Di-Organo Peroxide

7/25/2019 Di-Organo Peroxide

1/11


2/11

P a t e n t e d

S e p t . 1 1 . 2 , 1 9 5 0

2 , 5 2 2 , 0 1 6

U N I T E D

S T A T E S

P A T E N T

O F F I C E

G e o r g e H .

D e n i s o n , I n , San R a f a e l , and John E .

H a n s o n , R i c h m o n d , C a l i f . , a s s i g n o r s t o C a l i

f o r n i a

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

" S a n F r a n c i s c o ,

C a l i f . , a c o r p o r a t i o n o f Delaware

A p p l i c a t i o n D e c e m b e r

1 a ,

1 9 4 8 , S e r i a i N a ? Q Q ? d

' 1 3

C l a i m s . ( o m e n - e 6 1 0 )

l

The

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

t o

a

method o f

p r o d u c i n g d i - o r g a n o p e r o x i d e s and

p e r t a i n s more

p a r t i c u l a r l y

t o a method

o f

producing

d i - s a t u

r a t e d h y d r o c a r b o n p e r o x i d e s .

V a r i o u s

( i i - h y d r o c a r b o n p e r o x i d e s a r e u s e f u l

a s

g e r m i c i d e s ,

f u n g i c i d e s , b l e a c h i n g a g e n t s ,

p o l y

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

e t c . In p a r t i c u l a r , t h e

h i g h e r

m o l e c u l a r

w e i g h t

p e r o x i d e s ,

e s p e c i a l l y t h e

d i - s a t u r a t e d

hydrocarbon p e r o x i d e s , a r e d e s i r a b l e

a d d i t i v e s t o D i e s e l f u e l s f o r improving'the i g n i

t i o n

p r o p e r t i e s a s u s u a l l y e x p r e s s e d b y c e t a n e

numbers

7 ~

H e r e t o f o r e , v a r i o u s

p r o c e s s e s have

been pro

p o s e d

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

such p e r o x i d e s . H o w e v e r ,

t h e

p e r o x i d e s ,

e s p e c i a l l y - t h e d i - s a t u r a t e d hydro

c a r b o n p e r o x i d e s and t h e h i g h e r

m o l e c u l a r

weight

p e r

r i d e s , have not come i n t o

Widespread

u s e ' m a i n l y

b e c a u s e

t h e p r i o r methods n e c e s s a r i l y

employed

e x p e n s i v e c a t a l y s t s

o r e x p e n s i v e

a n d / o r

d i f i i c u l t l y

obtainable r e a c t a n t s . I n

s ome p r o c e s s e s

considerable d i ? i c u l t i e s are

encountered

in car

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

l a r g e o r commercial

s c a l e equipment such

a s m e t a l l i c

v e s s e l s .

Other

disadvantages o f t h e p r i o r

a r t

p r o c e s s e s a r e that

they r e s u l t i n

p o o r y i e l d ' s , a r e

hazardous t o c a r r y

out,

o r r e q u i r e complicated a p p a r a t u s .

I t

i s

t h e r e f o r e

a n

o b j e c t

o f

the

present

i n

vention

t o

provide a n

improved

a n d novel proc

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

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

t h e

above-mentioned

d i s a d v a n t a g e s .

Another'objectof

t h i s invention

s t o

p r o v i d e

a methodof t r e a t i n g

hydrocarbon hydroperoxide

with a c i d

under

certain mild

c o n d i t i o n s t o

con

v e r t

t h e

h y d r o p e r o x i d e to d i - h y d r o c a r b o n p e r

o x i d e .

A

f u r t h e r

o b j e c t i s t o p r o v i d e

aprocess-of

c o n v e r t i n g

r e l a t i v e l y

u n s t a b l e

h y d r o c a r b o n h y

d r o p e r o x i d e s o b t a i n e d f r o m a i r - b l o w i n g s a t u r

a t e d

h y d r o c a r b o n s t o more s t a b l e ( i i - h y d r o c a r

bon

p e r o x i d e s

by a c i d t r e a t m e n t under m i l d l c o n

ditions

'

A p a r t i c u l a r

o b j e c t o f

t h i s

i n v e n t i o n

i s

to

p r o v i d e a simple

and i n e x p e n s i v e

method o f pro

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

and p e r o x i d i c

c o m p o u n d s

from

s a t u r a t e d

hydrocarbons.

A p e c i a l o b j e c t o f

thisinvention i s

t o p r o v i d e

a

n o v e l

p r o c e s s

o f

making

( i i - ( h i g h e r h y d r o c a r ' e

h o n ) p e r o x i d e s w i t h o u t

t h e

n e c e s s i t y o f e m p l o y

expensivei materials.

_ I

" T h e s e ' a n ' d o t h e r o b j e c t s

w i l l

b e r e a d i l y l a p - v

1 0 .

20

25

40

45

a d v a n t a g e s

inherent

in

prior

art

processes.

p r e s e n t p r o c es s a l s o a f f o r d s t h e a d v a n t a g e s o f f

h i g h y i e l d s o f thedesired p r o d u c t s , o f s i m p l e

p a r e n t

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

t o

g e t h e r with t h e d r a w i n g ,

which

i l l u s t r a t e s

a

p r e

f e r r e d mode o f

c a r r y i n g

o u t

t h e

p r e s e n t i n v e n - .

t i o n .

o x i d e s , p a r t i c u l a r l y

s a t u r a t e d

h y d r o c a r b o n

h y

d r o p e r o x i d e s , by t r e a t m e n t w i t h a c i d under c e r

tain

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

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

t o d i e

h y d r o c a r b o n p e r o x i d e s . ' I n t h i s

m a n n e r ,

d i - h y

drocarbon

peroxides

c a n

be

obtained

i n a n

e f

? c i e n t and i n e x p e n s i v e manner w i t h o u t - t h e d i s

The

o p e r a t i v e

p r o c e d u r e s

and

o f

r e q u i r i n g s i m p l e

a p p a r a t u s .

An

e s p e c i a l l y e f f e c t i v e embodiment o f t h e

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

i n v o l v e s

a i r - b l o w i n g l r y d r o - .

c a r b o n s

t o

p r o d u c e h y d r o c a r b o n

h y d r o p e r o x i d e s _ , - ;

which

a r e

s u b s e q u e n t l y

t r e a t e d with a c i d

t o

o b -

t a i n t h e d i - h y d r o c a r b o n

p e r o x i d e s . A

a r t i c u l a r

f e a t u r e

o f t h e

p r e s e n t

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

t h e p r o c

e s s does

not r e q u i r e the

use o f

reactants other

t h a n

" h y d r o p e r o x i d e s and a c i d , t h e r e b y

a v o i d i n g

dependence u p o n expensive

reactants

s u c h a s

a l c o h o l s ,

k e t o n e s , a l d e h y d e s , h y d r o g e n p e r o x i d e

and

the

l i k e .

Thus,-the c o n v e r s i o n

i s

obtained

b y contacting

the hydro pero x ides i n p u re

form,

a s i d e from-preferred admixture

with

substan

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

s o l e l y w i t h

s u i t a b l e

a c i d s

o r aqueoussolutions

o f

a c i d s .

That

i s , the p r e s

ent pro cess i s carried

out

under

c o n d i t i o n s

wherein

thejhydroperoxides a nd a c i d

a r e

t h e o n l y

e s s e n t i a l

r e a c t a n t s .

R e s t a t e d ,

t h e acid i s t h e

s o l e e f f e c t i v e

agentfor t h e c o n v e r s i o n

o f a

hy

d r o c a r b o n h y d r o p e r o x i d e

d i r e ct l y t o

a

. d i - h y d r o

carbon

p e r o x i d e , 1 . e . , v t h e a u t o - c o n d e n s a t i o n

o f

h y d r o p e r o x i d e v t o , d i - h y d r o c a r b o n

p e r o x i d e

i s

ea

f e c t ' e d with hydroperoxide a n d acid a s t h e s o l e

reactants.

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

a d v a n t a g e s

o f t h e

p r e s e n t

p r o c e s s ,

v i t

i s

an

o u t s t a n d i n g

d e v e l o p

ment a n d m e r i t o r i o u s c o n t r i b u t i o n t o

' t h e a r t

o f

p r o d u c i n g d i i - h y d r o c a r b o n p e r o x i d e s . The p r e s

e n t - p r o ' c e s s i n v o l v e s a n unexpected

a n d

new

phenomenon o f c o n v e rs i o n o f h y d r o p e r o x i d e s t o

p e r o x i d e s

b y

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

a c i d u n d e r mild

c o n d i t i o n s . When such

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

i s c o m

b i n e d with

p r e p a r a t i o n

o f v t h e

h y d r o p e r o x i d e s

b y ' H l - i q u i d

p h a s e o x i d a t i o n '

o f h y d r o c a r b o n s i n

We h a v e f o u n d

t h a t


h y d r o p e r - _ _


3/11

2 , 6 2 2 , 0 1 6

3

accordance with

a

p r e f e r r e d embod iment o f the

p r e s e n t i n v e n t i o n ,

i t i s

found

t h a t ,

c o n t r a r y t o

the e x p e c t a t i o n s o f

the

p r i o r a r t , one c a n e i i i

c i e n t l y

and

e c o n o m i c a l l y

p r e p a r e d i - h y d r o c a r

bon

p e r o x i d e s

from hydrocarbon by s i m p l e op

e r a t i o n a l

s t e p s .

