g g e s t e d by E l l i s ^ - i s
KX + NlgSOg ?^
RNaSOg-+? NaX
( S tr e c k e r R e a c tio n )
T h i s r e a c t i o n w as t r i e d f o r th e p o s s i b l e s y n t h e s i s
o f a h ig h m o l e c u l a r w e ig h t s a l t w i t h a h i g h d e g r e e o f
s o l u b i l i t y an d a l a t h e r i n g c h a r a c t e r i s t i c .
F i f t y grams o f sodium s u l f i t e i n 100 grams o f w a t e r
was r e f l u x e d f o r t w e n t y - f o u r h o u r s i n c o n t a c t w i t h f i v e gram s
o f th e unknown c h l o r i d e ,
^ E l l i s , C a r l e t o n , C h e m is tr y o f P e tr o le u m D e r i v a t i v e s
V o l. 2 (New Y ork: R e i n h o l d t P u b l i s h i n g Company, 1 9 3 7 ) , p .8 0 4
TABLE I
SOHTBILITY OF THE CHLORINATED RESIDUE FROM PETROLEUM ACID SLUDGE
A.
INACTIVE SOLVENTS
1 . B e n z a ld e h y d e
8 . F o rm ald eh y d e
2 . C arbon B i s u l p h i d e
9. G ly c e rin e
3 . Camphor
(M e lte d )
(C o ld )
1 0 . P e tr o le u m E t h e r
4 . 1 - 4 D iox ane
1 1 . T u r p e n t i n e ( P in e n e )
5. E th y l E th e r
1 2 . T o lu en e
6. E th y l A c e ta te
13.
7 . E t h y l A lc o h o l
B.
(C o ld )
U rea
(W ater S o l u t i o n )
1 4 . X ylene
PARTIALLY OR SLIGHTLY ACTIVE SOLVENTS
1 . A o p ty l c h l o r i d e
5 . E t h y l A lc o h o l (H ot)
2 . Benzoyl c h l o r id e
6 . E th y le n e d i c h l o r i d e
3 . C arbon t e t r a c h l o r i d e
7 . M e s i t y l o x id e
4 . C h lo ro f o rm
8 . T in c tu re b e n z o in
C.
GOOD SOLVENTS
1 . A c e to n e
3 . B enzophenone
2 . A c e to p h e n o n e
4 . U re a
D.
(M e lte d )
REACTING SOLVENTS
1 . G ly c e rin e
(H ot) P o l y m e r i z e s . H ow ever, t h e
r e s i n fo rm e d h a s a s t r o n g a f f i n i t y f o r
w a t e r a n d a f t e r s e v e r a l h o u r s becom es v e r y
w e t.
2 . A n i l i n e - A d a r k brown o i l y m ass i s form ed*
T h e re i s an a p p a r e n t r e a c t i o n b e tw e e n t h e
c h l o r o p r o d u c t a n d a l l a m in e s .
3 . C o n c e n tra te d s u l f u r i c and n i t r i c a c id s a t t a c k
th e " c h lo ro ? d e r i v a t i v e s .
26
R e s u l t ? The s o l u t i o n was f i l t e r e d an d the f i l t r a t e
c o n t a i n e d o n l y a s m a ll q u a n t i t y of t h e unknown compound.
More th a n f o u r gram s re m a in e d u n co m bined an d u n d i s s o l v e d .
The f i l t r a t e
h a d a g oo d te n d e n c y t o foam w i t h a l i t t l e
a g i t a t i o n w h ic h i n d i c a t e s t h a t th e S t r e c k e r r e a c t i o n d id
ta k e p l a c e t o some e x t e n t .
Lowy an d H a r r o w ^ a n d D e g e r in g 3 d e s c r i b e t h e f o l l o w н
in g r e a c t i o n of o rg a n ic h a l i d e s :
2RX *t? KgS
----^
RSR +
2KK
S u l f i d e s and d i s u l f i d e s a r e p r e p a r e d by t h i s m e th o d .
Some of t h e unknown h a l o g e n compound m i x t u r e was r e f l u x a d
w i t h a s t r o n g s o l u t i o n o f p o ta s s iu m s u l f i d e .
R e s u l t ?? A d a r k o i l y m a t e r i a l
( p o s s ib ly h ig h
m o l e c u l a r w e ig h t t h i o e t h e r s ) was f o r m e d , b u t i t was n o t
e t h e r s o l u b l e w h ich m akes th e c o n c l u s i o n t h a t i t was t h i o н
e t h e r s o n ly p r o b l e m a t i c a l .
The w e l l known " G r i g n a r d ? s R e a c t i o n " d e s c r i b e d by
P o r t e r ^ was n e x t a t t e m p t e d .
The unknown compounded o r g a n i c
2Lowy, A le x a n d e r and H arro w , B e n ja m in , I n t r o d u c t i o n
t o O rg a n !c C h e m is tr y (New Y ork: Jo hn W iley & S o n s , 1928)
p . 194
3 D e g e r in g , E . F . f and o t h e r s , An O u t l i n e of O rg a n ic
C h e m is tr y
(New Y ork: B a rn e s an d N o b l e , 1 9 3 9 ) , p . 126
^ P o r t e r , G, W ., The C arbo n Compounds (New Y ork;
Ginn and Company, 1 9 5 1 ) , p . 75
27
h a l o g e n m i x t u r e was e t h e r i n s o l u b l e a n d a l l a t t e m p t s t o make
a n e t h e r s u s p e n d e d m i x t u r e r e a c t w i t h z i n c o r m agnesium
i
fa ile d .
A c e to n e , f o r a s o l v e n t , was t h o r o u g h l y d r i e d a n d
seemed t o b r i n g a b o u t a r e a c t i o n w i t h m e t a l l i c z in c *
H ow ever, G r i g n a r d r e a g e n t r e a c t s w i t h a k e t o n e to y i e l d a
t e r t i a r y a l c o h o l , 5 a n d , s i n c e p r e c i p i t a t i o n g r a d u a l l y to o k
p l a o e , e v i d e n t l y G r i g n a r d * s r e a g e n t was b e i n g f o r m e d a n d
i n s t a n t a n e o u s l y r e a c t e d w i t h some of t h e s o l v e n t t o fo rm
a n i n s o l u b l e h i g h m o l e c u l a r w e ig h t t e r t i a r y a l c o h o l ,
E l l i s 6 g i v e s t h e f o l l o w i n g sam ple e q u a t i o n s f o r
c o n d e n s a t i o n s and t h e p r o d u c t i o n
of o l e f i n s :
C .C .X .+ A lc KOH
RX+ H2 O + C:C
X .C .C .X + 2Na
0 :0 - 1 ' 2NaCL
HX+ RX + 2Na
? P? R:R + 2NaX
(W urtz)
The r e a c t i o n w i t h a l c o h o l i c KOH when a p p l i e d t o th e
p r e p a r e d o r g a n i c h a l i d e m i x t u r e y i e l d e d a d a r k b r o w n is h
?p re c ip ita te .
T h is was a pow der when d r y , a n d when t e s t e d
by h a l o g e n a b s o r p t i o n showed no u n s a t u r a t i o n .
The r e a c t i o n wl t h sodium t o a f f e c t Wurtz* o r
F i t t i g ? s c o n d e n s a t i o n w as d i f f i c u l t t o b r i n g a b o u t b e c a u s e
5I b i d . , p . 75
^ Illis,
o n . o i t . T p , 804
o f t h e i n s o l u b i l i t y o f th e m a t e r i a l i n s u l f u r i c e t h e r .
When d r y a o e to p h e n o n e w as em plo yed a s a s o l v e n t i t was
p o s s i b l e t o p r o d u c e a b l a c k s l u d g e - l i k e m a ss w hich h a r d e n
ed and became b r i t t l e
when d r y .
T h is m a t e r i a l e x h i b i t e d
some of th e p h y s i c a l c h a r a c t e r i s t i c s o f common a s p h a l t .
S i l v e r a c e t a t e s o l u t i o n r e a c t e d v e r y r e a d i l y w ith
an a c e t o n e s o l u t i o n o f th e h a l i d e t o y i e l d w h i t e s i l v e r
c h l o r i d e a n d a c a n p l e x i n s o l u b l e brown compound m i x t u r e .
Ammonia g a s was b u b b le d t h r o u g h a n a c e t o n e s o l u t i o n
o f t h e unknown h a l o g e n compound m i x t u r e .
urn c h l o r i d e w ere fo rm e d ; b u t ,
T r a c e s o f ammoni
g e n e r a l l y s p e a k i n g , th e
s o l u t i o n re m a in e d p r a c t i c a l l y u n c h a n g e d a s f a r a s c o u l d be
d e te rm in e d .
The m e th o d o f r e d u c t i on o f D e g e r in g 7 an d F i s h e r 8
was n e x t a p p l i e d .
F i r s t a c t i v a t e d h y d r e g e n was em ployed
as a re d u c in g a g e n t.
The p u r p o s e of t h i s e x p e r i m e n t was
to produce a pure h y d ro c a rb o n .
To a c c o m p l i s h t h i s , z i n o
d u s t was s u s p e n d e d i n a weak c o p p e r s u l f a t e s o l u t i o n
g i v i n g a Cu-Zn c o u p le ^ h ic h c a u s e d a c t i v a t e d h y d ro g e n t o
7D e g e r in g , o p . o i t . , p . 38
% i s h e r , H a r ry L . , l a b o r a t o r y M anual of O rg a n ic
C h e m is tr y
(New Y ork: Jo h n W iley a n d S o n s, 1 9 3 1 J , p . 53
be l i b e r a t e d .
Some o f t h e unknown m a t e r i a l was k e p t i n
c o n t a c t w i t h a co u p le of t h i s d e s c r i p t i o n .
The y i e l d o f
b e n z e n e a n d c a rb o n t e t r a c h l o r i d e s o l u b l e m a t e r i a l was s m a ll
(about
20
% ), b u t th e h a l o g e n c o n t e n t of t h i s r e c o v e r e d r e н
d u ced m a t e r i a l w as p r a c t i c a l l y n i l .
A s e c o n d m etho d o f r e d u c t i o n e x p l a i n e d by D e g e r in g 9
was t r i e d .
Some of t h e n a t e r i a l was r e f l u x e d w i t h h y d r i o d i c
a c id and r e d p h o sp h o ro u s.
The r e s u l t s i n t h i s p a r t i c u l a r
c a s e w ere a b o u t i d e n t i c a l w i t h t h o s e o b t a i n e d b y e m p lo y in g
th e c o u p le.
The y i e l d cf t h e h a l o g e n f r e e s o l u b l e m a t e r i a l
was a p p r o x i m a t e l y t w e n t y - f i v e p e r c e n t f o r t h i s m etho d o f
red u e t i o n .
Some o r g a n i c h a l i d e s a r e s u s c e p t i b e t o m e t a t h e s i s
a c c o r d i n g t o E l l i s * о , an d f o r t h i s r e a s o n t e n gram s o f t h e
m a t e r i a l was r e f l u x e d w i t h a s t r o n g s o l u t i o n o f sodium
o le a te
(a lc o h o l 7 0 $ ).
The a c t i o n w hich to o k p l a c e r e s e m b le d
t h a t o f th e m a t e r i a l when i t was p l a c e d i n b o i l i n g a l c o h o l .
As f a r a s c o u l d be d e t e r m in e d , no m e t a t h e s i s t o o k p l a c e b u t
a c o a g u l a t e d m ass was f o r m e d .
9I b i d . . p . 38
1C* E l l i s , o p . o i t . , p . 822
30
A s m a ll q u a n t i t y of some of t h e unknown m a t e r i a l was
p l a c e d i n a bomb
wi
th ammonium h y d r o x id e a n d p r e s s u r e
a p p l i e d by h e a t i n g t h e bomb s e v e r a l h u n d r e d d e g r e e s .
A c c o rd н
i n g to E l l i s 1--*-, am in es may b e p r o d u c e d by t h i s m eth o d b u t no
t r a c e s o f f i x e d o r g a n i c n i t r o g e n c o u l d b e d e t e c t e d by t h e
u s u a l o r g a n i c q u a l i t a t i v e t e s t d e s c r i b e d by Kamm.1-2
A n i l i n e seem ed t o d i s s o l v e o r r e a c t w ith a g r e a t
p e r c e n t a g e o f t h e compound m i x t u r e .
B e d i s t i l l a t i o n of th e
a n i l i n e y i e l d e d e i g h t e e n p e r c e n t o f a d a r k brown com ponent
o v e r a w ide t e m p e r a t u r e r a n g e ab o v e t h e b o i l i n g p o i n t o f
pure a n i l i n e .