To i l l u s t r a t e

b r i e ? y t h e p r e s e n t i n v e n t i o n , a

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

paraf?ns

a n d n a p h th e n e s

h a v i n g

a n average chain

length

o f

t e n

carbon

atoms

w a s

air-blown

i n

l i q

u i d

phase

t o

o b t a i n

h y d r o p e r o x i d e s .

T h i s ,

i n t e r

mediate

product was

t r e a t e d

with

a c i d t o produce

d i - h y d r o c a r b o n

p e r o x i d e s

having t h e formula

Ri-QO-R2, wherein

t h e

average chain l e n g t h .

o f each

o f the

hydrocarbon

g r o u p s R1 a n d R2 i s

about ten carbon

atoms.

p e r o x i d e s

a r e w a t e r - i n s o l u b l e

l i q u i d s .

p r o d u c t s

were formed undervarying c o n d i t i o n s

o f

o p e r a t i o n

i n accordancewith

t h e

p r e s e n t

i n

v e n t i o n .

The

l i q u i d p e r o x i d e products are par

t i c u l a r l y

s u i t e d

f o r

u s e

a s

a _ _

D i e s e l f u e l

i g n i t i o n

Such ( i i - h y d r o c a r b o n

N

s o l i d

U K

1 0

4

been

g e n er a l l y s t a t e d a s m i l d ;

t h e

c o n d i t i o n s ma y

be s a i d t o

be

intermediate between

d r a s t i c

con

d i t i o n s

o f

high temperature a nd

v e r y

low

tem

p e r a t u r e below 0

F . That i s , t h e

temperature i s

maintained

r e l a t i v e l y l o w ,

i . e . , about r o o m tem

p e r a t u r e ,

and

t h e

time

o f

c o n t a c t

o f

t h e a c i d

and

p e r o x i d e s a t

t h e

r e a c t i o n temperature

i s r e l a t i v e

l y

s h o r t .

T h e

t r e a t i n g

temperature

may

be from

about 0

F .

o r

b e t t e r from

about

3 5

F .

u p t o

about

1 5 0 F .

although

t h e higher

temperatures

a r e a c c om

panied by c o n s i d e r a b l e d e c o m p o s i t i o n .

The

r e

a c t i o n i s exothermic and

u s u a l l y

t h e

tempera

t u r e i s maintained by c o o l i n g below about 9 5

F .

'Ordinarily a n intermediate range

o f

5 0 F . t o

g 8 5 F .

i s more

s u i t a b l e , a n d 6 0 F . t o 8 0 F .

i s

pre

20

accelerator. Whereas both theliydroperoxid e

in-

termediate p r o d u c t as

well

as the


p e r o x i d e improve t h e i g n i t i o n c h a r a c t e r i s t i c o f

a D i e s e l

f u e l

( i . e _ . , r a i s e ' i t s cetane number), the

d i - h y d r o c a r b o n p e r o x i d e p r o d u c t

i s

c o n s i d e r a b l y

more

s t a b l e than

the hydroperoxide

under s t o r

age c o n d i t i o n s ,


a s e f f e c t e d

by co n

t a c t

with v a r i o u s

agents

i n

commercial D i e s e l

fuels.

In accordance with t h e p r e s e n t

i n v e n t i o n ,

hy

drocarbon hydroperoxide i s converted t o d i - h y

drocarbon

peroxide

by

treatment under

mild

con

d i t i o n s

with aqueous a c i d having a d i s s o c i a t i o n

c o n s t a n t

o f g r e a t e r than

1 0 - 3 .

With weaker a c i d s

the

r e a c t i o n

does

not proceed

t o

a n

appreciable

e x t e n t . The r e a c t i o n d o e s not e v o l v e h y dr o g e n

peroxide

o r o x y g e n a n d e v i d e n t l y

i s

not s t r a i g h t

forward; consequently no mecha n i sm

i s

postu

l a t e d .

The

a c i d

i s

u s u a l l y employed

i n amounts rang

i n g from 0 . 1 - 1 . 0 , o r u p

t o about

1 . 5

mols

o f a c i d

per mol o f h y d r o p e r o x i d e .

The

l a r g e r amounts

w i l l

ordinarily

be em pl o yed with acids of lower

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

A

moi r a t i o o f

about

0 . 3 t o 0 . 5

i s preferred f o r a c i d s o f me d i um

concentrations

o f 60% t o 80% i n o r d e r t o

obtain

h i g h conver

s i o n , s u c h

a s

above about 80% t o

90%.

e r a l , a c i d i n s u ? i c i e n t amounts

a nd strength

t o

give

a

substantial

conversion

s u c h

as

50%

or

more,

w i l l

be employed.

S u i t a b l e

a c i d s

( a g e n t s

c a p a b l e o f

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

a b a s e ,

e .

g . , c a u s t i c )

h a v i n g

dissociation

c o n

s t a n t s g r ea t e r

than

1 0 * 3 i n c l u d e

t h e p r e f e r r e d

mineral a c i d s such a s s u l f u r i c , h y d r o c h l o r i c , phos

p h o r i c , n i t r i c

a nd

hydrobromic a c i d s . Other

a c i d s

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

i n c l u d e

a c e t y l

c h l o

r i d e , o x a l i c a c i d , d i m e t h y l s u l f a t e , e t c .

S u l f u r i c

a c i d i s u s u a l l y

p r e f e r r e d

s i n c e i t g i v e s b e t t e r

y i e l d s a n d

i s

c h e a p e r .

The

a c i d i s used i n a t

l e a s t r e l a t i v e l y c o n c e n t r a t e d aqueous s o l u t i o n ;

depending

somewhat o n the nature o f the a c i d

u s e d ,

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

o f a c i d p r e f e r a b l y ranges

from about 5 0 t o

98%

i n aqueous s o l u t i o n f o r

o b t a i n i n g

h i g h

y i e l d s , a l t h o u g h

l e s s

d e s i r a b l y

l o w

e r

concentrations s u c h as t o

20%

may be s o m e

times u s e d . W ith

concentrations

lower than

a b o u t 50%, c o n v e r s i o n i s u s u a l l y i n c o mp l e t e ,

while

t h e p r e f e r r ed range o f

a c i d concentration

g i v e s maximum o n v e r s i o n .

The conditions

o f the process

o f converting

h y

d r o p e r o x i d e s

t o

d i - h y d r o c a r b o n p e r o x i d e h a v e

In gen-

40

0 0

7 0

7 5

f e r r e c l .

For b e s t r e s u l t s ,

the

time o f

contact

a t r e a c

t i o n t e m p e r a t u r e s h o u l d n o t b e unduly p r o l o n g e d

and i s

u s u a l l y

l e s s

than 9 0

m i n u t e s , p r e f e r a b l y

below

6 0

minutes.

The

minimum

time

i s

d e t e r

mined by minimum mixing

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

consistent

with

m a i nt en a n c e of

the l o w

t em pera

t u r e s . Short

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

o f

the a c i d

phase

with

the organic phase o f from a few seconds

u p

t o

3

minutes, which a r e

e s p e c i a l l y

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

t o

avoid

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

are

most con

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

The l o n g e r

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

u s u a l l y

n e c e s s a r i l y

employed

i n

b a t c h w i s e

o p e r a t i o n .

The h i g h e r t h e

temperature t h e

s h o r t e r

t h e c o n t a c t

time

may e

s t a t e d

as the general

r u l e t o f o l l o w .

Hydrocarbon


which

may b e

c o n v e r t e d

t o i i i - h y d r o c a r b o n p e r o x i d e s i n

a c c o r d

ance

with

t h e p r e s e n t i n v e n t i o n a r e p r e f e r a b l y

s a t u r a t e d


h y d r o p e r o x i d e s , i n c l u d i n g

p a r a f f i n ,

naphthene and mixed p a r a f f i n - n a p h

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

o r t e r t i a r y

t y p e s .

S u i t a b l e para?ins from

which

the hydroperoxide

may

be d e r i v e d

a r e normal

p a r a f ? n s such

a s ,

f o r e x a m p l e , b u t a n e , p e n t a n e ,

h e x a n e ,

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

d e c a n e , d o d e c

a n e ,

t e t r a d e c a n e ,

h e x a d e c a n e , e t c .

and

t h e i r

branched chain isomers s u c h a s i s o b u t a n e , i s o

p e n t a n e s , i s o h e x a n e s ,

i s o h e p t a n e s ,

i s o o c t a n e s ,

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

o r

mixtures t h e r e o f .

Naphthene h y d r o p e r o x i d e s m a y

b e

d e r i v e d

from

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

c y c l o p e n t a n e , c y c l o h e x a n e ,

c y c l o

h e p t a n e , c y c l o o c t a n e , and

t h e

l i k e .