To b e c o n s i s t e n t w i t h t h e s t a t e m e n t o f
D e g e r i n g l S , i t i s l o g i c a l t o c o n c lu d e t h a t h ig h m o l e c u l a r '
w e ig h t a d d i t i o n p r o d u c t s w ere f o r m e d .
A tte m p ts w ere made t o d r y d i s t i l l some o f t h e
compound m i x t u r e w ith z i n c d u s t .
A c c o r d in g t o D e g e rin g ^ 4
t h i s s h o u l d p r e v e n t th e f o r m a t i o n o f HC1 w ith a s u b s e q u e n t
y i e l d o f z i n c c h l o r i d e and u n s a t u r a t e d h y d r o c a r b o n .
13-I b i d . . p , 804
Y ork:
^Kamm, O l i v e r , Q u a l i t a t i v e O rg a n ic A n a l y s i s
Jo h n W iley and S o n s , 1931) p . 1г3
13
D e g e r in g , o p . b i t . , p . 37
14L o c . c i t .
(New
R e s u l t ?? C h a r r i n g w ith a g r e a t i n c r e a s e i n v o lu m e ,
and t h e c h a r r e d m a t e r i a l seem ed t o p o s s e s s no h a l o g e n
a b s o r p t i o n po w er.
D e g e r in g ^ 5 e x p l a i n s th e p r e p a r a t i o n o f e t h e r s a n d
i s o c y a n i d e s by m e t a t h e s i s o f h a l o g e n compounds w i t h sodium
a l c o h o l a t e an d sodium c y a n i d e .
When u s i n g th e p e t r o le u m
c h l o r o d e r i v a t i v e a s a s u b s t i t u t e f o r th e h a l o g e n compound,
t h e s e r e a c t i o n s f a i l e d to y i e l d a s u f f i c i e n t q u a n t i t y o f
a n y p r o d u c t t h a t c o u l d be i s o l a t e d b y f r a c t i o n a t i o n o r
fra c tio n a l c ry s ta lliz a tio n .
The C ohen^6 m eth o d o f " F r i e d e l a n d C r a f t " r e a c t i o n
e m p lo y in g ALClg a s a c a t a l y s t was a p p l i e d t o c a u s e a
r e a c t i o n b e tw e e n t h e p o ly h a lo g e n compound m i x t u r e a n d
a.
b.
c.
d.
e.
A n ilin e
B enzene
A c e to p h e n o n e
B enzophenone
P y rid in e
I n a l l c a s e s some r e a c t i o n o b v i o u s l y to o k p l a c e w i t h t h e
l i b e r a t i o n o f h y d ro g e n c h l o r i d e , b u t i n t h e c a s e s o f a . ,
e . , a n d d . t h e r e a c t i o n was p a r t i c u l a r l y v i o l e n t .
h y d r o g e n c h l o r i d e i s a n e c e s s a r y p r o d u c t cf
15
1 fi
I b i d . . p . 38
Cohen, o p . cijfc. , IV, p p . 2 6 2 -2 6 4
S in c e
th e . " F r i e d e l a n d
52
C r a f t " r e a c t i o n , i t i s l o g i c a l to c o n c lu d e t h a t t h i s r e н
a c t i o n d i d ta k e p l a c e t o v a r y i n g d e g r e e s i n a l l f i v e c a s e s .
A f t e r c a r r y i n g t h e m ethod th r o u g h i n t h e c u s to m a r y m anner
f o r e a c h s o l v e n t , i n no c a s e was i t p o s s i b l e t o r e c o v e r a
r e p r e s e n t a t i v e q u a n t i t y o f a compound fro m th e y i e l d e d
m ix tu re .
F r a c t i o n a l c r y s t a l l i z a t i o n , f r a c t i o n a t i o n , and
s e l e c t i v e s o l u b i l i t y w ere a l l t r i e d i n a tte m p tin g t o i s o l a t e
a co m p o n en t.
C a t a y t i o V a lu e
A t t e m p t s w ere made t o em ploy some o f t h i s m a t e r i a l
a s a h a l o g e n c a r r i e r o r s u b s t i t u t e f o r alum inum c h l o r i d e
b u t no e v i d e n c e was s e c u r e d t o s u b s t a n t i a t e i t s w o r t h i n
th is re sp e c t.
The d r y in g s p e e d o f d r y in g o i l s was n o t i n c r e a s e d
by a s u s p e n s i o n o f a s m a l l q u a n t i t y o f t h e o r g a n i c h a l i d e .
As e x p l a i n e d a b o v e , g l y c e r i n e when b o i l e d w i t h a
s m a ll p e r c e n t a g e o f th e m a t e r i a l showed d e f i n i t e i n d i c a t i o n s
of p o ly m e riz a tio n ,
When s m a ll q u a n t i t i e s o f t h e h a l o g e n compound m ix н
t u r e w ere p u t on m o i s t dyed c l o t h s no t r a c e s o f b l e a c h i n g
w ere d e t e c t e d i n an y c a s e .
T h is i n d i c a t e d t h a t t h e l i b e r a н
t i o n o f f r e e c h l o r i n e due t o i n s t a b i l i t y w as v e r y s m a l l .
33
The Q h l o r i n a t i o n of S lu d g e s fro m D i f f e r e n t O r i g i n s
A s e c o n d a r y p ro b le m o r i g i n a t i n g from t h e p r o d u c t i o n
o f o r g a n i c h a l i d e s fro m p e t r o le u m a c i d s l u d g e i s
th e wide
v a r i a t i o n o f r e s u l t i n g p r o d u c t s due t o th e u s e o f d i f f e r e n t
s l u d g e s p r o d u c e d by v a r i o u s r e f i n e r y p r a c t i c e s .
The r e s u l t s o b t a i n e d b y s y n t h e s i z i n g p r o d u c t s fro m
v a r i o u s s l u d g e s i n d i c a t e t h a t t o p ro d u c e a p l a s t i c m a t e r i a l
w ith d e f i n i t e c h a r a c t e r i s t i c s an a c id slu d g e o f a d e f i n i t e
q u a lity is re q u ire d .
T h is n a t u r a l l y c a l l s f o r a r e f i n e r y c o n t r o l o f t h e
q u a l i t y of a c i d s l u d g e s w h ich i n t r o d u c e s e x p e n s e , and t h e r e н
by i n d i r e c t l y i n c r e a s e s t h e c o s t ' o f p r o d u c t i o n o f s y n t h e s i z e d
p ro d u c ts.
On t h e o t h e r hand* t h i s l i m i t a t i o n on t h e q u a l i t y
o f raw m a t e r i a l s a l s o i n d i c a t e s t h a t a l l s l u d g e s may n o t be
u s e d f o r c h l o r i n a t i n g p u r p o s e s u n l e s s a demand e x i s t s f o r a
v a r ie ty of -c h lo rin a te d p ro d u c ts.
R e s u l t s p ro v e t h a t a c i d
w h ich was u s e d a s a c a t a l y s t i n t h e a l k y l a t i o n p r o c e s s an d
c o n t a i n e d o n ly t e n t o tw e n t y p e r c e n t com bined h y d r o c a r b o n
was r e a d i l y c h l o r i n a t e d .
A c id , w h ic h w as u s e d i n a " S t r a t c o l d "
a c i d t r e a t i n g p r o c e s s f o r c r a c k e d g a s o l i n e and c o n t a i n e d a b o u t
e i g h t y p e r c e n t com bined h y d r o c a r b o n , m s l e s s e a s i l y
c h lo rin a te d .
S i n c e , h o w e v e r, t h e s p e n t c a t a l y t i c a c i d s t i l l
p o s s e s s e d w o rth a s a t r e a t i n g a c i d i t
a d is c a r d slu d g e .
c a n n o t be r e g a r d e d a s
I t would h av e b e e n more f a v o r a b l e h a d t h e
r e s u l t s o f t h e s e c o m p a r a tiv e t e s t s p r o v e d t h e r e v e r s e .
34
F ig u re 2 I s a g ra p h ic a l
r e p r e s e n t a t i o n of th e
f o l l o w ! n g d a t a * and e x p r e s s e s t h e c o r r e l a t i o n b e tw e e n s l u d g e
a c id s t r e n g t h and th e p e r c e n t o f c h lo r in e p r e s e n t I n th e
f i n a l p ro d u c t.
S lu d g e S am ple
S lu d g e A c id
S tre n g th -
A.
B*
0.
S.
B.
F.
P e r g e n t C h lo rin e
S i P ro d u c t
7 . 0 г H2 SO4
4 0 .5
4 9 .5
5 4 .7
6 0 .8
8 1 .0
2 .7
1 5 .2
1 6 .8
1 9 .3
1 9 .9
2 3 .2
A d e s c r i p t i o n o f t h e v a r i o u s s a m p le s i s a s f o llo w s :
A.
by
" S t r a t c o l d " c o ld a c id t r e a t slu d g e produced
t r e a t i n g c r a c k e a g a s o l i n e s . R i c h f i e l d O il C o rp o ra tio n *
3.
L ig h t l u b r i c a t i n g
o i l a c i d t r e a t s lu d g e *
U nion O i l Company.
0*
F i f t y - f i f t y b l e n d o f s a m p le s B. a n d E .
D?
R i c h f ie l d O il C o rp o ra tio n a l k y l a t i o n p ro c e s s
a c i d w hich was s u b s e q u e n t l y u s e d f o r t r e a t i n g s t r a i g h t r u n
g a s o lin e s *
гл
" B la c k A c id " s l u d g e fro m g a s o l i n e a c i d t r e a t s *
U nion O i l Company*
F*
S h e l l O i l Company a l k y l a t i o n p r o c e s s a c i d
s u b s e q u e n tly u se d f o r t r e a t i n g s t r a i g h t run g a s o lin e s a t
t h e W i l s h i r e O i l Company R e f i n e r y .
F i g u r e 3 r e p r e s e n t s t h e c o r r e l a t i o n b e tw e e n th e
av e ra g e m o le c u la r w e ig h t o f each o f th e f i n a l p ro d u c ts
c
to
o
o
10
C\3
o
10
H
o
?X jcl
lO
o
o
3?
d e s c rib e d in F ig u re 2, and th e p e rc e n ta g e of c h lo rin e p r e s н
e n t in each o rg a n ic h a lid e m ix tu re .
The t a b u l a t e d r e s u l t s , w h ic h i n d i c a t e a n i n c r e a s e
i n m o l e c u l a r w e ig h t w i t h a d e c r e a s e i n c h l o r i n e c o n t e n t ,
a re as fo llo w s:
S lu d g e Sam ple
Per cent
C h lo rin e
A.
B.
0.
B.
E.
Fi
2*?
1 5 .2
1 6 .8
1 9 .3
1 9 .9
2 3 .2
. A v e ra g e
M o le c u la r W eight
475
380
375
Hot d e t e r m in e d
357
332
A n o th e r v e r y i n t e r e s t i n g p r o p e r t y c h a r a c t e r i s t i c o f
a d e c r e a s e i n c h l o r i n e c o n t e n t i s t h e i n c r e a s i n g te n d e n c y
o f th e p ro d u c t to m e lt.
W h ile i t was i m p o s s i b l e t o c o a g u l a t e
t h e y e llo w f l o o p r o d u c e d fro m s lu d g e F . by h e a t i n g i t i n h o t
w a t e r , th e m a t e r i a l , f r o m sam ple D. o b v i o u s l y m e l t e d t o fo rm
a y e llo w -b r o w n m a s s .
H ow ever, i n e v e r y c a s e when t h e m a t e r н
i a l was c o a g u l a t e d by h e a t t h e p r o d u c t was e x c e e d i n g l y
b r i t t l e when' c o l d .
The p r o p e r t y of a m a t e r i a l . t o m e l t when s u b j e c t e d
t o h e a t, i s e x c e e d in g ly v a lu a b le *
S i n c e t h i s te n d e n c y t o
m e l t i n c r e a s e s w ith a d e c r e a s e i n c h l o r i n a t i o n , t h i s i s
d e f i n i t e l y i n th e f a v o r o f t h e w e a k e r a c i d s l u d g e s w hich
a r e c h e a p e r an d more h i g h l y s p e n t .
38
A tte m p te d S y n t h e s i s o f G h lo ro D e r i v a t i v e s
A s - a f i n a l s t e p a few a t t e m p t s were made t o p r e p a r e
s y n th e tic o rg a n ic h a lid e s s i m i l a r to th e ch lo ro d e r iv a tiv e s
w i t h th e h o p e o f g a i n i n g some v a l u a b l e i n f o r m a t i o n c o n c e r n н
in g t h e i r n a t u r e .
An a l m o s t i n f i n i t e num ber of p r e p a r a t i o n s
c o u l d b e t r i e d , b u t t h i s p r o j e c t h ad to h av e i t s l i m i t a t i o n s
so much i n t e r e s t i n g w ork r e m a in s t o b e done o n t h i s p h a s e o f
t h e p r o b le m .
An a c c o u n t o f t h e few s y n t h e s i z i n g p r o c e s s e s t r i e d ,
a l l o f w h ich g av e n e g a t i v e r e s u l t s , i s a s f o l l o w s :
A.
D i e t h y l s u l f a t e was a g i t a t e d i n c o n t a c t w i t h
sodium h y p o c h l o r i t e .
R e s u l t ?- no p r e c i p i t a t e .
The
sodium h y p o c h l o r i t e was n e u t r a l i z e d d u r i n g t h e a g i t a t i o n .
R e s u l t ? no p r e c i p i t a t e .
B.
S o l u t i o n r e m a in e d w a t e r w h i t e .
B enzene s u l p h o n i c a c i d w as p r e p a r e d by r e f l u x i n g
b e n z e n e w ith fu m in g s u l f u r i c a c i d a n d t h e e n t i r e p r o d u c t
was n e u t r a l i z e d w ith sodium c h l o r i t e .
R e su lt ? a w a te r
c le a r c o lo rle ss s o lu tio n ^
C*
P o ta s s iu m b e n z e n e s u l p h o n a t e was d i s s o l v e d i n
sodium h y p o c h l o r i t e s o l u t i o n .
R e s u l t ? no p r e c i p i t a t e .
T h is was a c i d i f i e d w i t h s u l f u r i c a c i d .
R e su lt ? a c le a r
c o lo rle s s so lu tio n .
D.
P o ta s s iu m h y d r o g e n s u l p h o n a t e was p u t i n t o
sodium h y p o c h l o r i t e s o l u t i o n .
R e s u lt ? a f t e r s ta n d in g , th e
s o l u t i o n t u r n e d y e llo w and t h e y e l l o w o o l o r c o u l d be
rem oved b y o r g a n i c s o l v e n t s .
A s m a ll q u a n t i t y o f w h i t e
f l o e was d e p o s i t e d i n th e c o n t a i n e r *
The s o l u t i o n was
a c i d i f i e d w i t h s u l f u r i c a c i d b u t no change a p p e a r e d t o
ta k e p la c e .
T h a t i s , t h e a c i d s o l u t i o n w as a l s o y e l l o w
an d y i e l d e d i t s c o l o r t o a n o r g a n i c s o l v e n t .
CHAPTER V I I
SUMMARY
The s u s c e p t i b i l i t y of p e t r o l e u m a c i d s l u d g e t o
r e a c t w i t h v a r i o u s c h e m i c a l s was i n v e s t i g a t e d f i r s t .
The
r e a c t i o n o f a c i d s l u d g e ?w ith sodium h y p o c h l o r i t e p r o v e d
v e r y i n t e r e s t i n g so I n v e s t i g a t i o n was c o n t i n u e d on t h e
c h lo ro d e r iv a tiv e s o f th i s r e a c tio n ,
A t y p i c a l p r o d u c t , l i g h t i n c o l o r , h i g h i n m o le c u н
l a r w e i g h t , a n d c o n t a i n i n g a h i g h p e r c e n t o f c h l o r i n e was
s u b j e c t e d t o v a r i o u s c h e m ic a l a n d p h y s i c a l t e s t s .
The
s u i t a b i l i t y o f t h i s p r o d u c t f o r com pounding c o a t i n g , m a t e r н
i a l s was e s t a b l i s h e d t o a f a i r d e g r e e .
Many of i t s
p r o p e r t i e s i n d i c a t e d t h a t some v a r i e t i e s o f t h e c h l o r o
d e r i v a t i v e s may p o s s i b l y b e u s e d i n p l a s t i c f o r m u l a s ,
A c o m p a ris o n o f t h e r e a c t i v i t y o f v a r i o u s a c i d
s l u d g e s w i t h t h e r e a g e n t p r o v e d t h a t some s l u d g e s a r e
more r e a d i l y c h l o r i n a t e d t h a n o t h e r s a n d h e n c e y i e l d
d i f f e r e n t p ro d u c ts.
T h i s p h a se of t h e work a l s o i n d i c a t e d
t h a t t h e more c o s t l y s l u d g e s ,
( t h a t i s , t h o s e w hich a r e
n o t so h i g h l y s p e n t , } a r e more l a b i l e a s f a r a s th e
a s s im il a ti o n o f c h lo rin e i s concerned,
A v a lu a b le p ro p e rн
t y c h a r a c t e r i s t i c o f and i n f a v o r o f t h e l e s s h i g h l y c h l o r i n a t e d p r o d u c t s , r e s u l t i n g f r o m more t h o r o u g h l y s p e n t
a c i d , i s t h e i r p r o p e r t y t o m e l t and c o a g u l a t e when e x p o s e d
to h e a t.
CONCLUSION
The im p o r ta n c e o f -th is p r o b le m , w h ich was s t r e s s e d
i n th e f i r s t p a r t o f t h i s r e p o r t , i n d i c a t e s t h a t more
e x p e r i m e n t a t i o n on t h e p r e p a r a t i o n of c h l o r o d e r i v a t i v e s
w ould be e x c e e d i n g l y w o r t h w h i l e .
The m a in p ro b le m f o r
c o n t i n u e d r e s e a r c h w ould be th e u t i l i z a t i o n o f t h e more
h ig h ly sp en t a c id s because th e y a r e v e ry p l e n t i f u l and
do y i e l d i n t e r e s t i n g and p r o b a b l y v a l u a b l e p r o d u c t s when
su b m itte d to c h l o r i n a t i o n .
The r e s e m b la n c e o f th e m a t e r i a l o b t a i n e d b y c h l o r н
i n a t i n g a c i d s l u d g e i s com pared w i t h T o r n e s i t i n t h e
A p p e n d ix .
T o r n e s i t , a p r o d u c t p r e p a r e d by c h l o r i n a t i n g
r u b b e r , h a s many i n d u s t r i a l a p p l i c a t i o n s a n d w as u s e d t o
p r e p a r e th e c o a t i n g n a t e r i a l s p a i n t e d on t h e T r y lo n a n d
P e r i s p h e r e a t th e New York W o rld ? s F a i r .
of T o rn e sit,
As i n t h e c a s e
1he c h l o r i n a t e d a c i d s l u d g e p r o d u c t d i d n o t
o f i t s e l f p ro v e t o be a good s y n t h e t i c p l a s t i c ; b u t b y
c o m b in in g i t w ith p l a s t i c i z i n g a g e n t s i t i s o b v io u s t h a t
c o a t i n g compounds r e s e m b l i n g th o s e p r e p a r e d from T o r n e s i t
c o u l d be r e a d i l y made w i t h a s u b s e q u e n t s a v i n g o f a n
i n d u s t r i a l w a s te m a t e r i a l .
BIBLIOGRAPHY
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t o S o c o n y Yaoumn O i l Company. C h e m ic al A b s t r a c t s . 1 9 3 6 ,
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481 p p .
APPENDIX
TABLE II
A COMPARISON OF THE PROPERTIES OF TORNESIT AND THE
CHLORINATED RESIDUE FROM PETROLEUM ACID SLUDGE
?PROPERTY
Powder or granule
CHLORO DERIVATIVE FROM
PETROLEUM ACID SLUDGE
Same
Colored-opaquemottled-translucent
Slight
Amber-translucent,
also opaque
Musty (Slight HC1)
Slight
Slight (Bitter)
Vл{5. forking properties
Thermoplastic
Not determined
f | | . Molding conditions
212 F.
1^7. Compression Ratio
*#
(Vol. loose powder)
H
(Vol. solid
)
W B , Tendency to oold flow
?w*
лj9, Extruding qualities
2 to 3
Various melting points
(Depends on per cent 01)
Not determined
None
None
Fair
Not determined
1.5
1 plus
TORNESIT
>1.
form
?* ?
*. Available
*
'* i
Color and Clarity
*^'4
Odor
Taste
|||4
P
hysical properties
to. Specific Gravity
.. Specific Volume in3/lb .
18.4
Not determined
4 2 . Refractive index
$ THERMAL PROPERTIES
1.56
Not determined
* 3 . Burning rate
Not inflammable
Same
?JL4. Effect of heat
it
^ ll. Heat distortion
Decomposes noticeably
above 120 C.
60 C,
Same (Chars with
liberation of HC1)
Not determined
70 - 110 C.
Softening point
PHYSICAL CHEMICAL PROPERTIES
;-*J.5W ,
Gradual darkening
?Jl7. Effect cf sunlight
1,8; Effect of aging
| )
.4.9. ffater absorption
Hot:
Cold:
R:,
л20. General Resistance to:
Acids (weak)
Acids (strong)
Alkalies (weak)
Alkalies (strong)
Alcoholates
Ketones
Esters
Hydrocarbons (aromatic)
Hydrocarbons (aliphatic)
Mineral Oils
Animal Oils
Vegetable Oils
Wide range of
melting points
Same
Varies with composition Same
S li^ it Decomposition
None
Same
None
Excellent
Excellent
Excellent
Excellent
Excellent
Poor
Poor
Poor
Good
Good
Poor
Poor
Excellent
Poor
Good
Fair
Good
Soluble
Good
Fair
Excellent
Good
Good
Good
VIEW OF THE LITERATURE AND HISTORICAL INFORMATION
I.
LITERATURE DEALING WITH THE EXACT PROBLEM
A v e r y l i m i t e d am ount o f i n f o r m a t i o n w hich d e s c r i b e s
t h e u s e o f , a c i d s lu d g e a s a w hole f o r s y n t h e t i c p u r p o s e s i s
a v a ila b le .
More o f t e n th e m a t e r i a l , I f n o t s u b j e c t e d t o
a c i d r e c o v e r y p r o c e s s e s , h a s b e e n u s e d a s a c r u d e raw s o u r c e
fro m w hich one c h e m ic a l h a s b e e n i s o l a t e d o r h a s b e e n
s y n t h e s i z e d a s a com ponent p a r t .
G a m e r 1 s t a t e s , nThe u s u a l l a r g e p a t e n t l i s t a p p e a r s
c o v e r i n g a v a r i e t y o f m eth o d s f o r u t i l i z i n g a c i d s l u d g e .
I n m o st c a s e s th e o b j e c t i n v ie w i s t h e r e c o v e r y o f s u l f u r i c
a c id ."
E l l i s d e s c r i b e s th e i s o l a t i o n o f s u l p h o n i c a c i d s , 2
s u l f a t e d com po un ds,5 a n d t h e s y n t h e s i s o f a l c o h o l s from
p e tro le u m a c id s lu d g e .^
^ G a r n e r , F . H ,, P e tr o le u m T e c h n o lo g y i n 1958 (The .
I n s t i t u t e o f P e tr o le u m , V o l . 4 , , London: The A d e l p h i ,
1 9 3 9 ) , p . 511
2E l l i s , C a r l e t o n , C h e m is tr y o f P e tr o le u m D e r i v a t i v e s
(V o l. 2 . New Y ork: C h e m ic al C a t a l o g Company, 1 9 3 4 ) , p . 3 5 3
3I b i d . , p p . 1 0 1 3 -1 6
4 I b i d . , p . 1023
Beardо d i s c u s s e s th e r e a c t i o n o f v a r i o u s h y d r o c a r b o n s
w ith s u l f u r i c a c i d b u t does n o t in c lu d e any a p p l i c a t i o n f o r
th e r e s u l t i n g p r o d u c ts .
B i r d 6 a d d e d w ater- t o a c i d s lu d g e a n d by e f f e c t i n g a
r e a c t i o n b e tw e e n t h e h y d r o l y z e d p r o d u c t an d a h a l o g e n a t i n g
a g e n t he fo rm e d a r e s i n o u s p r o d u c t s u i t a b l e f o r a c o a t i n g
m a te ria l.
H i l l 7 c o n t r i b u t e s v a l u a b l e i n f o r m a t i o n by e l a b o r a t i n g
on
t h e c o m p o s iti o n o f a c i d s l u d g e .