A l s o ,

t h e

hydroperoxide

d e r i v a t i v e s o f a l k y l

s u b s t i t u t e d

naphthenes

such

a s methyl

c y c l o p e n t a n e ,

dimeth

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

c l o p e n t a n e s , t r i m e t h y l c y c l o p e n t a n e s and t h e sim

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

may e

employed. The a l k y l

s u b s t i t u e n t s may

l s o

b e

p r o p y l ,

i s o p r o p y l ,

b u t y l ,

i s o b u t y l , t e r t i a r y

b u t y l ,

e t c . In c a s e o f t h e l o n g e r a l k y l s u b s t i t u e n t s ,

p a r t i c u l a r l y o f t h e branched c h a i n t y p e ,

t h e

hy

droperoxide g r o u p may be

attached

e i t h e r

o n

the

n a p hth en e r i n g a s i n the c a s e o f dimethylcyclo

pentane, f o r

example, o r o n

t h e

a l k y l c h a i n ,

t h u s

forming a naphthene s u b s t i t u t e d a l k y l

hydro

p e r o x i d e . P r e f e r r e d a r e t h e

secondary

a nd e s p e

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

h y d r o p e r o x i d e s ,

i . e . , wherein t h e

hydroperoxide

g r o u p , OOH, s

attached t o a secondary o r t e r t i a r y carbon atom,

respectively.

While s a t u r a t e d hydroperoxides a r e o r d i n a r i l y

employed

i n

the

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

w h e n

a

D i e s e l

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

d e s i r e d ,

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

containing ole?nic

bond s o r

aromatic

groups c a n

b e s i m i l a r l y

c o n v e r t e d

t o

t h e

( i i - h y d r o c a r b o n

p e r


4/11

2 , 5 2 9 , 5 0 1 . 1 6

o x i d e s

i n a c c o rd a n c e w i t h t h e p r o c e s s o r

t h e

p r e s

e n t i n v e n t i o n .

H y d r o p e r o x i d e s

d e r i v e d from o l e ~

?ns

s u c h

a s o c t e n e s ' ,

d e c e n e , 2

e t h y l h e x e i i e , e t c . ,

ma y

h u s

b e u s e d . H y d r o p e ro x i d e s ' l o f

i s o b u t y l e n e ,

a l k y l b e n z e n e s ' , such a s t o l u e n e , x y l e n e ,

e t h y l

b e n - i

' z e n e ,

i s o b u t y l

b e n z e n e ,

o c t y l b e n z e n e s , c e t y l

ben

z e n e s ,

e t c ,

a n d

s i m i l a r

s u b s t i t u t e d

n a p h t h a l e n e s

may

e employed. 1 _ _

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

t h e r e may

h e

u s e d h y d r o c a r b o n p e r o x i d e s which

a r e s u b s t i t u t e d t o s u c h minor e x t e n t t h a t t h e

s u b s t i t u e n t s

d o

n o t

a p p r e c i a b l y a f f e c t t h e e s s e n

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

c h a r a c t e r o f t h e h y d r o p e r o x i d e .

T h u s ,

t h e r e may b e e m p l o y e d

i n

t h e p r e s e n t

i n

v e n t i o n o r g a n o h y d r o p e r o x i d e s , w h e r e i n t h e o r

gano

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

bon

group

a s t h e main

c h a r a c t e r

o f

s u c h o r g a n o

r a d i c a l ,

w i t h o u t e x c l u d i n g t h e

p r e s e n c e

o f m i n o r

s u b s t i t u e n t s

s u c h .

a s

c h i o r o , p r o m o , n i t r o , e t c .

which a r e m e r e l y i n e r t o r which do n o t change

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

c h a r a c t e r

o r t h e o r

g a n o

r a d i c a l . F o r e x a m p l e , c h l o r o - t e r t i a r y

b u t y l

h y d r o p e r o x i ' d e , b r o m o 7 t e r t i a r y - b u t y 1 h y

d r o p e r o x i d e , a n d a n a l o g o u s h y d r o p e r o x i d e s d e

r i v e d f r o m 1 , l ~ 4 d i b r o m o - 2 ~ m e t h y l p r o p a n e , 1

c h l o r o e l - b r o m o - 2 - m e t h y l

p r o p a n e , 1 , 2 - d i c h l o r o

2 , 3 e d i m e t h y l b u t a n e , - 1 - ? u o r o - 2 - m e t h y l p r o p a n e ,

l - ?uoro 3 - methyl b u t a n e , l - c h l o r o - Z - p h e n y l

p r o p a n e , l ~ b r o m o - 2 - b e n z y l

p r o p a n e ,

1 - c h l o r o e 2

n a p h t h y l

p r o p a n e , l - c h l o r o - i l e c y c l o h e x y l p r o

p a n e,

1 , 1

~ dich1oropheny1-2f,2,2etrichloroethane,

a n d the

l i k e

a s w e l l

as t h e i r h om olo g ues

maybe

employed. 7

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

i s

a p p l i c a b l e t o t h e

i n

d i v i d u a l

h y d r o p e r o x i d e s o r m i x t u r e s

t h e r e o f .

S u i t a b l e

m i x t u r e s

may c o n t a i n , f o r e x a m p l e , s e v

e r a l hydroperoxides o f

any

o ne o r m o r e

o f

the

v a r i o u s t y p e s s u c h a s p a r a l i i n , n a p h t h e n e " ,

mixed

p a r a ? i n - n a p h t h e n e

and

a r o m a t i c

h y d r o p e r o x i d e s .

S u i t a b l e h y d r o p e r o x i d ' e s may

b e d e r i v e d from

v a r i o u s

p e t r o l e u m


f r a c t i o n s ,

s u c h

a s

s t r a i g h t - r u n

g a s o l i n e s which

may o n t a i n

both

p a r a i ? n s

and

n a p h t h e n e s ,

o t h e r

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

t i l l a t e s , e . g . ,

f r a c t i o n s

h a v i n g

A S ' I I M

50% b o i l i n g .

p o i n t

w i t h i n t h e range 2 0 0

t o

4 5 0 F .

o r

3 2 5 t o

650 F . ,

etc.

7 , I .

W h i le a n i n d i v i d u a l hydroperoxide alone may

be

r e a d i l y

c o n v e r t e d

t o a

di-hydrocarb0n p e r o x i d e

i n

accordance with

t h e p r e s e n t

i n v e n t i o n ,

the

more a c t i v e pure

h y d r o p e r o x i d e s ,

e s p e c i a l l y those

o f

lower

molecular W e i g h t , c a n

be

d i l u t e d

with

a

s u b s t a n t i a l l y i n e r t s o l v e n t , such

a s

a

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

such a s

p e n t a n e , hexane, e t c ,

o r

l i g h t o i l ,

such

a s p a l e o i l , k e r o s e n e , e t c , i n o r d e r

t o

c o n t r o l more

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

O r d i n a r i l y , a 5 5 0 % ,

p r e f

1 0

30

3 5

4 0

e r a b l y

5 - ' 2 5 % , s o l u t i o n o f h y d r o p e r o x l d e s i n a_

d i l u e n t i s

employed

i n o r d er t o o b t a i n

e a s i l y

c o n f

t r o l l a b l e

a c i d - t r e a t i n g

c o n d i t i o n s a n d / o r h i g h

conversion

_

The

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

i s e s p e c i a l l y s u i t e d

f o r pre

p a r i n g

s t a b l e ' c e t a n e e i m p r o v i n g D i e s e l f u e l a d d i

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

w e i g h t

h y d r o

c a r b o n h y d r o p e r o x i d e s h a v i n g

a t

l e a s t 8

c a r b o n

atoms

and up t o a b o u t

1 8

c a r b o n

atoms

i n

t h e

hydrocarbon c h a i n . .

The h y d r o p e r o x i d e s .

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

f e e d s t o c k

f o r

t h e

p r e s e n t

p r o c e s s may g e n e r a l l y

b e . m ' e p a r e d v

i n any s u i t a b l e manner. The p r o c e s s o f o b t a i n i n g

h y d r o p e r o x i d e s by t r e a t i n g a n a l c o h o l w i t h h y -

d r o g e n

p e r o x i d e and a n h y d r o u s

s o d i u m

s u l p h a t e

i s

d e s c r i b e d i n

P a t e n t N o . 2 , 2 2 3 , 8 0 7 ; I n

a c c o r d

60

5 .

6

a n t e w i t h

P a t e n t

N o . 2 , 3 8 3 , 9 1 9 , ' t e r t i a r y a l k y l h y

d r o p e r o x i d e s

m a y b e

r e c o v e r e d

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

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

a l i p h a t i c

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

c a r b o n

atomwith

an

oxygen-containing

g a s

and

i n

t h e

p r e s e n c e o f hydrogen

b r o m i d e . Patent

N o .

2 , 4 3 0 , 8 6 4

d i s c l o s e s

a method o f

o b t a i n i n g

pure

n a p h t h e n e , h y d r o p e r o x i d e ' s

b y

l i q u i d p h a s e o x i d a

t i o n o f

n a p h t h e n e s .

S c h u l t z e t a l . P a t e n t s

2 , 3 1 7 , 9 6 8 and 2 , 3 6 5 , 2 2 0

d i s c l o s e

a m o r e v g e n e r a l

method o f l i q u i d p h a s e

o x i d a t i o n

o f p e t r o l e u m

d i s t i l l a t e s

c o n t a i n i n g , f o r

e x a m p l e ,

b o t h . p a r a f l i n s

a n d .

n a p h t h e n e s ,

t o

p r o d u c e o x y g e n a t e d hydro

_ :

carbons,

i n wh i c h

the

chemically

r e a c t i v e o x y g e n

c o n t e n t

i s e x p r e s s e d i n terms o f oxygen f a c t o r .

In

s u c h

oxidation

p r o c e s s e s i t

i s

d e s i r a b l e t o

p u r i f y

t h e

f e e d m a t e r i a l by removal o f ox i d a t i o n

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

o t h e r m a t e r i a l s which m a y

have

d e l e t e r i o u s action o n hydroperoxides,

e . g . ,

sulfur

a n d '

nitrogen-compounds,

m a n y

n a t u r a l l y o c c u r

r i n g

s u l f u r , n i t r o g e n , o x y g e n - c o n t a i n i n g com

pounds.

.

A p a r t i c u l a r l y

a d v a n t a g e o u s

f e a t u r e o f t h e

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

r e s i d e s i n

p r e p a r i n g d i - h y d r o

c a r b o n p e r o x i d e s from h y d r o c a r b o n s , e s p e c i a l l y

s a t u r a t e d hydrocarbons. S u c h

p r o c e s s

i n v o l v e s

l i q u i d . phase o x i d a t i o n o f s u i t a b l e hydrocarbons

with a n

oxygen-containing

gas

u n d er c o n t r o l l e d

c o n d i t i o n s

and t h e r e a f t e r

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

a n t

i h y d r o p e r o x i d c - c o n t a i n i n g

p r o d u c t t o

a c i d

treatment under c e r t a i n m i l d t r e a t i n g c o n d i t i o n s

t o p r o d u c e ( i i - h y d r o c a r b o n p e r o x i d e s . T h i s p r e s - i

ent

process c o n s t i t u t e s a n imp r o v ement

over

the

Schultz

e t

a 1 .

p r o c e s s

o f

the aforementioned

P a t e n t s

2 , 3 1 7 , 9 6 8

and

2 , 3 6 5 , 2 2 0 . Therebyfthe

o c t a n e - improving h y d r o p e r o x i d e -

c o n t a i n i n g

product

o f

Schultz e t a 1 . i s converted

t o

s u p e r i o r

octane -

i m p r o v i n g di -


peroxides,

wh i c h are m o r e

s t a b l e i n

storage u p o n admixture

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

base

f u e l s

a n d w h i c h

are

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

l e s s c o r r o s i v e . In

g e n e r a l , t h e

d i

hydrocarbon

p e r o x i d e s

produced from hydrooar~

bon s in

t h i s

m a n n e r

are

low

i n c o s t ,

permanent

and

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

and

without a d v e r s e q u a l i

t i e s from t h e s t a n d p o i n t

o f

m a r k e t a b i l i t y ,

and

where u s e d t o promote i g n i t i o n , o f c o n s i s t e n t l y

h i g h

i g n i t i o n

q u a l i t y .

Where t i s desired t o p r o d u c e a n a d d i t i v e f o r

improving

t h e

i g n i t i o n q u a l i t i e s ,

1 .

e . ,

c e t a n e

num

b e r , o f D i e s e l

f u e l s

a nd the l i k e ,

t h e p r e s e n t

i m

provement p r o c e s s i s


a p p l i c a b l e

e i

t h e r in conjunction with the process

o f

Patent N .

2 , 3 6 5 , 2 2 0 , w h e r e i n c h a r g - i n g s t o c k s c o r r e s p o n d i n g

t o v a n ASTM

50% b o i l i n g

p o i n t w i t h i n

t h e

range

325 t o 6 5 0

F .

a r e

employed,

o r Patent

No.

2 , 3 1 7 , 9 6 8 ,

wherein

t h e c h a r g i n g

s t o c k b o i l s w i t h

i n

the range 200

t o 4 5 0 F . For t h i s purpose the

hydrocarbon o i l

t o

be

o x i d i z e d

s h o u l d be

f r e e

from

l a r g e

p r o p o r t i o n s

o f a r o m a t i c

r i n g

s t r u c t u r e s a nd

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

d r o c a ' r b o n s .

While s t r a i g h t - r u n

p e t r o l e u m

d i s

t i l l a t e s are often

used

t o

advantage a s i n i t i a l ma

t e r i a l s ,

f r a c t i o n s

c o n t a i n i n g

l a r g e

p e r c e n t a g e s

o f

branched c h a i n compounds a r e u s u a l l y

p r e f e r r e d .

O r d i n a r i l y , p e t r o l e u m

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

t r e a t e d

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

re?ned b e f o r e

o x i d a

t i o n f o r

optimum

r e s u l t s . O i l s

c o n t a i n i n g

h i g h

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

y i e l d i n g o c t a n e - i m p r o v i n g

compounds

t h a n

a r e

o i l s o f h i g h p a r a f h n i o i t y ,

a l t h o u g h

t h e t r e a t m e n t

7 5 ' o f - o i l s o f ' h i g h - a r o m a t i c c o n t e n t w i t h r e l a t i v e l y


5/11

2 , 5 2 2 , 0 1 6

7

s t r o n g

s u l f u r i c

a c i d

o r a n e q u i v a l e n t chemical r e

agent

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

with l i q u i d

s o l v e n t s

such a s

l i q u i d

s u l f u r

d i o x i d e ,

p h e n o l , a n i l i n e , f u r

f u r a l , n i t r o b e n z e n e and

t h e l i k e

i n

removing

aromatic components

f o r reducing

t h e i r concen

t r a t i o n ,

s u ? i c e s

t o

improve

t h e i r

a m e n a b i l i t y

t o

treatment i n a c c o r d a n c e w i t h the invention.

Av c o n v e n i e n t

means

of following

t h e c o u r s e o f

the

o x i d a t i o n

p r o c e s s r e s i d e s

i n t h e

oxygen f a c

t o r determination. The oxygen f a c t o r " o f a n

o i l

i s

determined a s

f o l l o w s :

A t o 1 0

m l .

sample

o f o i l a t approximately 6 8 F . i s a c c u r a t e l y

p i p e t

t e d

i n t o

a 2 5 0

m l . g l a s s stoppered ? a s k . 2 0 ml. o f

a

mixture

c o n s i s t i n g o f 6 0

v olume

per cent o f

C .

P .

g l a c i a l

a c e t i c a c i d and 40 volume per cent

o f chloroform a r e added t o the o i l , f o l l o w e d by 2 . 0

m l .

of

a saturated aqueous s o l u t i o n o f potassium

i o d i d e . The mixture i s shaken

v i g o r o u s l y

f o r 3

minutes

a nd

then d i l u t e d with about

5 0

m l . o f

d i s t i l l e d w a t e r .

The

l i b e r a t e d

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

with 0 . 1

normal

standardized

sodium

t h i o s u l f a t e

s o l u t i o n ,

adding s t a r c h

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

b e f o r e

t h e

end p o i n t i s r e a c h e d . C o n s i d e r a b l e shaking i s

necessary near

the end o f

the

t i t r a t i o n . O x y g e n

f a c t o r = ( t i t e r , _ i n m l . > < n o r n i a l i t y o f t h i o s u l f a t e x

1120)

/

(vol ume

of sample in

ml.)

The o x i d a t i o n s t e p o f the p r o c e s s i s

p r e f e r a b l y

c a r r i e d out within the temperature range

o f 2 5 0

F . t o 3 5 0

F .

P r e f e r a b l y , the oxidation i s c a r r i e d

out

with the a i d o f

a

small am o u nt o f feed stock

f r om the previous run. An am o u nt o f feed stock

between about 0.5%

a nd

5% i s u s u a l l y d e s i r e d .

With t h e petroleum d i s t i l l a t e s r e f e r r e d t o h e r e i n

above a n d mentioned i n the

Schultz

e t a l . p a t e n t s ,

a t m o s p h e r i c

p r e s s u r e i s n o r m a l l y .

s u i i i c i e n t ; w i t h

o t h e r f e e d s ,

e s p e c i a l l y

l o w e r

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

b o n s , superatmospheric p r e s s u r e s ,

e .

, g . ,

u p

t o

3 5 0 - 4 0 0 atmospheres,

p r e f e r a b l y

below

1 0 0

a t

m o s ' p h e r e s ' , may b e

employed.

The o x i d a t i o n

with a n o x ygen - co ntain in g gas s u c h as a i r i s c o n

t i n u e d f o r a time not

m a t e r i a l l y

l o n g e r than i s

necessary t o g i v e a n o i l o f maximum o x y g e n fac

t o r

o b t a i n a b l e ,

a n d

a l s o

t o

prevent und u e forma

t i o n "

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

In

g e n e r a l

t h e

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

t o produce

an

o x ygen f a c t o r o f a t l e a s t

2 5 0

a n d

preferably

a b o v e

800

a n d a - neutralization

n u m b e r

o f not

morethan

1 5 .

Itis u s u a l l y most

d e s i r a b l e

f o r

b e s t conversion o f hydroperoxides t o employ an

e x c e s s o f

oxygen-containing

g a s . For

example,

s u f f i c i e n t a i r

i s employed s o that the e i i i u e n t gas

i s

not c o m p l e t e l y d e o x y g e n a t e d .