He s t a t e s , ??A cid s lu d g e
is
a p o t e n t i a l so u rce o f h y d rocarbon su lp h o n ic a c i d s . "
T h is
i n f o r m a t i o n t e n d s t o s u g g e s t t y p e s o f r e a c t i o n s w hich s h o u ld
be c h a r a c t e r i s t i c o f p e t r o l e u m a c i d s l u d g e ,
Holzman an d S u k n a ro w s k i8 s u b s t a n t i a t e t h e f i n d i n g s
o f H i l l an d g iv e t h e f o l l o w i n g a n a l y s e s o f a c i d s lu d g e w i t h
a c o m p le te d e s c r i p t i o n of. t h e m eth o d s of a n a l y s i s :
оBeard, L. C . , " G e n e r a l L a b o r a t o r i e s , o f S t a n d a r d O il
Company o f Hew Y o r k ," O i l and Gas J o u r n a l . Y o l. 2 8 , No. 4 2 ,
March 6 , 1930 ( T u l s a , Oklahom a: P e tr o le u m P u b l i s h i n g Company)
6B i r d , J . C . , U n i t e d S t a t e s P a t e n t 1 . 9 1 7 . 8 6 9 . J u l y
1 1 , 1 9 3 3 , t o S t a n d a r d O i l Company, C h e m ic al A b s t r a c t s . 19 33,
No. 2 7 , Column 4 6 6 6 .
7H i l l , J . B e n n e t t , "W aste P ro b le m s i n th e P e tr o le u m
I n d u s t r y , ? I n d u s t r i a l a n d E n g i n e e r i n g C h e m i s t r y . Y o l. 3 1 ,
P a r t 2 , No. 2 , p . 1 3 6 1 , November, 1939
h o l z m a n , E . a n d S u k n a r o w s k i, S t e f a n , " A n a l y s i s o f
A c id S lu d g e s fro m M in e r a l O i l T r e a t m e n t s , " I n d u s t r i a l a n d
E n g i n e e r i n g C h e m is tr y ?A n a l y t i c a l - E d i t i o n . 7 :3 7 8 - 3 8 0 , 1 9 3 5 .
S lu d g e Sample
A.
B.
C.
M in e r a l O i l
1 5 .4 $
4 . 7 fa
5 9 .2 $
S u l p h o n ic A c id s
3 7 .0 $
6 3 .2 $
1 7 .9 $
F r e e S u l f u r i c A c id
4 5 .5 $
2 9 .3 $
2 0 .8 $
In s o lu b le M a tte r
o * i$
0 .0 9 $
1*6$
(S u lfu ro u s a n h y d rid e n e g l e c t e d . )
The p r e s e n c e o f l a r g e q u a n t i t i e s o f s u l p h o n i c a c i d s
. a s d e t e r m i n e d by t h e s e two i n v e s t i g a t o r s l i k e w i s e shows why
t h e p r o p e r t i e s o f a c i d s lu d g e s h o u l d re s e m b le t h o s e o f
su lp h o n ic a c id s .
II.
LITERATURE PERTAINING TO RELATED PROBLEMS
H a lo g e n a te d r u b b e r , w h ich i s c o m m e r c ia lly r e f e r r e d
t o a s T o r n e s i t , i s now m a n u f a c tu r e d i n th e U n i t e d S t a t e s . 9
Ellis**-0 t h o r o u g h l y d e s c r i b e s th e p r e p a r a t i o n , p r o p e r t i e s ,
a n d u s e o f t h i s p r o d u c t w h ic h , fro m th e d e s c r i p t i o n g i v e n ,
a p p e a r s t o b e a r a r e m a r k a b le s i m i l a r i t y t o th e p r o d u c t fo rm e d
b y t h e c h l o r i n a t i o n o f p e t r o le u m a c i d s l u d g e .
The p r o p e r t i e s
o f T o r n e s i t a s g iv e n by Hodgman-*-**- a r e co m pared w i t h t h o s e
9E l l i s , C a r l e t o n , C h e m is tr y o f S y n t h e t i c R e s i n s . T o l ,
2 (New Y ork: R e i n h o l d t P u b l i s h i n g C o r p o r a t i o n , 1 9 5 5 ) , p . 1117
10I b i d . , p p . 1 1 0 5 -28
"^Hodgman, 0 . D . , C h em ical .T a b l e s fro m th e Handbook o f
C h e m is try a n d P h y s i c s ( C l e v e l a n d , O h io : C hem ical R ubber
P u b l i s h i n g Company, 1938) p p . 573-58 9
8
o f c h l o r i n a t e d a c i d s l u d g e i n t h e A p p e n d ix .
Berger-*-** u t i l i z e d s l u d g e d e r i v e d fro m r e f i n i n g
h y d r o c a r b o n s w ith an a c t i v e m e t a l h a l i d e such a s alum inum
t r i o h l o r i d e to s y n th e s iz e a p l a s t i c
re sin .
To a c c o m p l is h t h i s ,
B e r g e r c o n d e n s e d th e s l u d g e w i t h r e l a t e d a l k y l h a l i d e s .
H is
p r o d u c t, a c c o rd in g to th e p r o p e r t i e s g iv e n , i s s i m i l a r to a
p r o d u c t fo rm e d b y c h l o r i n a t i n g p e t r o l e u m a c i d s l u d g e .
Biroh-1-^ i n h i s e x t e n s i v e r e p o r t , " A p p l i c a t i o n o f
H y p o c h l o r i t e P r o c e s s , " e x p l a i n s w hat may t a k e p l a c e d u r i n g
h y p o c h lo rite t r e a t s i f th e a g i t a t e d m a te r ia ls a re n o t k ep t
out of c o n ta c t w ith a c id .
He e x p l a i n s , " . . . . h y p o c h l o r i t e
s o lu tio n s a re p a r t i c u l a r l y s u ita b le f o r t r e a t i n g cracked
d i s t i l l a t e s b e c a u s e t h e low c o n c e n t r a t i o n o f h y p o c h l o r o u s
a c i d due t o t h e p r e s e n c e o f e x c e s s o f a l k a l i i s a s a f e g u a r d
a g a in s t th e danger of
*c
h lo rin a tio n .*
The te r m c h l o r i n a t i o n
i s s t r i c t l y s p e a k in g i n c o r r e c t s i n c e i t a p p e a r s u n l i k e l y t h a t
any d i r e c t s u b s t i t u t i o n o c c u rs ; th e a c t i o n p ro b a b ly o o n s is ts
m a i n l y i n th e a d d i t i o n o f h y p o c h l o r o u s a c i d t o u n s a t u r a t e d
compounds w ith th e f o r m a t i o n o f c h l o r h y d r i n s . "
The r e p o r t
d o e s n o t g i v e a n y m ore i n f o r m a t i o n c o n c e r n in g - t h e p r o d u c t o r
^ B e r g e r , H, G ., U n i t e d S t a t e s P a t e n t 2 . 0 4 5 . 8 2 4 . June
9 , 1 9 3 6 , t o Socony Vacumn O i l Company. C h e m ic a l A b s t r a c t s .
1 9 3 6 , No. 3 0 , Column 5 3 2 7 .
T%
B irc h , S. F . , " A p p lic a tio n of H y p o c h lo rite P r o c e s s ,"
O il a n d Gas J o u r n a l . V o l. 2 8 , May 2 3, 1 9 2 9 .
( T u l s a , Oklahoma:
P e tr o le u m P u b l i s h i n g Company, 1930) p . 174
o h l o r h y d r i n s fo rm e d b u t , b e c a u s e of t h e d e s c r i b e d r e a c t i o n ,
compounds o f t h e c h l o r h y d r i n c l a s s a r e p r o b a b l y f o rm e d i n
l a r g e q u a n t i t i e s when sodium h y p o c h l o r i t e i s a d d e d t o a c i d
slu d g e .
M o r r e l l , B a r r y , a n d L an g to n
T4
w r i t e of t h e v a l u e o f
c h l o r i n a t e d n a p h t h a l e n e s , "The m e l t i n g a n d b o i l i n g p o i n t s o f
c h l o r i n a t e d n a p h t h a l e n e s i n c r e a s e w i t h th e number o f c h l o r i n e
ato m s i n t h e m o le c u le and t h e m e l t i n g r a n g e of t h e c o m m e rc ia l
p r o d u c t s i s 6 0 ░ - 1 25░C .
They a r e im p e r v io u s t o m o i s t u r e a n d
do n o t b u r n . "
Carmody^-5 h a s p a t e n t e d t h e p r e p a r a t i o n o f a r e s i n w i t h
a c i d s lu d g e f r o m a n o t h e r s o u r c e , " a b r i g h t , g l o s s y , d a r k
brown r e s i n i s o b t a i n e d a s a r e s i d u e i n d i s t i l l i n g m i x t u r e s
o f a c i d s lu d g e a n d p u r e s t i l l
re sid u e s r e s u ltin g r e s p e c tiv e ly
fro m a c i d wash and f r a c t i o n a t i o n o f l i g h t o i l s p r o d u c e d i n
b y - p r o d u c t c o k in g o f c o a l , . . . . . "
H ass-^ i n d i r e c t l y p o in ts o u t th e la c k of in fo rm a tio n
l ^ M o r r e l l , R. A . , B a r r y , T. H e d le y , L a n g to n , H. M .,
S y n t h e t i c R e s in s and A l l i e d P l a s t i c s (London, E n g la n d :
O x fo rd U n i v e r s i t y P r e s s , 1 9 3 7 ) , p* 224
?^?^Carmody, W. H . , U n i t e d S t a t e s P a t e n t 2 . 1 4 9 . 2 7 5 . J u l y
3 , 1 9 3 9 . A b s t r a c t s . V o l. 2 5 , 19 3 9 , J o u r n a l o f I n s t i t u t e o f
P e tr o le u m T e c h n o l o g i s t s
( E d g b a s to n , B irm ingham , E n g la n d :
I n s t i t u t e o f P e t r o l e u m , 1939)
^ % a s s , H. B . , a n d o t h e r s , The C h l o r i n a t i o n o f M ethane
an d I t s H om ologues. D u n s ta n d , D r. A. E . , a n d o t h e r s , e d i t o r s ,
The S c i e n c e o f P e tr o le u m
(London, E n g la n d : O x fo rd U n i v e r s i t y
P r e s s , 1 9 3 8 ) , p p . 2 7 8 7 -93
10
on h i g h m o l e c u l a r w e i g h t c h l o r i n a t e d h y d r o c a r b o n s w h ich
c o u l d e a s i l y be p r o d u c e d i n m i x t u r e s from a c i d s l u d g e s from
d if fe re n t sou rces.
"The m e th a n e h om ologues h i g h e r t h a n th e
p e n t a n e s a r e d i f f i c u l t t o o b t a i n i n th e p u r e f o im a n d t h e i r
c h lo r in a tio n has been r e l a t i v e l y l i t t l e
s tu d ie d w ith th e
e x c e p t i o n o f a c o n s i d e r a b l e amount of work on p a r a f f i n w a x ."
W ith h i s d i s c u s s i o n on "The C h l o r i n a t i o n o f M ethane a n d I t s
H o m o lo g u e s," he i n c l u d e s a l o n g t a b l e o f d a t a on o h l o r o compounds w h ich c o n t a i n s v a l u a b l e i n f o r m a t i o n by w hich
d e f i n i t e c h lo ro -c o m p o u n d s ca n be com pared w i t h c h l o r i n a t e d
s lu d g e p r o d u c t s .
CHAPTER I I I
THE MATERIALS USED
I.
EQUIPMENT
No s p e c i a l e q u ip m e n t was n e c e s s a r y f o r t h e I n v e s t i g a н
tio n .
H ow ever, f o r a more e x t e n s i v e s t u d y , p l a s t i c p r e s s e s
an d p l a s t i c t e s t i n g a p p a r a t u s would a i d much i n o b t a i n i n g
v a l u a b l e d a t a on s y n t h e s i z e d p l a s t i c s .
A m e c h a n i c a l m ix e r
and some l a r g e o r d i n a r y e q u ip m e n t, two l i t e r
b eak ers,
la rg e
B u c h n er f u n n e l , a n d s e v e r a l two l i t e r g r a d u a t e d c y l i n d e r s
w ere u s e d d u i i n g much of t h e r e s e a r c h .
An a n a l y t i c a l b a l a n c e
a n d " m o l e c u l a r w e ig h t d e t e r m i n a t i o n " a p p a r a t u s w ere n e c e s s a r y
e q u ip m e n t.
A t h e r m o s t a t i c a l l y c o n t r o l l e d c o n s ta n t te m p e ra tu re
oven was a v a i l a b l e an d s e r v e d t o g r e a t a d v a n ta g e when t e s t i n g
th e s t a b i l i t y of v a r io u s p ro d u c ts .
II.
CHEMICALS
I n a d d i t i o n t o t h e u s u a l c h e m ic a ls f o u n d i n an
a n a l y t i c a l l a b o r a t o r y , th e o n ly c h e m ic a ls r e q u i r e d w ere a
l a r g e s u p p ly o f sodium h y p o c h l o r i t e a n d c h l o r i n a t e d l i m e .