For

i n c r e a s e d

y i e l d i t i s sometimes

d e s i r a b l e

t o

c a r r y out t h e

o x i d a t i o n i n

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

r e a c t i n g

agent s u c h a s a l k a l i n e earth

metals

o r c o m p o u n d s

o f

a l k a l i n e

e a r t h

m e t a l s ,

a l k a l i

m e t a l s ,

i r o n

group

metals and metals o f

the

right-hand column o f

group I I

o f t h e

p e r i o d i c t a b l e which form

s a l t s

with a c i d s produced'during t h e

o x i d a t i o n ; such

a g e n t s , e . ' g . , a l k a l i metal carbonates and bicar

bonates

o r d i l u t e

aqueous

s o l u t i o n s o f

a l k a l i metal

hydro x ides are used i n suf?cient am o u nt

to

pre

vent

accumulation

o f

a p p r e c i a b l e amounts o f

a c i d s

which

tend t o promote

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

a c t i o n s .

Neutralization

c a n l i k e w i s e be e f f e c t e d

i n a separate stream withdrawn from the

oxida

t i o n

chamber and

returned

t h e r e t o

a f t e r t r e a t

ment. The p a r t i a l l y

o x i d i z e d

o i l

should

not be

allowed t o rem ain

a t o r

near

o x i d i z i n g

tempera

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

length

o f

time subse

quent

t o

t h e attainment

o f

t h e

d e s i r e d

oxygen

f a c t o r

due

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

wh i c h c o n

t i n u e a t the expense o f the d e s i r e d product. I t i s

t h e r e f o r e

o f

importance t o q u i c k l y

c o o l

the

o i l a s ,

f o r e x a m p l e , b y q u e n c h i n g w i t h

w a t e r

t o a tem

1 0

15

20

25

40

45

50

55

60

65

7 0

7 5

8

p e r a t u r e b e l o w -t h a t a t which

s e c o n d a r y

r e a c t i o n s

t a k e p l a c e

r a p i d l y ,

n a m e l y ,

t o

a

temperature

b e

low about

2 5 0

F . a n d p r e f e r a b l y a s low

a s 1 0 0

F .

I t i s sometimes d e s i r a b l e t o w a s h t h i s p a rt i a l l y

o x i d i z e d o i l

with d i l u t e c a u s t i c s o l u t i o n ( s u c h a s

u p

t o

5%

c a u s t i c ) t o

remove

a c i d i c

substances

a n d

s a l t s

or

soaps

o f

organic

a c i d s before

pro

ceeding

with

the

subsequent treatment.

A

5%

aqueous c a u s t i c s o l u t i o n i n

an

amount

e q u i v a l e n t

t o about that t h e o r e t i c a l l y r e q u i r e d t o e f f e c t n e u

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

u s e d . A

m a t e r i a l l y

s t r o n g e r

c a u s t i c

s o l u t i o n

tends t o d e s t r o y o r r e

move

the

desired hydroperoxides, as does

a

sub

s t a n t i a l e x c e s s o f the c a u s t i c . In most c a s e s i t

i s

advantageous t o d i s p e n s e with t h e c a u s t i c

wash

and p r o c e ed w i t h t h e s u b s e q u e n t t r e a t m e n t .

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

p a r t i a l o x i d a t i o n , q u e n c h i n g a n d c a u s t i c w a s h i n g

a

c h o se n

feed stock

a s

w e l l as analytical meth

ods f o r the

determination

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

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

n u m b e r

are

given

i n

U.

S .

Patents

N o s . 2 , 3 6 5 , 2 2 0

and

2 , 3 1 7 , 9 6 8 t o S c h u l t z e t a l .

I t

i s o r d i n a r i l y

not

advantageous t o concen

t r a t e the hydroperoxides,

n u c h a s

obtained from

the aforementioned o x i d a t i o n

p r o c e s s ,

b e f o r e

t h e

s u b s e q u e n t a c i d t r e a t m e n t . S u c h c o n c e n t r a t i o n

i s

sometimes d e s i r a b l e and may be

e f f e c t e d by

f r a c t i o n a l

d i s t i l l a t i o n , p r e f e r a b l y

under

r e d u c e d

p r e s s u r e , by

s o l v e n t

e x t r a c t i o n , such

a s

with 90%

a q u e o u s methanol or by

c h em i c a l

means

or

com

binations

o f

s u c h methods. A s chemical m e a n s

the hydroperoxi des may be extracted o r p r e c i p i

tated a s s a l t s

by treatment with

a n

a l k a l i

o r

b a s i c

metal

com po und s,

su c h a s a l k a l i n e earth

metal

h y d r o x i d e s

o r

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

from

the

mixture

the

s a l t

may

be

d i s s o l v e d

i n

water a n d acidi?ed with

d i l u t e a c i d

t o reform

t h e h y d r o p e r o x i d e .

Referring n o w to

t h e a c i d

t r e a t i n g s t e p : The

p r e f e r r e d

f e e d t h e r ef o r

i s

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

above

d e s c r i b e d

l i q u i d phase o x i d a t i o n o f s u b s t a n t i a l l y

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

unconcentrated

feed

mixture

usually has a

hydroperoxide

con

t e n t o f about

8 t o

15%,

although

hydrocarbon

s o l u t i o n s

r e s u l t i n g from oxidation

o r

from d i s

s o l u t i o n

o f

hydroperoxides i n hydrocarbons may

contain g r e a t e r o r

smaller amounts

o f

hydro~

peroxides s u c h a s

from

5 t o 25% a n d be e f f e c

t i v e l y t r e a t e d by a c i d . As n o t e d a b o v e , t h e

hy

droperoxides

are p r e f e r a b l y i n d i l u t e s o l u t i o n s f o r

t h e a c i d

t r e a t i n g

s t e p .

The

i l l u s t r a t i v e

f e e d s t o c k

c o n t a i n i n g 8

t o 15% h y d r o p e r o x i d e s

( h a v i n g

an

average of

ten carbo n atoms) w i l l h a v e

a n o x y

gen f a c t o r

ranging

f r om

800

t o 1 5 0 0 . To

cause

c o n v e r s i o n o f the hydroperoxides

t o

dihydrocar

bon p e r o x i d e s i n such

a

f e e d s t o c k , i t

has

been

found i n

g e n e r a l that

treatment with between 0 . 1

a n d 0 . 7 5

p o u n d

o f 50% t o 98% a c i d ,

e . g . ,

s u l

f u r i c a c i d , p e r g a l l o n o f

t h e

p a r t i a l l y o x i d i z e d

unconcentrated f e e d

s t o c k

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

I t has f u r t h e r been found

t h a t

under t h e mild

Operating c o n d i t i o n s ,

s u c h a s

a t

a temperature o f

6 0 t o

8 0 F . , e t c . , a s hereinabove s e t

f o r t h ,

a

t r e a t m e n t w i t h a b o u t

1 A ;

t o

1 % ;

pound o f 75%

s u l f u r i c

a c i d

p e r g a l l o n o f t h e above

f e e d

g i v e s

optimum

r e s u l t s .

While

f o r

the

purpose

o f

ob

t a i n i n g

optimum

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

time t h e more

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

a n d / o r

h i g h e r

a c i d t o

h y d r o

peroxide a r e u s e d ,

lower

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

the

lower

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

ma y

b e e m p l o y e d . Thus,

f o r con

v e r s i o n s o f ; above about 50%,

the

mol r a t i o

o f

a c i d t o hydroperoxide may range from 0 . 1

t o 1 . 0 ,

or u p t o 1 . 5 mols o f

acid

per mol o f

hydroper

o x i d e . F o r

e x a m p l e , t h e f o l l o w i n g

t a b l e

p r e s e n t s


6/11

2,522,015

data

showing

t h e

r e s u l t s o f

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

s t o c k ,

such a s r e f e r r e d t o a b o v e ,

having

a n oxygen f a c

t o r o f 1 0 7 0 a nd

hydroperoxide

content o f

about

10% o r about 2 . 2 mols

p e r

g a l l o n , the hydro

peroxides

having

a n average

o f about

ten

carbon

atoms.

The

r e a c t i o n

temperature

w a s

maintained

a t about 7 0 F . a n d

s u l f u r i c

a c i d o f 75% concen

t r a t i o n

w a s used

a t

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

TABLE I

Amount

f M01 A c i d ] Oxygen

A c i d

( L b s J Mol h y d r o - F a c t o r o f

g a l . o f f e e d p e r o x i d e P r o d u c t

s t o c k )

0 . 2 5 0 . 4 7 8 1 6 2

0 . 1 6 5 0 . 3 1 7 1 7 . 7

0 .

1 0 0 .1 9 1 3 0 3

0 .

0 5 0 .

0 9 5 4 5 2

I t

w i l l

be

seen that the

optimum vminimum

amo unt o f a c i d correspondsto a r a t i o o f about

0 . 3

mols

o f a c i d

p e r

mol

o f h y d r o p e r o x i d ' e .

P r e f e r a b l y t h e

t r e a t i n g time

i s

kept t o a min

imum w e l l

below

the 9 0 minutes

noted above i n

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

a m p l e ,

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

o x y g e n a t e d p r o d u c t

produced

from

a

mixed

para?in-naphthene p e

troleum

d i s t i l l a t e

b o i l i n g i n

the

range

3 0 8

t o

3 6 6

F .

the s l u d g e which

i s

a n

o i l - i n s o l u b l e material

f o rme d when u sin g a

contact

time o f over

20

-minutes a n d ' w h i c h may be

separated

a n d d i s

posed

o f , i s

p r a c t i c a l l y e l i m i n a t e d by

l i m i t i n g t h e

contact time t o

l e s s

than about 3

minutes.