P e tr o le u m s u l f u r i c a c i d s lu d g e w as s u p p l i e d by l o c a l o i l
r e f i n i n g c o m p a n ie s .^
^S ee ack no w led gm en t s h e e t
CHAPTER I T
SPECIAL METHODS OF ANALYSIS
F o r t h e d e t e r m i n a t i o n o f m o l e c u l a r w e i g h t s by t h e
f r e e z i n g an d b o i l i n g p o i n t m e th o d s , a o e to p h e n o n e and a c e t o n e
were u s e d r e s p e c t i v e l y a s s o l v e n t s e x c e p t f o r a few p a r t i н
c u l a r c a s e s when t h e h a l o g e n c o n t e n t o f th e m a t e r i a l was
o b v i o u s l y s m a ll a n d b en zen e was u s e d f o r a s o l v e n t .
For
c a l c u l a t i o n s 5 6 .5 d e g r e e s C e n t i g r a d e p e r 100 gram s o f
s o l v e n t was u s e d a s th e c r y o s c o p i c c o n s t a n t f o r a o e t o p h e n o n e ,1
a n d 2 2 .2 d e g r e e s C e n t i g r a d e p e r 100 c c , of s o l v e n t a t b o i l н
in g te m p e ra tu re as th e b o i l i n g p o in t c o n s ta n t f o r a c e t o n e , 2
an d 3 2 . 0 d e g r e e s C e n t i g r a d e p e r 100 c c . o f s o l v e n t a t t h e
b o ili n g p o in t f o r b e n z e n e .^
(In a l l c a se s th e av erag e
m o l e c u l a r w e ig h t o f e a c h p r o d u c t m s d e t e r m i n e d b e c a u s e th e
d e r i v a t i v e s t e s t e d w ere m i x t u r e s of com plex compounds
d e r i v e d from a c i d s l u d g e . )
To d e t e r m in e s u l f u r c o n t e n t , a d i g e s t i o n o f s a m p le s
w ith fu m in g n i t r i c a c i d a n d p o ta s s iu m c h l o r a t e was c a r r i e d
^W ashburn, Edward W . , e d i t o r , I n t e r n a t i o n a l C r i t i c a l
T ab le s
( P u b l i s h e d f o r t h e N a t i o n a l R e s e a r c h C o u n c il of t h e
U n ite d S t a t e s , T o l . 4 . New Y ork: M cG raw -H ill Book Company,
1 9 2 8 ) , p . 183
2Hodgman, C. D . , C h em ical T a b le s fro m th e Handbook of
C h e m is try and P h y s i c s
( C l e v e l a n d , O hio: C h e m ic a l R ubber
P u b l i s h i n g Company, 1 9 3 8 ) , p . 1043
%
Loc . c i t .
15
on.
When th e s o l u t i o n was c l e a r ,
t h e s u l f u r was p r e c i p i t a н
t e d i n th e form o f b a riu m s u l p h a t e .
A c a r b o n - h y d r o g e n c o n t e n t was d e t e r m in e d i n one
p a r t i c u l a r c a s e and th e m eth o d o f Cohen^ was f o l l o w e d .
T h is
p a r t i c u l a r m ethod m o d i f i e s th e r e g u l a r c o m b u s tio n m e th o d b y
th e u s e of f u s e d l e a d ohrom ate i n th e b u r n in g tu b e i n o r d e r
to a v o id e r r o r due to th e p re se n c e o f h alo g en s o r s u l f u r .
To d e t e r m in e th e p e r c e n t a g e of c h l o x i n e i n d a r k
p r o d u c t s th e s i l v e r - t h i o c y a n a t e ? f e r r i c alum m ethod was
used.
S m a ll s a m p le s ( 0 , 1 t o .0 5 g ram s) w ere d i g e s t e d i n
a c e t o n e a n d m e t a l l i c so dium was a d d e d s l o w l y .
th i s s p e c ia l m o d ific a tio n ,
F o llo w in g
th e m etho d a s e x p l a i n e d b y S c o t t 5
was c a r r i e d t o c o m p l e t i o n .
To t i t r a t e
t h e m i n e r a l a c i d p r e s e n t i n s lu d g e th e
m ethod em ployed b y th e U nion O i l Company o f C a l i f o r n i a was
a p p lie d .
T h is m ethod c a l l s f o r t h e u s e o f a s m a ll sam ple
t o w hich a s m a ll q u a n t i t y o f c a r b o n t e t r a c h l o r i d e i s a d d e d .
To t h i s s o l u t i o n a b o u t 50 c c . o f s a t u r a t e d c a l c i u m c h l o r i d e ,
n e u t r a l t o bro m o ph eno l b l u e , i s a d d e d an d t h e a c i d i s t i t r a t e d
t o th e b lu e e n d p o i n t o f t h e i n d i c a t o r w i t h a s t a n d a r d
4C ohen, J . B . , P r a c t i c a l O rg a n ic C h e m is try (London,
E n g la n d : M a c m illa n a n d Company,? 1 9 2 8 7 7 p . 15
^ S e o t t , W i l f r e d W,, S t a n d a r d M ethods of C hem ical
A n a l y s i s (New Y ork: D. Van N o s t r a n d , 1 9 3 5 ) , p . 149
p o t a s s i u m h y d r o x id e s o l u t i o n .
V i o l e n t s h a k in g m u st be
r e s o r t e d to d u rin g th e t i t r a t i o n .
Many m eth o d s f o r t h e a n a l y s i s of p e t r o l e u m a c i d
s lu d g e have b ee n s u g g e s t e d i n t h e w r i t i n g s o f v a r i o u s
e x p e r i m e n t e r s , b u t th e m eth od o f Holzman a n d S u k n aro w sk i,о
w h ich i d e n t i f i e s o n l y g ro u p s r a t h e r t h a n p a r t i c u l a r com pounds,
was f o u n d m o st s u i t a b l e .
h o l z m a n , E . a n d S u k n a r o w s k i, S t e f a n , " A n a l y s i s o f
A c id S lu d g e s fro m M i n e r a l O i l T r e a t m e n t s , " I n d u s t r i a l a n d ,
E n g i n e e r i n g C h e m is t r y ?A n a l y t i c a l E d i t i o n . 7 .;3 7 8 -3 8 0 , 1935
CHAPTER V
PREPARATION AND DESCRIPTION OF VARIOUS DERIVATIVES
B ecause o f t h e h i g h p e r c e n t a g e o f s u l p h o n i c a c i d s
p r e s e n t i n a c i d s l u d g e , some r e a c t i o n s s u g g e s t e d by Camming^
w ere a p p l i e d .
The a c i d s lu d g e u s e d f o r th e f o l l o w i n g t e s t s
c o n t a i n e d 81$ s u l f u r i c a c i d .
E x p e rim e n t 1^.
A sam ple o f s lu d g e was v i g o r o u s l y r e f l u x e d w i t h
g la c ia l a c e tic a c id .
The p r o c e s s fo rm e d a b r i g h t p u r p l e -
c o l o r e d v i s c o u s s o l u t i o n w h ich d e f i e d a l l a t t e m p t s t o g i v e
u p t h e p u r p l e com ponent b y s e l e c t i v e s o l u b i l i t y .
E v id e n tly
t h e dye o r p u r p l e c o n s t i t u e n t was v e r y s u s c e p t i b l e t o
h y d r o l y s i s b e c a u s e t h e a d d i t i o n o f a s m a ll q u a n t i t y o f
w a te r d e s tro y e d th e c o lo r .
E t h y l a l c o h o l , a c e t o n e , an d
e t h y l e t h e r a l s o d e s t r o y e d t h e c o l o r w hich i n d i c a t e d t h e
im p o s s ib il ity of u sin g th e s e s o lv e n ts f o r e x t r a c t i o n p u rн
poses.
A d d itio n a l a c e t i c a c i d m e re ly a c te d a s a d i l u e n t
w h ile c a r b o n t e t r a c h l o r i d e a n d k e r o s e n e w ere v e r y l i g h t l y
t i n t e d by a g i t a t i o n w i t h th e s o l u t i o n .
E th y l a c e ta te
seem ed t o p o s s e s s t h e g r e a t e s t po w er o f s e l e c t i v e s o l u b i l н
i t y and t u r n e d i n t e n s e l y c o l o r e d when a g i t a t e d w ith a s m a ll
q u a n tity of th e p ro d u c t.
A tte m p ts t o r e c o v e r th e p u r p l e
^"Gumming, W i llia m , S y s t e m a t i c O rg a n ic C h e m is tr y
(New Y ork: D. Van N o s t r a n d , 1 9 3 1 ) , p. 324
m a t e r i a l from th e e t h y l a c e t a t e f a i l e d .
Expe r i m e n t 2^.
A q u a n t i t y of s l u d g e was t r e a t e d w i t h sodium
n i t r a t e u n t i l no more h e a t was g e n e r a t e d .
The am ount o f
s a l t r e q u i r e d was a p p r o x i m a t e l y t h e b a s i c e q u i v a l e n t of t h e
a c id p re se n t.
A s o l i d m a t e r i a l was fo rm e d w h ich was r e a d i l y
rem oved by f i l t r a t i o n a n d d r i e d ,
Q u a l i t a t i v e t e s t s proved
t h a t t h e pow dered p r o d u c t , l i g h t brown i n c o l o r , c o n s i s t e d
o f o rg a n ic n i t r a t e s .
B oth s t r o n g p o ta s s iu m h y d r o x id e s o l u н
t i o n an d e t h y l a l c o h o l a c t e d a s good s o l v e n t s f o r th e unknown
m a t e r i a l , b u t t h e p r o d u c t w o uld n o t u n d e r g o c r y s t a l l i z a t i o n .
A s m a l l sam ple was e n c l o s e d i n t i n f o i l a n d s u b j e c t e d t o a
v i o l e n t blow b u t i t d i d n o t e x h i b i t t h e e x p l o s i v e p r o p e r t y
c h a r a c t e r i s t i c o f some o t h e r n i t r a t e d o r g a n i c com pounds.
E x p e rim e n t 3 ,
N i t r i c a c i d was s l o w l y a d d e d t o f i f t y gram s o f
a c id slu d g e .
The r e a c t i o n was e x c e e d i n g l y v i o l e n t , an d
b e c a u s e o f t h i s t h e v e s s e l was e n c l o s e d i n p a c k e d i c e .
The
p r o d u c t fo rm e d was r e c o v e r e d a s i n E x p e r im e n t 1 , b u t i t s
c o l o r was more of a g o ld e n brown..
T h is p r o d u c t a p p e a r e d
e x c e e d i n g l y s t a b l e when s u b m i t t e d t o num erous t e s t s c h a r a c t e r н
is tic
o f " n i t r o " com pounds.
E x p e rim e n t 4 .
A l l a t t e m p t s t o e f f e c t n i t r a t i o n b y th e u s e of
th e n i t r a t e s o f ca d iu m , z i n c , i r o n , c o p p e r , c o b a l t , m agnesium ,
17
an d m an g an ese gave v i o l e n t r e a c t i o n s r e q u i r i n g c o o l i n g .
T h is c a n be e x p l a i n e d by t h e f a c t t h a t , u n l i k e t h e sodium s a l t ,
t h e s e compounds c o n t a i n fro m two t o s i x m o l e c u l e s o f w a t e r o f
c r y s t a l l i z a t i o n w h ich a c t u a l l y c a u s e t h e e q u i v a l e n t of a
la rg e h e a t of d ilu tio n .
As f a r a s c o u l d be d e t e r m in e d , t h e
p r o d u c t fo rm e d i n e a c h c a s e c o r r e s p o n d e d t o t h o s e fa rm e d i n
E x p e r im e n ts 1 a n d 3 ,
B e ca u se of t h e h i g h c o s t of f i x e d n i t r o g e n and t h e
v i o l e n c e of th e r e a c t i o n s o f p r a c t i c a l l y a l l f i x e d n i t r o g e n
compounds w i t h a c i d s lu d g e , i t a p p e a r e d w is e t o a t t e m p t
o t h e r r e a c t i o n s w h ich m ig h t b e more e a s i l y b r o u g h t a b o u t
on a c o m m e rc ia l s c a l e .
T h i s was a l s o s u g g e s t e d on a c c o u n t
o f t h e g r e a t s t a b i l i t y o f th e n i t r a t e d p r o d u c t .
E x p e r im e n t j5.
An e x c e s s o f c o n c e n t r a t e d sodium c h l o r i d e
s o l u t i o n was a d d e d t o a q u a n t i t y o f a c i d s lu d g e a n d a
h e a v y b l a c k r e s i d u e was r e c o v e r e d b y f i l t r a t i o n .
A ll
a t t e m p t s t o u s e th e r e s i d u e f o r t h e p r o d u c t i o n o f p l a s t i c н
lik e n a te ria ls fa ile d .
The r e s i d u e , when d r i e d , a p p e a r e d
v e r y carb o n aceo u s and u n r e a c t i v e .