For c o n t r o l

p u r p o s e s i t

h a s been a s c e r t a i n e d

t h a t

w h e n

t h e

temperature

i s

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

above

1 5

20

25

30

indicated

the reduction

in the value of the o x y g e n

factor serves as

a c r i t e r i o n

for the

m a i nt en a n c e

a nd attainment o f optimum c o n d i t i o n s f o r t h e

a c i d treatment. In general i t has

been

observed

t h a t i n t r e a t i n g f e e d s t o c k s o b t a i n e d from l i q u i d

phase o x i d a t i o n i t i s not a d v i s a b l e t o

attempt

t o a c i d t r e a t to e x t i n c t i o n o f

oxygen

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

the

a d d i t i o n a l treatment

necessary

t o

chemically

e?ect the

l a s t

p o r t i o n s

o f oxygen f a c t o r respon

s i v e

c om po u nds t e n d s t o cause

decomposition

o f

the p e r o x i d e s .

Hence,

c o n d i t i o n s

o f

a c i d t r e a t

ment

a r e p r e f e r a b l y adjusted t o g i v e a r e d u c t i o n

t o

about 1 0

t o

20%

o f

the

o r i g i n a l o x y g e n

fac

t o r

v a l u e .

c o n t a i n i n g

8%

hydroperoxides

having

a n

average

o f ten

carbon

atoms

in the

m o l e c u l e ,

s u c h

con

v e r s i o n y i e l d s a

r e a c t i o n

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

about

5% o 6 1 / 2 % di-hydrocarbon p e r o x i d e .

B at c h w i s e

acid treatment c a n

be

a pplied

to

h y d r o p e r o x i d e - c o n t a i n i n g

m i x t u r e s

s u c h a s

t h e

above~mentioned

p a r t i a l l y

oxygenated i l .

I t has

been

found t h a t

t h e y temperature

may

be r e a d i l y

c o n t r o l l e d

t o

t h e d e s i r e d v a l u e , f o r example, by

adding

t h e

t o t a l s u l f u r i c

a c i d

employed i n s e v ~

e r a l

d u m p s with a c o l d water w a s h between each

dump

t o

counteract

the

heat

evolved i n the r e

a c t i o n .

When r e a t i n g the

above-mentio-ned

o x y

g e n a t e d o i l f e e d s t o c k t h e 1 % ; p o u n d p e r

g a l l o n

o f s u l f u r i c - a c i d w a s

conveniently

added i n

four

d ump s

t o g e t h e r

with

t h e

i n t e r m e d i a t e c o l d

water

washes f o r c o o l i n g .

Instead

o f

using

c o l d water

washes

f o r

c o o l i n g , e x t e r n a l c o ol i n g and/or r e

f r i g e r a t i n g

c o i l s

i n s e r t e d

i n t o t h e

mixing

c h am

b c r may be

employed t o c o n t r o l

the tempera ture.

The a c i d t r e a t e d o i l i s p r e f e r a b l y

Washed

w i t h

water a f t e r the l a s t a c i d treatment

t o

remove

e x c e s s

a c i d , i s

then Washed with

d i l u t e

c a u s t i c

u n t i l n e u t r a l , and ? n a l l y w i t h w a t e r u n t i l

s a l t

and c a u s t i c - f r e e .

I t i s

p r e f e r a b l e

t o u s e a

10%

F o r example,

in treating. a

feed stock

60

7 0

10

e x c e s s

o f 5%

a q u e o u s

c a u s t i c

o v e r

t h a t r e q u i r e d

f o r

n e utr al iz atio n.

Mixing o f t h e

a c i d

and hydroperoxide c o n t a i n

i n g

f e e d

f o l l o w e d

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

i n

a

c o n t i n u o u s

manner

h a s

been found p r e f e r a b l e i n

order

t o

o b t a i n

minimum

contact

t i m e .

Various

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

mixing

n o z z l e s ,

e t c . , m a y b e e m p l o y e d . A n e ? i c i e n t

s e p a r a t o r

o r

s e r i e s o f s e p a r a t o r s of v a r i o u s de

s i g n s

may b e u s e d , f o l l o w e d by c o n t i n u o u s water

w a s h o f

t h e

non-aqueous p e r o x i d e p h a s e . Ex

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

m a y

b e

a p p l i e d t o t h e

mixer

i t s e l f and/or t o t h e f e e d streams t o t h e mixer

as w e l l as the mi x ed e i i i u e n t stream in order t o

maintain t h e d e s i r e d temperature

p r e f e r a b l y a t

6 0 t o 8 0 F .

The

water-washed

product i s

then

c a u s t i c

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

o r b a t c h w l s e ,

a s noted h e r e i n a b o v e . A p a r t i c u l a r l y

e f f e c t i v e

p r o c e d u r e

f o r

o b t a i n i n g optimum

s h o r t

c o n t a c t

t i m e

and

h i g h

y i e l d s w i t h o u t

a p p r e c i a b l e

d e l e t e

r i o u s

s i d e

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

t h e

s t e p s o f

mixing

the hydroperoxide a n d

a c i d by

m e a n s o f

a

spray

n o z z l e ,

then

i m m e d i a t e l y

p a s s i n g t h e

r e s u l t a n t

mixture

t o

' a s e t t l e r ,

from which

the a c i d

l a y e r

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

d r a w n

o f f .

With immediate d i l u

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

with

w a t e r ,

s l u d g e

f o r m a t i o n

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

v e n t e d .

With l o n g

" i n t e r v a l s b e f o r e

d i l u t i o n ,

s l u d g e tends t o be formed i n the a c i d .

The

t r e a t e d

upper

l a y e r a s immediately s e p a r a t e d

from

the

acid

i s

appreciably

reduced i n o x y g e n

f a c t o r .

U p o n s t a n d i n g o u t o f c o n t a c t w i t h t h e

acid

l a y e r

f o r

a short

t i m e ,

s u c h

as 5- 20 minutes,

p r e f e r a b l y a b o u t 1 0 m i n u t e s , t h e oxygen f a c t o r

o f t h e s e p a r a t e d

upper l a y e r

d r o p s

f u r t h e r t o

t h e

d e s i r e d

low

v a l u e ,

showing

c o m p l e t i o n

o f

t h e

r e a c t i o n .

T h e n h e

product s

water- and

c a u s t i c

washed.

Where

the h y d r o p e r o x i d e s have

been

concen

t r a t e d , s u c h

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

o f

t h e

l i q u i d p h a s e

o x i d a t i o n p r o d u c t

t o y i e l d a mix

ture h a v i n g a n increased o x ygen f a c t o r

o f

at

l e a s t 1 0 0 0 , p r e f e r a b l y

about

3 0 0 0

t o 7 0 0 0 ,

o r

u p

t o 1 5 , 0 0 0 ,

t h e c o n c e n t r a t e v may be a c i d - t r ea t e d a s

d e s c r i b e d a b o v e,

e x c e p t

a

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

g r e a t e r

am o u nt

o f a c i d per g a l l o n o f

f e e d

s t o c k i s used

t o

o b t a i n t h e h e r e i n b e f o r e - i n d i c a t e d proper a c i d

hydroperoxide r a t i o and

t o g i v e a

?nal product

having

a n

oxygen

f a c t o r

not g r e a t e r than about

20% 0 f t h e oxygen f a c t o r o f t h e c o n c e n t r a t e .

W h e r e

the hydroperoxides

a r e

separated

from

t h e

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

i . e . , by

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

s a l t s ,

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

t h e h y d r o p e r ' o x i d e and

c o n v e r s i o n

t o d i - h y d r o

carbon p e r o x i d e s

can becarried

o u t i n

one opera

t i o n by

e m p l o y i n g

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

form

t h e

h y d r o p e r o x i d e

from t h e

s a l t p l u s

enough a c i d

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

e l l - h y dr o c a r b o n peroxide.

For

s ome purposes,

the (ii-hydrocarbon per

o x i d e c o n t a i n i n g product thus o b t a i n e d i n t h e

a b o v e - d e s c r i b e d b a t c h w i s e o r

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

t r e a t i n g

methods

i s ready f o r

u s e ;

f o r

example,

when

the

o i l feed

s t o c k chosen f o r

oxidation

i s

s u i t a b l e f o r use a s a D i e s e l f u e l , the product i s

n o w

a n

improved

D i e s e l

f u e l .

I f ,

however,

t h e

o i l f e e d s t o c k s e l e c t e d i s not

a

s u i t a b l e D i e s e l

f u e l

a s ,

f o r i n s t a n c e , by

r e a s o n

o f i t s

low b o i l i n g

range o r

i f

the

o b j e c t

i s

t o produce a

blending

agent

w h i c h may be ad d ed t o

' a

Diesel

f u e l

stock

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

o c t a n e number, t h e

a c i d - t r e a t e d

oxygenated o i l may be added t o a base

s t o c k

i n

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

octane number.


7/11

2 , 5 2 2 , 0 1 6

F

It isfrequently

d e s i r a b l e ,

however, t o o b t a i n

t h e ( i i - h y d r o c a r b o n p e r o x i d e s i n s u b s t a n t i a l l y

p u re

or m o r e concentrated form,

a n d in

s u c h

cases the

di-hydrocarbon

peroxides may be con

centrated by

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

o t h e r

s u i t a b l e

means,

f o r

e x a m p l e ,

by

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

a d s o r p t i o n

fractionation o r by combinations o f

such methods.