E x p e r im e n t 6>.
To t e s t t h e s u s c e p t i b i l i t y o f a c i d s l u d g e t o
f r e e h a l o g e n s , a E50 gram sam ple was s l o w l y d i s t i l l e d w h ile
c h l o r i n e g a s was b u b b le d th r o u g h t h e h e a t e d m s s .
Much
c h l o r i n e g a s p a s s e d o v e r b u t d e f i n i t e t r a c e s of b e n z y l
18
c h l o r i d e were d e t e c t e d .
P u n g e n t f u m e s , which, c a u s e d th e
e y e s t o w a t e r an d w h ich s m e l l e d e x a c t l y l i k e t h e b e n z y l
compound, w ere so p l e n t i f u l t h a t e x t r a c a u t i o n h a d t o be
ta k e n .
A tte m p ts to i d e n t i f y t r a c e s o f m a t e r i a l s c o r r e s p o n d н
in g to c h lo ro fo rm o r ca rb o n t e t r a c h l o r i d e f a i l e d .
E x p e rim e n t 7 .
F i f t y gram s o f d r y sodium c h l o r i d e w ere a d d e d
to f i f t y gram s o f a c i d s lu d g e and t h e m a t e r i a l was h e a t e d
i n a gas g e n e r a to r .
G r e a t v o lu m e s o f h y d r o g e n c h l o r i d e
g a s w ere p ro d u c e d a n d no t r a c e o f o r g a n i c compounds c o u l d
be d e t e c t e d i n t h e " o v e r - h e a d . "
E x p e r im e n t 8 .
S u s p e c t i n g the p o s s i b i l i t y o f f o r m i n g c a r b o n
d i s u l f i d e w i t h a c i d s l u d g e , a q u a n t i t y of t h e w a ste m a t e r н
i a l m s a d d e d to s u l f u r .
C h l o r i n e was p a s s e d i n t o t h e r e t o r t
w h i l e t h e m i x t u r e was h e a t e d , and a few gram s o f i o d i n e w ere
added f o r c a t a l y t i c p u rp o se s.
I f a n y c a r b o n d i s u l f i d e w as
f o rm e d , th e o b j e c t was to h a v e i t r e a c t w i t h f r e e c h l o r i n e
i n t h e p r e s e n c e o f t h e i o d i n e c a t a l y s t t o p ro d u c e c a rb o n
te tra c h lo rid e .-
No t r a c e s o f th e c a rb o n t e t r a c h l o r i d e c o u ld
be d e te c te d in th e d i s t i l l a t e , b u t t e s t s i n d i c a t e d th e
p r e s e n c e o f a good y i e l d of s u l f u r m o n o c h l o r i d e .
E x p e r im e n t j3.
S u l f u r an d a c i d s l u d g e s were r e f l u x e d t o g e t h e r
f o r one h o u r w ith th e hope o f fo rm in g a c h e a p , i n t e r e s t i n g
19
p r o d u c t b u t no d e f i n i t e r e a c t i o n a p p e a r e d to t a k e p l a c e .
A f t e r t h e m a t e r i a l was c o o l t h e f r e e
s u l f u r , i n th e p l a s t i c
a l l o t r o p i c f o r m , c o u ld be r e c o v e r e d b y w a t e r w a s h in g .
E x p e r im e n t 1 0 .
One h u n d r e d gram s o f a c i d s lu d g e were n e u t r a l i z e d
w ith m ilk of lim e .
The p r e c i p i t a t e was e x c e e d i n g l y w h i t e
a n d c o n t a i n e d lim e o r g a n i c s a l t s i n a d d i t i o n t o q u a n t i t i e s
o f c a lc i u m s u l f a t e .
By f i l t r a t i o n , when t h e m i x t u r e was h o t ,
s m a l l q u a n t i t i e s o f c a lc i u m s a l t s o f s u l p h o n i c a c i d s c o u l d
be r e c o v e r e d ; b u t g e n e r a l o b s e r v a t i o n l e d t o th e c o n c l u s i o n
t h a t no com m ercial p r o c e s s c o u ld r e s u l t fro m su c h a n i n н
e f f i c i e n t means f o r s e p a r a t i o n .
Expe r im e n t 1 1 .
C h l o r i d e o f lim e was n e x t a d d e d t o a l a r g e
sample o f s lu d g e a n d t h e p r e c i p i t a t e was i n t e n s e l y y e l l o w .
The y e l l o w c o m p o n e n t, w hich l a t e r p r o v e d t o be a l k y l h a l i d e s ,
was r e a d i l y s o l u b l e i n h o t a l c o h o l .
By means o f s o x h l e t
e x t r a c t i o n t h e o r g a n i c h a l i d e s w ere r e c o v e r e d , a n d d u r i n g
t h e p r o c e s s t h e y c o a g u l a t e d i n t h e h o t a l c o h o l a n d form ed
s o f t brown d r o p l e t s w i t h a h i g h s p e c i f i c g r a v i t y .
On
re m o v a l fro m th e h o t a l c o h o l , t h e s e d r o p l e t s w ou ld c o n g e a l
t o form h a r d b r i t t l e m a s s e s o f o r g a n i c h a l i d e s .
E x p e rim e n t 1 3 .
To e l i m i n a t e th e n e e d f o r e x t r a c t i o n i n E x p e r i н
m ent 1 1 , a q u a n t i t y of a c i d s lu d g e was n e u t r a l i z e d w i t h
sodium h y p o c h l o r i t e , an d a f t e r s t a n d i n g t w e n t y - f o u r h o u r s
g r e a t q u a n t i t i e s of y e l lo w o r g a n i c h a l i d e s w ere d e p o s i t e d .
T h ese c o u ld r e a d i l y be r e c o v e r e d by f i l t r a t i o n * a n d when
d r y t h e p r o d u c t seemed so i n t e r e s t i n g t h a t an e x t e n s i v e
s t u d y o f t h e m a t e r i a l was m ade.
C h a p t e r s i x d i s c u s s e s th e p r o p e r t i e s o f t h e p r o d u c t s
fo rm e d from v a r i o u s s l u d g e s by t h i s m e th o d .
The e c o n o m ic s
f o r c o m m ercia l a p p l i c a t i o n an d v a r i o u s m o d i f i c a t i o n s u s e d
f o r p r e p a r i n g t h e p r o d u c t a r e a l s o c o n s id e r e d *
CHAPTER VI
T h is c h a p t e r c o n t a i n s a s t u d y o f t h e " O h lo ro "
d e r i v a t i v e fro m a g i v e n p e t r o le u m a c i d s l u d g e a n d i n c l u d e s
a c o m p a ris o n o f t h e c h l o r i n a t e d m a t e r i a l s fro m v a r i o u s
s a m p le s o f s l u d g e ,
I.
PREPARATION AND STUDY <F THE "CHLORO" DERIVATIVE
P re p a ra tio n
To 1000 gram s o f 8 1 $ a l k y l a t e a c i d s lu d g e
w h ich h a d b e e n u s e d f o r g a s o l i n e t r e a t i n g , 1500 gram s o f
d i s t i l l e d w a t e r c o n t a i n i n g 200 grams o f d i s s o l v e d sodium
c h l o r i d e w ere s l o w l y a d d e d .
The m i x t u r e was a l l o w e d t o
s t a n d s e v e r a l h o u r s a f t e r w h ic h tim e a muddy b r o w n - b la c k
p r e c i p i t a t e was f i l t e r e d o f f w ith t h e a i d o f a B u c h n er
fu n n e l,
W ith o u t w a s h in g o r d r y i n g t h e p r e c i p i t a t e , t h e
e n t i r e y i e l d was p l a c e d i n a tw o l i t e r b e a k e r a n d 1000 c c ,
o f 1 6 $ sodium h y p o c h l o r i t e was a d d e d .
The r e a c t i o n was
v i o l e n t due t o t h e p r e s e n c e o f a c i d b u t th e above q u a n t i t y
o f NaGlO r e p r e s e n t e d a n e x c e s s , and t h e r e f o r e some re m a in e d
u n re a c te d upon.
The ab o v e m i x t u r e was a l l o w e d t o s t a n d
t w e n t y - f o u r h o u r s a f te r* - s to ic h p e r i o d of t i m e t h e t a n
p r e c i p i t a t e , w hich h a d s e t t l e d t o th e b o tto m , was f i l t e r e d
o f f w ith a B u chn er f u n n e l a n d w ashed s e v e r a l t i m e s w i t h
d i s t i l l e d w a te r.
a p p r o x i m a t e l y 10$#
The p r o d u c t was t h e n d r i e d .
See F i g u r e I .
Y ie ld ?
IX .7 .iClZ) CTPIHGTH
. -J
s c d i u i .: h
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23
C ost of P re p a r a tio n
A ci d S l u d g e . . . . . . . . . . .
R e g a rd e d n i l
Sodium c h l o r i d e . . . . . . .
0.010
Sodium h y p o c h l o r i t e . . .
0 .0 7 - 2 5 0 p e r g a l l o n
T o ta l. . .
0 ,0 8 г p e r 100 gram s
o r 350 p e r pound
A s s a y of M a t e r i a l
P h y sic a l P r o p e r tie s
C o l o r Tan
Odor M usty
S p e c if ic G ra v ity 1 .0 p lu s
D ry am orphous pow der
C ry sta lliz a tio n te s ts fa ile d
N ot T h e r m o p l a s t i c (Decomposes when h e a t e d )
Not T h e r m o s e t t i n g (
?
w
" j
2 . 0 $ l o s s of w e i g h t on s t a n d i n g a t 1 0 0 ░F .
f o r two w eeks
T ery g r a d u a lly darkens w ith t r a c e s o f
c h lo r in e h ein g l o s t
M o l e c u l a r w e ig h t ? w i t h a c e to p h e n o n e
- - w i t h a c e to n e
345
330
322
S u l f u r on f i n i s h e d m a t e r i a l
A v erag e 2^00$
S u l f u r r e c o v e r e d fro m w a t e r a f t e r f i v e
gram s o f m a t e r i a l s t o o d i n c o l d
w a te r tw e n ty -fo u r h o u rs
0 .0 5 $
In so lu b le fix e d s u lfu r
C h lo rin e on f i n i s h e d m a te r ia l
H alo g e n c o n t e n t l o s t by 5 gram s
sta n d in g in w a te r
R e sid u a l f ix e d c h lo r in e
1 .9 5 $
23$
.$
1 0
22$
C a rb o n -H y d rc g e n r a t i o ;
b y c o m b u s tio n .
F u s e d l e a d ch ro m a te was u s e d i n c o m b u s tio n
t u b e b e c a u s e of th e h a l o g e n an d s u l f u r c o n t e n t ;
C a rb o n ..................... ..
7 3 .3 $
H y d ro g en .
...................................... T ra o e
24
Summary o f I n d i o a t e d R e s u l t s
A v erag e m o l e c u l a r w e i g h t
352
C h lo rin e
2 2 .0 $
S u lfu r
1 .9 5 $
C arbon
7 3 .3 $
H y d ro g en
T ra c e
Oxygen
By d i f f e r e n c e 2 .7 5 $
The r e s i s t a n c e to s o l v e n t s o f t h e c h l o r o d e r i v a t i v e
a p p e a r s t o be a v a l u a b l e p r o p e r t y of th e p r o d u c t .
T h erefo re,
i n T a b le 1 a c o m p le te l i s t o f t h e e f f e c t s o f v a r i o u s s o l н
v e n ts i s d e s c rib e d .
A s o l v e n t d e r i v e d fro m a h a l o g e n seem s t o y i e l d
p a r t i a l s o l u b i l i t y w h ile a s o lv e n t c o n ta in in g a c a rb o n y l
g ro u p seem s t o y i e l d t o t a l s o l u b i l i t y i n many e a s e s .
C hem ioal N a tu r e and R e a c t i o n s
An i m p o r t a n t r e a c t i o n o f c h l o r o d e r i v a t i v e s
s u g g e s t e d by E l l i s ^ - i s
KX + NlgSOg ?^
RNaSOg-+? NaX
( S tr e c k e r R e a c tio n )
T h i s r e a c t i o n w as t r i e d f o r th e p o s s i b l e s y n t h e s i s
o f a h ig h m o l e c u l a r w e ig h t s a l t w i t h a h i g h d e g r e e o f
s o l u b i l i t y an d a l a t h e r i n g c h a r a c t e r i s t i c .
F i f t y grams o f sodium s u l f i t e i n 100 grams o f w a t e r
was r e f l u x e d f o r t w e n t y - f o u r h o u r s i n c o n t a c t w i t h f i v e gram s
o f th e unknown c h l o r i d e ,
^ E l l i s , C a r l e t o n , C h e m is tr y o f P e tr o le u m D e r i v a t i v e s
V o l. 2 (New Y ork: R e i n h o l d t P u b l i s h i n g Company, 1 9 3 7 ) , p .8 0 4
TABLE I
SOHTBILITY OF THE CHLORINATED RESIDUE FROM PETROLEUM ACID SLUDGE
A.
INACTIVE SOLVENTS
1 . B e n z a ld e h y d e
8 . F o rm ald eh y d e
2 . C arbon B i s u l p h i d e
9. G ly c e rin e
3 . Camphor
(M e lte d )
(C o ld )
1 0 . P e tr o le u m E t h e r
4 . 1 - 4 D iox ane
1 1 . T u r p e n t i n e ( P in e n e )
5. E th y l E th e r
1 2 . T o lu en e
6. E th y l A c e ta te
13.
7 . E t h y l A lc o h o l
B.
(C o ld )
U rea
(W ater S o l u t i o n )
1 4 . X ylene
PARTIALLY OR SLIGHTLY ACTIVE SOLVENTS
1 . A o p ty l c h l o r i d e
5 . E t h y l A lc o h o l (H ot)
2 . Benzoyl c h l o r id e
6 . E th y le n e d i c h l o r i d e
3 . C arbon t e t r a c h l o r i d e
7 . M e s i t y l o x id e
4 . C h lo ro f o rm
8 . T in c tu re b e n z o in
C.
GOOD SOLVENTS
1 . A c e to n e
3 . B enzophenone
2 . A c e to p h e n o n e
4 . U re a
D.
(M e lte d )
REACTING SOLVENTS
1 . G ly c e rin e
(H ot) P o l y m e r i z e s . H ow ever, t h e
r e s i n fo rm e d h a s a s t r o n g a f f i n i t y f o r
w a t e r a n d a f t e r s e v e r a l h o u r s becom es v e r y
w e t.
2 . A n i l i n e - A d a r k brown o i l y m ass i s form ed*
T h e re i s an a p p a r e n t r e a c t i o n b e tw e e n t h e
c h l o r o p r o d u c t a n d a l l a m in e s .
3 . C o n c e n tra te d s u l f u r i c and n i t r i c a c id s a t t a c k
th e " c h lo ro ? d e r i v a t i v e s .
26
R e s u l t ? The s o l u t i o n was f i l t e r e d an d the f i l t r a t e
c o n t a i n e d o n l y a s m a ll q u a n t i t y of t h e unknown compound.
More th a n f o u r gram s re m a in e d u n co m bined an d u n d i s s o l v e d .
The f i l t r a t e
h a d a g oo d te n d e n c y t o foam w i t h a l i t t l e
a g i t a t i o n w h ic h i n d i c a t e s t h a t th e S t r e c k e r r e a c t i o n d id
ta k e p l a c e t o some e x t e n t .
Lowy an d H a r r o w ^ a n d D e g e r in g 3 d e s c r i b e t h e f o l l o w н
in g r e a c t i o n of o rg a n ic h a l i d e s :
2RX *t? KgS
----^
RSR +
2KK
S u l f i d e s and d i s u l f i d e s a r e p r e p a r e d by t h i s m e th o d .
Some of t h e unknown h a l o g e n compound m i x t u r e was r e f l u x a d
w i t h a s t r o n g s o l u t i o n o f p o ta s s iu m s u l f i d e .
R e s u l t ?? A d a r k o i l y m a t e r i a l
( p o s s ib ly h ig h
m o l e c u l a r w e ig h t t h i o e t h e r s ) was f o r m e d , b u t i t was n o t
e t h e r s o l u b l e w h ich m akes th e c o n c l u s i o n t h a t i t was t h i o н
e t h e r s o n ly p r o b l e m a t i c a l .
The w e l l known " G r i g n a r d ? s R e a c t i o n " d e s c r i b e d by
P o r t e r ^ was n e x t a t t e m p t e d .
The unknown compounded o r g a n i c
2Lowy, A le x a n d e r and H arro w , B e n ja m in , I n t r o d u c t i o n
t o O rg a n !c C h e m is tr y (New Y ork: Jo hn W iley & S o n s , 1928)
p . 194
3 D e g e r in g , E . F . f and o t h e r s , An O u t l i n e of O rg a n ic
C h e m is tr y
(New Y ork: B a rn e s an d N o b l e , 1 9 3 9 ) , p . 126
^ P o r t e r , G, W ., The C arbo n Compounds (New Y ork;
Ginn and Company, 1 9 5 1 ) , p . 75
27
h a l o g e n m i x t u r e was e t h e r i n s o l u b l e a n d a l l a t t e m p t s t o make
a n e t h e r s u s p e n d e d m i x t u r e r e a c t w i t h z i n c o r m agnesium
i
fa ile d .
A c e to n e , f o r a s o l v e n t , was t h o r o u g h l y d r i e d a n d
seemed t o b r i n g a b o u t a r e a c t i o n w i t h m e t a l l i c z in c *
H ow ever, G r i g n a r d r e a g e n t r e a c t s w i t h a k e t o n e to y i e l d a
t e r t i a r y a l c o h o l , 5 a n d , s i n c e p r e c i p i t a t i o n g r a d u a l l y to o k
p l a o e , e v i d e n t l y G r i g n a r d * s r e a g e n t was b e i n g f o r m e d a n d
i n s t a n t a n e o u s l y r e a c t e d w i t h some of t h e s o l v e n t t o fo rm
a n i n s o l u b l e h i g h m o l e c u l a r w e ig h t t e r t i a r y a l c o h o l ,
E l l i s 6 g i v e s t h e f o l l o w i n g sam ple e q u a t i o n s f o r
c o n d e n s a t i o n s and t h e p r o d u c t i o n
of o l e f i n s :
C .C .X .+ A lc KOH
RX+ H2 O + C:C
X .C .C .X + 2Na
0 :0 - 1 ' 2NaCL
HX+ RX + 2Na
? P? R:R + 2NaX
(W urtz)
The r e a c t i o n w i t h a l c o h o l i c KOH when a p p l i e d t o th e
p r e p a r e d o r g a n i c h a l i d e m i x t u r e y i e l d e d a d a r k b r o w n is h
?p re c ip ita te .
T h is was a pow der when d r y , a n d when t e s t e d
by h a l o g e n a b s o r p t i o n showed no u n s a t u r a t i o n .
The r e a c t i o n wl t h sodium t o a f f e c t Wurtz* o r
F i t t i g ? s c o n d e n s a t i o n w as d i f f i c u l t t o b r i n g a b o u t b e c a u s e
5I b i d . , p . 75
^ Illis,
o n . o i t . T p , 804
o f t h e i n s o l u b i l i t y o f th e m a t e r i a l i n s u l f u r i c e t h e r .
When d r y a o e to p h e n o n e w as em plo yed a s a s o l v e n t i t was
p o s s i b l e t o p r o d u c e a b l a c k s l u d g e - l i k e m a ss w hich h a r d e n
ed and became b r i t t l e
when d r y .
T h is m a t e r i a l e x h i b i t e d
some of th e p h y s i c a l c h a r a c t e r i s t i c s o f common a s p h a l t .
S i l v e r a c e t a t e s o l u t i o n r e a c t e d v e r y r e a d i l y w ith
an a c e t o n e s o l u t i o n o f th e h a l i d e t o y i e l d w h i t e s i l v e r
c h l o r i d e a n d a c a n p l e x i n s o l u b l e brown compound m i x t u r e .
Ammonia g a s was b u b b le d t h r o u g h a n a c e t o n e s o l u t i o n
o f t h e unknown h a l o g e n compound m i x t u r e .
urn c h l o r i d e w ere fo rm e d ; b u t ,
T r a c e s o f ammoni
g e n e r a l l y s p e a k i n g , th e
s o l u t i o n re m a in e d p r a c t i c a l l y u n c h a n g e d a s f a r a s c o u l d be
d e te rm in e d .
The m e th o d o f r e d u c t i on o f D e g e r in g 7 an d F i s h e r 8
was n e x t a p p l i e d .
F i r s t a c t i v a t e d h y d r e g e n was em ployed
as a re d u c in g a g e n t.
The p u r p o s e of t h i s e x p e r i m e n t was
to produce a pure h y d ro c a rb o n .
To a c c o m p l i s h t h i s , z i n o
d u s t was s u s p e n d e d i n a weak c o p p e r s u l f a t e s o l u t i o n
g i v i n g a Cu-Zn c o u p le ^ h ic h c a u s e d a c t i v a t e d h y d ro g e n t o
7D e g e r in g , o p . o i t . , p . 38
% i s h e r , H a r ry L . , l a b o r a t o r y M anual of O rg a n ic
C h e m is tr y
(New Y ork: Jo h n W iley a n d S o n s, 1 9 3 1 J , p . 53
be l i b e r a t e d .
Some o f t h e unknown m a t e r i a l was k e p t i n
c o n t a c t w i t h a co u p le of t h i s d e s c r i p t i o n .
The y i e l d o f
b e n z e n e a n d c a rb o n t e t r a c h l o r i d e s o l u b l e m a t e r i a l was s m a ll
(about
20
% ), b u t th e h a l o g e n c o n t e n t of t h i s r e c o v e r e d r e н
d u ced m a t e r i a l w as p r a c t i c a l l y n i l .
A s e c o n d m etho d o f r e d u c t i o n e x p l a i n e d by D e g e r in g 9
was t r i e d .
Some of t h e n a t e r i a l was r e f l u x e d w i t h h y d r i o d i c
a c id and r e d p h o sp h o ro u s.
The r e s u l t s i n t h i s p a r t i c u l a r
c a s e w ere a b o u t i d e n t i c a l w i t h t h o s e o b t a i n e d b y e m p lo y in g
th e c o u p le.
The y i e l d cf t h e h a l o g e n f r e e s o l u b l e m a t e r i a l
was a p p r o x i m a t e l y t w e n t y - f i v e p e r c e n t f o r t h i s m etho d o f
red u e t i o n .
Some o r g a n i c h a l i d e s a r e s u s c e p t i b e t o m e t a t h e s i s
a c c o r d i n g t o E l l i s * о , an d f o r t h i s r e a s o n t e n gram s o f t h e
m a t e r i a l was r e f l u x e d w i t h a s t r o n g s o l u t i o n o f sodium
o le a te
(a lc o h o l 7 0 $ ).
The a c t i o n w hich to o k p l a c e r e s e m b le d
t h a t o f th e m a t e r i a l when i t was p l a c e d i n b o i l i n g a l c o h o l .
As f a r a s c o u l d be d e t e r m in e d , no m e t a t h e s i s t o o k p l a c e b u t
a c o a g u l a t e d m ass was f o r m e d .
9I b i d . . p . 38
1C* E l l i s , o p . o i t . , p . 822
30
A s m a ll q u a n t i t y of some of t h e unknown m a t e r i a l was
p l a c e d i n a bomb
wi
th ammonium h y d r o x id e a n d p r e s s u r e
a p p l i e d by h e a t i n g t h e bomb s e v e r a l h u n d r e d d e g r e e s .
A c c o rd н
i n g to E l l i s 1--*-, am in es may b e p r o d u c e d by t h i s m eth o d b u t no
t r a c e s o f f i x e d o r g a n i c n i t r o g e n c o u l d b e d e t e c t e d by t h e
u s u a l o r g a n i c q u a l i t a t i v e t e s t d e s c r i b e d by Kamm.1-2
A n i l i n e seem ed t o d i s s o l v e o r r e a c t w ith a g r e a t
p e r c e n t a g e o f t h e compound m i x t u r e .
B e d i s t i l l a t i o n of th e
a n i l i n e y i e l d e d e i g h t e e n p e r c e n t o f a d a r k brown com ponent
o v e r a w ide t e m p e r a t u r e r a n g e ab o v e t h e b o i l i n g p o i n t o f
pure a n i l i n e .
To b e c o n s i s t e n t w i t h t h e s t a t e m e n t o f
D e g e r i n g l S , i t i s l o g i c a l t o c o n c lu d e t h a t h ig h m o l e c u l a r '
w e ig h t a d d i t i o n p r o d u c t s w ere f o r m e d .
A tte m p ts w ere made t o d r y d i s t i l l some o f t h e
compound m i x t u r e w ith z i n c d u s t .
A c c o r d in g t o D e g e rin g ^ 4
t h i s s h o u l d p r e v e n t th e f o r m a t i o n o f HC1 w ith a s u b s e q u e n t
y i e l d o f z i n c c h l o r i d e and u n s a t u r a t e d h y d r o c a r b o n .
13-I b i d . . p , 804
Y ork:
^Kamm, O l i v e r , Q u a l i t a t i v e O rg a n ic A n a l y s i s
Jo h n W iley and S o n s , 1931) p . 1г3
13
D e g e r in g , o p . b i t . , p . 37
14L o c . c i t .