The hydrocarbonaceous m a t e r i a l s e p a r a t e d from

t h e d i - h y d r o c a r b o n

p e r o x i d e s

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

thereof may b e r e c i r c u l a t e d t o t h e

a i r - b l o w i n g

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

ment a s i s

t h e

o r i g i n a l

f e e d s t o c k , i n

order

t o

r e n d e r i t ' m o r e s u i t a b l e f o r

c o n v e r s i o n

t o hydro

p e r o x i d e s . In many a s e s i t w i l l be

found

p r e f e r

a b l e

t o

c o n c e n t r a t e

by

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

h i s

method

. i s i l l u s t r a t e d and more f u l l y d e s c r i b e d b e l o w .

Ordinarily,

i t i s preferable t o concentrate the

d i - h y d r o c a r b o n p e r o x i d e s by removing t h e r e l a

t i v e l y

l o w e r - b o i l i n g

m a t e r i a l from t h e m i x t u r e .

The p o r t i o n removed ma y c o n t a i n

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

o n l y

i n e r t

hydrocarbons

which

m a y

b e

r e c y c l e d

a f t e r

s u i t a b l e treatment t o t h e o x i d a t i o n s t e p o f

. t h e process or maybe otherwise

u t i l i z e d or d i s

c a r d e d . -

The

i s t i l l a t i o n r e s i d u e may vary b e

tween a b o u t 5%

and

40% o f

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

depending on c o n d i t i o n s o f p r e v i o u s

treatment

a n d expected u s e s ; f o r example, where the

u n

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

about

5-10%

p e r o x i d e s ,

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

may be c a r r i e d out u n t i l

only

about

2 0 % o f

t h e o r i g i n a l

volume remains i n

t h e s t i l l .

The

bottoms

remaining i n t h e s t i l l may contain

t h e


p e r o x i d e s

i n

amounts from

about 20-70% o r

more,

u s u a l l y o f the

order

o f

40% or i n s ome

c a s e s

t o

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

p e r o x i d e s . For

e x a m p l e , w h e n t h e

a c i d t r e a t

ment d e s c r i b e d

a b o v e

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

o f

the p r o c e s s i s

a p p l i e d t o

a hydroperoxide f e e d

d e r i v e d from l i q u i d - p h a s e o x i d a t i o n o f a hydro

carbon f r a c t i o n h a v i n g a n average

o f

ten carbon

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

peroxide-containing

o i l

w i l l

h a ve

a n

o x y g e n

f a c t o r o f

n o t

g r e a t e r than 6 0 0 and p r e f e r a b l y l e s s

than 3 0 0 . I t

has

been found

t h a t

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

by f r a c t i o n a l

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

may

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

a t

a

subatmospheric

p r e s s u r e , s u c h a s 10- 30mm.

o f mercury

or

l o w e r .

Satisfactory

pressures

are

determined by

t h e

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

t h e charging

s t o c k

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

In

g e n e r a l ,

a

higher

p r e s s u r e

i s ' u s a b l e with a l i g h t e r charging

s t o c k . The tem

p e r a t u r e

d e s i r a b l y

i s

maintained b e l o w 3 5 0 F . ,

p r e f e r a b l y

below 2 5 0 F . , and

e s p e c i a l l y

o f t h e

order

o f 2 0 0

F .

S o l v e n t

e x t r a c t i o n

may

be used

i n p l a c e o f

f r a c t i o n a l d i s t i l l a t i o n o r f o l l o w i n g

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

i n

order

t o further

concentrate the p e r o x i d e s . Al-

though

a

v a r i e t y

o f

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

may b e

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

a q u e o u s

a l i p h a t i c a l c o h o l s such a s

i s o p r o p y l a l c o h o l

e t c . ,

polyhydroxy a l c o h o l s such a s

e t h y l e n e

g l y c o l ,

g l y c e r o l , e t c . ,

e t h e r s and

e s t e r s o f t h e

l a t t e r

c l a s s

such a s d i e t h y l e n e g l y c o l , monomethyl

e t h e r ,

g l y c o l

d i a c e t a t e , e t c . , p y r i d i n e

and i t s

homo

l o g u e s , w a t e r - s o l u b l e k e t o n e s , such

a s

a c e t o n e , i t

i s

p r e f e r a b l e t o

use a q u e o u s methanol as

the

ex

t r a c t i o n a g e n t . The p e r o x i d e s may be e x t r a c t e d

from

t h e

m i x t u r e w i t h

7 5

t o 95%,

p r e f e r a b l y

about

90%,

aqueous

methanol

by

continuous o r

b a t c h w i s e e x t r a c t i o n . T h e r e a f t e r , t h e e x t r a c t

phase may

b e

d i l u t e d

with water

t o f r e e t h e

p e r o x i d e s a s a n

o i l y

l a y e r .

The

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

the

p e r o x i d e s from t h e

a q u e o u s

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

phase

may

a l s o

b e

c a r r i e d

o u t

by

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

p r e f e r a b l y

under r e d u c e d p r e s s u r e s , t o v a p o r i z e

t h e a l c o h o l and w a t e r . I f

d e s i r e d , t h e

e x t r a c t

s o

obtained may be

subjected

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

in

"

: 1 5

25

30

85

40

50

65

60

65

7 0

1 2

o r d e r t o

f u r t h e r

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

d i - h y d r o c ' a r b o n

peroxides.

As a

?nal

s t e p , the product may

e

wa s h ed with

a small

amo unt

o f c a u s t i c , s u c h a s

5 - 40%

c a u s t i c ,

f o r example 1

t o 2%

o f 15% c a u s t i c ,

and

then

water wash ed. In

case

the peroxide

c o n c e n

t r a t e i s

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

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

most

d e s i r a b l e , i n a d d i t i o n , t o water wash b e f o r e

t h e

caustic

wash ,

H

,

R e f e r r i n g t o t h e d r a w i n g ,

one

p r e f e r r e d em

bodiment

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

i s

c a r r i e d o u t

a s f o l l o w s : _ A s u i t a b l e

f e e d , such a s

a

petroleum

f r a c t i o n

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

p a r a ? i n s and

n a p h t h e n e s "

and b o i l i n g i n t h e r a n g e ~ o f 3 0 8 t o

3 6 6

F . i s i n t r o d u c e d v i a

l i n e

I through pump

a nd

l i n e 3

i n t o a n o x i d i z i n g

chamber, such

a s

o x i d i z e r 4 , f o r

c o n v e rt i n g t h e

h y d r o c a r b o n s t o

h y d r o p e r o x i d e s ; a i r o r o t h e r

o x i d i z i n g agent

i s

i n t r o d u c e d i n t o o x i d i z e r 4 through l i n e

5 .

Ordi

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

though

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

o r

w i t h o u t

r e c y c l e

o f

t h e

e f f l u e n t o x y g e n a t e d hydrocarbon

may be

u s e d .

D i s t r i b u t i n g

means ( n o t shown)

m a y

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

o x i d i z e r 4 t o p r o v i d e

e f l i c i e n t

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

a nd hydrocar

b o n s .

At

the s t a r t o f t h e

o x i d a t i o n ,

t h e

o x i d i z e r

a nd t h e f e e d m a t e r i a l s a r e

heated

t o o x i d i z i n g

temperature.

A f t e r

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

t h e ? r s t

hour o f t h e o p e r a t i o n , c o o l i n g i s employed t o

c o n t r o l t h e

exothermic

r e a c t i o n .

The

r a t e o f i n

troduction o f a i r

o r other

s u i t a b l e means, s u c h

a s i n t e r n a l

o r e x t e r n a l

c o o l e r s ,

may

be used t o

c o n t r o l

t h e temperature w i t h i n t h e

o x i d i z e r a t

the

d e s i r e d temperature o f

a b o u t - 3 0 0

F . Par

t i a l l y

d e o x y g e n a t e d

g a s , t o g e t h e r

w i t h

e n t r a i n e d

l i q u i d

o r

gaseous

hydrocarbon

and

r e a c t i o n

prod

u c t s

l e a v e the

o x i d i z e r

4 v i a

l i n e

6 through a

c o o l i n g and condensing

u n i t

1 and e n t e r s e p a

r a t o r

8

where the mixture s s e p a r a t e d , the water

l a y e r

formed t h e r e i n b e i n g d i s p o s e d

o f s e p a r a t e

l y .

G a s a n d

u n c o n d e n s e d v a pors

are r em o v e d

v i a

l i n e 9 . The hydrocarbonaceous

l i q u i d

i s

with

drawn

from condensing

u n i t 8 through l i n e I 0

and pump

I I a n d

r e c i r cu l a t e d t o o x i d i z e r

4 v i a

l i n e

3 .