(New
R e s u l t ?? C h a r r i n g w ith a g r e a t i n c r e a s e i n v o lu m e ,
and t h e c h a r r e d m a t e r i a l seem ed t o p o s s e s s no h a l o g e n
a b s o r p t i o n po w er.
D e g e r in g ^ 5 e x p l a i n s th e p r e p a r a t i o n o f e t h e r s a n d
i s o c y a n i d e s by m e t a t h e s i s o f h a l o g e n compounds w i t h sodium
a l c o h o l a t e an d sodium c y a n i d e .
When u s i n g th e p e t r o le u m
c h l o r o d e r i v a t i v e a s a s u b s t i t u t e f o r th e h a l o g e n compound,
t h e s e r e a c t i o n s f a i l e d to y i e l d a s u f f i c i e n t q u a n t i t y o f
a n y p r o d u c t t h a t c o u l d be i s o l a t e d b y f r a c t i o n a t i o n o r
fra c tio n a l c ry s ta lliz a tio n .
The C ohen^6 m eth o d o f " F r i e d e l a n d C r a f t " r e a c t i o n
e m p lo y in g ALClg a s a c a t a l y s t was a p p l i e d t o c a u s e a
r e a c t i o n b e tw e e n t h e p o ly h a lo g e n compound m i x t u r e a n d
a.
b.
c.
d.
e.
A n ilin e
B enzene
A c e to p h e n o n e
B enzophenone
P y rid in e
I n a l l c a s e s some r e a c t i o n o b v i o u s l y to o k p l a c e w i t h t h e
l i b e r a t i o n o f h y d ro g e n c h l o r i d e , b u t i n t h e c a s e s o f a . ,
e . , a n d d . t h e r e a c t i o n was p a r t i c u l a r l y v i o l e n t .
h y d r o g e n c h l o r i d e i s a n e c e s s a r y p r o d u c t cf
15
1 fi
I b i d . . p . 38
Cohen, o p . cijfc. , IV, p p . 2 6 2 -2 6 4
S in c e
th e . " F r i e d e l a n d
52
C r a f t " r e a c t i o n , i t i s l o g i c a l to c o n c lu d e t h a t t h i s r e н
a c t i o n d i d ta k e p l a c e t o v a r y i n g d e g r e e s i n a l l f i v e c a s e s .
A f t e r c a r r y i n g t h e m ethod th r o u g h i n t h e c u s to m a r y m anner
f o r e a c h s o l v e n t , i n no c a s e was i t p o s s i b l e t o r e c o v e r a
r e p r e s e n t a t i v e q u a n t i t y o f a compound fro m th e y i e l d e d
m ix tu re .
F r a c t i o n a l c r y s t a l l i z a t i o n , f r a c t i o n a t i o n , and
s e l e c t i v e s o l u b i l i t y w ere a l l t r i e d i n a tte m p tin g t o i s o l a t e
a co m p o n en t.
C a t a y t i o V a lu e
A t t e m p t s w ere made t o em ploy some o f t h i s m a t e r i a l
a s a h a l o g e n c a r r i e r o r s u b s t i t u t e f o r alum inum c h l o r i d e
b u t no e v i d e n c e was s e c u r e d t o s u b s t a n t i a t e i t s w o r t h i n
th is re sp e c t.
The d r y in g s p e e d o f d r y in g o i l s was n o t i n c r e a s e d
by a s u s p e n s i o n o f a s m a l l q u a n t i t y o f t h e o r g a n i c h a l i d e .
As e x p l a i n e d a b o v e , g l y c e r i n e when b o i l e d w i t h a
s m a ll p e r c e n t a g e o f th e m a t e r i a l showed d e f i n i t e i n d i c a t i o n s
of p o ly m e riz a tio n ,
When s m a ll q u a n t i t i e s o f t h e h a l o g e n compound m ix н
t u r e w ere p u t on m o i s t dyed c l o t h s no t r a c e s o f b l e a c h i n g
w ere d e t e c t e d i n an y c a s e .
T h is i n d i c a t e d t h a t t h e l i b e r a н
t i o n o f f r e e c h l o r i n e due t o i n s t a b i l i t y w as v e r y s m a l l .
33
The Q h l o r i n a t i o n of S lu d g e s fro m D i f f e r e n t O r i g i n s
A s e c o n d a r y p ro b le m o r i g i n a t i n g from t h e p r o d u c t i o n
o f o r g a n i c h a l i d e s fro m p e t r o le u m a c i d s l u d g e i s
th e wide
v a r i a t i o n o f r e s u l t i n g p r o d u c t s due t o th e u s e o f d i f f e r e n t
s l u d g e s p r o d u c e d by v a r i o u s r e f i n e r y p r a c t i c e s .
The r e s u l t s o b t a i n e d b y s y n t h e s i z i n g p r o d u c t s fro m
v a r i o u s s l u d g e s i n d i c a t e t h a t t o p ro d u c e a p l a s t i c m a t e r i a l
w ith d e f i n i t e c h a r a c t e r i s t i c s an a c id slu d g e o f a d e f i n i t e
q u a lity is re q u ire d .
T h is n a t u r a l l y c a l l s f o r a r e f i n e r y c o n t r o l o f t h e
q u a l i t y of a c i d s l u d g e s w h ich i n t r o d u c e s e x p e n s e , and t h e r e н
by i n d i r e c t l y i n c r e a s e s t h e c o s t ' o f p r o d u c t i o n o f s y n t h e s i z e d
p ro d u c ts.
On t h e o t h e r hand* t h i s l i m i t a t i o n on t h e q u a l i t y
o f raw m a t e r i a l s a l s o i n d i c a t e s t h a t a l l s l u d g e s may n o t be
u s e d f o r c h l o r i n a t i n g p u r p o s e s u n l e s s a demand e x i s t s f o r a
v a r ie ty of -c h lo rin a te d p ro d u c ts.
R e s u l t s p ro v e t h a t a c i d
w h ich was u s e d a s a c a t a l y s t i n t h e a l k y l a t i o n p r o c e s s an d
c o n t a i n e d o n ly t e n t o tw e n t y p e r c e n t com bined h y d r o c a r b o n
was r e a d i l y c h l o r i n a t e d .
A c id , w h ic h w as u s e d i n a " S t r a t c o l d "
a c i d t r e a t i n g p r o c e s s f o r c r a c k e d g a s o l i n e and c o n t a i n e d a b o u t
e i g h t y p e r c e n t com bined h y d r o c a r b o n , m s l e s s e a s i l y
c h lo rin a te d .
S i n c e , h o w e v e r, t h e s p e n t c a t a l y t i c a c i d s t i l l
p o s s e s s e d w o rth a s a t r e a t i n g a c i d i t
a d is c a r d slu d g e .
c a n n o t be r e g a r d e d a s
I t would h av e b e e n more f a v o r a b l e h a d t h e
r e s u l t s o f t h e s e c o m p a r a tiv e t e s t s p r o v e d t h e r e v e r s e .
34
F ig u re 2 I s a g ra p h ic a l
r e p r e s e n t a t i o n of th e
f o l l o w ! n g d a t a * and e x p r e s s e s t h e c o r r e l a t i o n b e tw e e n s l u d g e
a c id s t r e n g t h and th e p e r c e n t o f c h lo r in e p r e s e n t I n th e
f i n a l p ro d u c t.
S lu d g e S am ple
S lu d g e A c id
S tre n g th -
A.
B*
0.
S.
B.
F.
P e r g e n t C h lo rin e
S i P ro d u c t
7 . 0 г H2 SO4
4 0 .5
4 9 .5
5 4 .7
6 0 .8
8 1 .0
2 .7
1 5 .2
1 6 .8
1 9 .3
1 9 .9
2 3 .2
A d e s c r i p t i o n o f t h e v a r i o u s s a m p le s i s a s f o llo w s :
A.
by
" S t r a t c o l d " c o ld a c id t r e a t slu d g e produced
t r e a t i n g c r a c k e a g a s o l i n e s . R i c h f i e l d O il C o rp o ra tio n *
3.
L ig h t l u b r i c a t i n g
o i l a c i d t r e a t s lu d g e *
U nion O i l Company.
0*
F i f t y - f i f t y b l e n d o f s a m p le s B. a n d E .
D?
R i c h f ie l d O il C o rp o ra tio n a l k y l a t i o n p ro c e s s
a c i d w hich was s u b s e q u e n t l y u s e d f o r t r e a t i n g s t r a i g h t r u n
g a s o lin e s *
гл
" B la c k A c id " s l u d g e fro m g a s o l i n e a c i d t r e a t s *
U nion O i l Company*
F*
S h e l l O i l Company a l k y l a t i o n p r o c e s s a c i d
s u b s e q u e n tly u se d f o r t r e a t i n g s t r a i g h t run g a s o lin e s a t
t h e W i l s h i r e O i l Company R e f i n e r y .
F i g u r e 3 r e p r e s e n t s t h e c o r r e l a t i o n b e tw e e n th e
av e ra g e m o le c u la r w e ig h t o f each o f th e f i n a l p ro d u c ts
c
to
o
o
10
C\3
o
10
H
o
?X jcl
lO
o
o
3?
d e s c rib e d in F ig u re 2, and th e p e rc e n ta g e of c h lo rin e p r e s н
e n t in each o rg a n ic h a lid e m ix tu re .
The t a b u l a t e d r e s u l t s , w h ic h i n d i c a t e a n i n c r e a s e
i n m o l e c u l a r w e ig h t w i t h a d e c r e a s e i n c h l o r i n e c o n t e n t ,
a re as fo llo w s:
S lu d g e Sam ple
Per cent
C h lo rin e
A.
B.
0.
B.
E.
Fi
2*?
1 5 .2
1 6 .8
1 9 .3
1 9 .9
2 3 .2
. A v e ra g e
M o le c u la r W eight
475
380
375
Hot d e t e r m in e d
357
332
A n o th e r v e r y i n t e r e s t i n g p r o p e r t y c h a r a c t e r i s t i c o f
a d e c r e a s e i n c h l o r i n e c o n t e n t i s t h e i n c r e a s i n g te n d e n c y
o f th e p ro d u c t to m e lt.
W h ile i t was i m p o s s i b l e t o c o a g u l a t e
t h e y e llo w f l o o p r o d u c e d fro m s lu d g e F . by h e a t i n g i t i n h o t
w a t e r , th e m a t e r i a l , f r o m sam ple D. o b v i o u s l y m e l t e d t o fo rm
a y e llo w -b r o w n m a s s .
H ow ever, i n e v e r y c a s e when t h e m a t e r н
i a l was c o a g u l a t e d by h e a t t h e p r o d u c t was e x c e e d i n g l y
b r i t t l e when' c o l d .
The p r o p e r t y of a m a t e r i a l . t o m e l t when s u b j e c t e d
t o h e a t, i s e x c e e d in g ly v a lu a b le *
S i n c e t h i s te n d e n c y t o
m e l t i n c r e a s e s w ith a d e c r e a s e i n c h l o r i n a t i o n , t h i s i s
d e f i n i t e l y i n th e f a v o r o f t h e w e a k e r a c i d s l u d g e s w hich
a r e c h e a p e r an d more h i g h l y s p e n t .
38
A tte m p te d S y n t h e s i s o f G h lo ro D e r i v a t i v e s
A s - a f i n a l s t e p a few a t t e m p t s were made t o p r e p a r e
s y n th e tic o rg a n ic h a lid e s s i m i l a r to th e ch lo ro d e r iv a tiv e s
w i t h th e h o p e o f g a i n i n g some v a l u a b l e i n f o r m a t i o n c o n c e r n н
in g t h e i r n a t u r e .
An a l m o s t i n f i n i t e num ber of p r e p a r a t i o n s
c o u l d b e t r i e d , b u t t h i s p r o j e c t h ad to h av e i t s l i m i t a t i o n s
so much i n t e r e s t i n g w ork r e m a in s t o b e done o n t h i s p h a s e o f
t h e p r o b le m .
An a c c o u n t o f t h e few s y n t h e s i z i n g p r o c e s s e s t r i e d ,
a l l o f w h ich g av e n e g a t i v e r e s u l t s , i s a s f o l l o w s :
A.
D i e t h y l s u l f a t e was a g i t a t e d i n c o n t a c t w i t h
sodium h y p o c h l o r i t e .
R e s u l t ?- no p r e c i p i t a t e .
The
sodium h y p o c h l o r i t e was n e u t r a l i z e d d u r i n g t h e a g i t a t i o n .
R e s u l t ? no p r e c i p i t a t e .
B.
S o l u t i o n r e m a in e d w a t e r w h
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