When,

i n b a t c h w i s e o p e r a t i o n , t h e hydrocar

b o n has been t r e a t e d

t o

the degree

d e s i r e d ,

a s

measured by

the

o x ygen f a c t o r a n d n e u t r a l i z a

t i o n

number

o f

samples

withdrawn

a t s u i t a b l e

i n t e r v a l s

o r

o t h e r c o n t r o l means,

the

oxygenated

hydrocarbons

a r e

withdrawn from

o x i d i z e r

4

by

m e a n s

o f l i n e

l 2

a n d

pump [ 3 . Preferably

the

o x i d a t i o n

product

withdrawn from o x i d i z e r

4

i s

r a p i d l y c o o l e d i n c o o l i n g means M o about 1 0 0

F . a n d then

may

be

passed

t o a n intermediate

surge

o r

storage tank I 5 .

In

c o n t i n u o u s t y p e

o p e r a t i o n ,

p a r t o f t h e oxy

genated

hydrocarbons may

b e

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

through l i n e s i t

a nd

3

t o

o x i d i z e r 4

a nd

i t i s

sometimes advantageous t o r e c i r c u l a t e t h e main

body

o f

hydrocarbons i n

o x i d i z e r 4 by

p a s s i n g

hydrocarbons

v i a

a

c l o s e d

c i r c u i t including l i n e s

I 2 , l 6 a n d 3 a n d pump 1 3 . I n some i n s t a n c e s ,

two o r more o x i d i z e r s i n s e r i e s may

be

s u b s t i

t u t e d f o r

o x i d i z e r 4 , i n which

c a s e

the hydro

carbons

are

c i r c u l a t e d

f r om

the ?rst

o x i d i z e r t o

subsequent o x i d i z e r s

a nd a r e withdrawn from

the l a s t o x i d i z e r i n the s e r i e s .

The

hydroperoxide i n t e r m e d i a t e i s then taken

from s u r g e

o r

s t o r a g e tank

l 5 a n d passed

v i a

l i n e

I

a n d pump

l 8

through

c o o l e r

l 9 .

W ith

a d d i t i o n

o f metered amounts o f

a c i d

i n t r o d u c e d

through l i n e 2 0

a nd

pump |

t h e

hydroperoxide

containing

mixture

p a s s e s through l i n e 2 2

a nd

a

mixing n o z z l e

2 3 o r o t h e r s u i t a b l e mixing

d e v i c e


8/11

3 2 , . 6 2 2 5 1 1 1 6

3 3

wherein e ? i c i e n t

c o n t a c t

between

t h e

a c i d and

hydroperoxide i s

o b t a i n e d ,

c a u s i n g . t h e c o n v e r - W

s i o n

o f t h e h y d r o p e r o x i d e t o ( i i - h y d r o c a r b on

p e r o x i d e .

The r e a c t i o n mixture p a s s e s through

c o o l i n g

means

2 4 w h i c h ,

w i t h c o o l e r

l 9 , > m - a y " f o r m

p a r t

o f

a

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

c a p a c i t y

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

s y s t e m

t o m a i n t a i n

t h e d e s i r e d t e m p e r a t u r e ,

such s 80 F.

The a c i d - p e r o x i d e m i x t u r e

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

i n t o a

s u i t a b l e

separator

s y s t e m ,

s u c h a s a

r a v i

t y s e p a r a t o r 2 5 , wherefrom t h e a c i d . a n d per

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

m i x t u r e

a r e

s e p a r a t e l y

2 6 . 1 5

c h a r g e d t h r o u g h l i n e s to and 2 1 , , r e s p e c t i v e l y .

P r e f e r a b l y t h e a c i d i s separatedtrom t h e 3 p . e r

o x i d e - c o n t a i n i n g mixture a s s o o n r a s l p o s s i b l e s a f t

er contact.

Thence

the

p e r o x i de - c o nta i n i n g

mixture p a s s e s through a surgedrum 2 8 , ,

. l i n e 2 9

and pump 3 0 v t o a t r e a t i n g u n i t

comprisingyior

example,

a lower

s e c t i o n . d : f o r

c a u s t i c i - i w a s h l a z n d

a n upper s e c t i o n 3 2

f o r

subsequent

w a t e r

wash.

C a u s t i c

such

a s

2 0

Beqaqueous

c a u s t i c

i s

i n t r o

duced i n t o l o w e r s e c t i o n 3 | through

l i n e . 3 3

a n d

d i s c h a r g e d

a s

s p e n t c a u s t i c through l i n e

3 4 .

The

10

ca u stic -wa shed

peroxides a n d

h y d r o c a r b o n s

p a s s

from s e c t i o n 3 . through

l i n e

3 5 t o

water-wash

s e c t i o n 3 2 having water i n l e t l i n e 3 6 a n d

water

outlet line 31.

. . p -

The caustic

land wate1' ~washed pernxid eecon

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

? o w s

t h r o u g h e ? l u e n t . l i n e 3 . 8

through h e a t i n g means 3 9 which may

be a

heat

e x c h a n g e r . o i "

t h e l i k e , t o a . f r a c t i o n a l d i s t i l l a t i o n

column,

s u c h . a s vacuum ?ashtower t i l . T h e r e i n

t h e

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

. c o n s i s n

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

t a k e n o y e r h c a d

v i a

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

i n t o

s e p a r a t o r

dmim

i t

a n d

t h e n c e

t h r o u g h

l i n e

M, pumpiidand v a l u e - c o n t r o l l e d l i n e s i t s a n d

l i t

t o t e e d l i n e > . l

_ . - i - c r r e c i r c u l a t i o n .

t h r o u g h t h e s y s

a n d f u r t h c r ~ c x i < 1 a t i o m

o r ' a r e

removed

from

t h e s y s t e m v i a y a l v e e c o n t m e d l i - n e a s .

I f

de

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

cecus m a t e r i a l

may e acid

r e a t e d

a s

i s

the

prim

f e e d s t o c k .

Part

o f

t i e ouerheadccndensate

i s r e t u r n e d re?ux t o r t o w e ' r

cc

M a i n e - s o o n

trolled

line ( 3 9 . s u i t a b l e a u a c u u t m generating

f

: m e a n s , such . a w s t e a m

. e i e c t o r

5 E 3 .

attached

t o

drum at is pro

ed

wmmamram the-desired

vacuum-in the

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

? a s h

tower

0 : . T h e

tower

i t

i s a l s o p r o v i d e d with s u i t a b l e heating

means u c h steam r e b c j i l c r

5 3 3

or the i l e s .

Con

c e n t r a t e d

p e r o x i d e - w i t h d r a w n

f r o m

t o w e r

w i t h

t h r o u g h l i n e ' 5 2 , pump 5 3

and c e o i l i n g m e a - n s 5 4

passes

to product storagc.

. : , T h e d rawin g o f . t h e

above-described

cmbcdi ;

omits s a k e ' o f

s i m p l i c i t y

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

v a l v e s , f l o w , l e v e l . a n d ' p r e s s u n e c o n t r o l l e r s ,

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

r e g u l a t o r s

and t h e

l i k e , a s w i l l be

readily

s u p p l i e d

by

one skilledh e a r t .


are

not

prepared

from

l i q u i d phase

oxidation I o f i i y d r o c a r h c n s

such a s

o x i d i z e r i t , t h e i l l u s t r a t e d

e q u i p m e n t .

i n t h e

l i n e . o f flow p r i o r t o

the surge

or s t o r a g e

tank

i t :

be o m i t t e d , a nd h y d r c p e r o x i d e s p r e f e r a b l y

o l u t i o n

i n a n i n e r t

s o l v e n t , such a s

l i q u i d

hydro

c a r b o n s ,

are

i n t r o d u c e d

i n t o

t h e s y s t e m s t a r t i n g

with

line

ll

and

p t u m p l f i .

A s

i l l u s t r a t i v e

o f

the present invention the 0 1 m

lowing examples

are

given:

.

E x ample 1 . - l . 6 . 5

c .

c . of

technical .dimethyl

c y c l o p e n t y l

h y d r o p e r o x i d e

. (

a b o u t 8 5 %

u r i t y and

h a v i n g

an

o x ygen f a c t o r of 1 1 , 7 1 7 . 0 9 ) wa s d i l u t e d

t o

1 6 5 c c. with i l - p i i n t a n e a n d

t h e

r e s u l t a n t s o l u

tion

(an o x ygen f a c t o r o f

" 1 0 8 4 ) treated with

. 2 5

1 4

j m l 2 5 ' i l b t / i g a l .

o f r ( 5 %

s u l f u r i c

a c i d a t 4 0 - 5 0 F . o v e r

a n j h o m i p e r i o d . A f t e r s e p a r a t i n g from

t h e

aque

ous acid phase, the u p p e r o i l y l a y e r

wa s

water

W a shed a nd

n e u t r a l i z e d with sodium b i c a r b o n a t e .

1 l T p o n

evaporating o f f

the

n-pentane,

1 3 . 6

c . c .

o f

product

was

r e c o v e r e d ,

which

h a d a n

o x y g e n

f a c t o r

o f 4 3 7 0 .

At 0.5%

concentration

i n

a n

u n

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

h a v i n g a

cetane n um be r o f

about 4 1 , the product

caused

a n

increase o f

a n

average

. o f 1 2 . 2

cetane

numbers. . A t

the

same

concentration i n the same f u e l , t e c h n i c a l

di

methyl c y c l o p e n t y l h y d r o p e r o x i d e o f a b o u t 60%

p u r i t y

gave

o n l y a cetane numberincrease

o f

6 . 5 .

E x a m p l e

2 . - - > - T o 100

c .

o .

o f

8 8 . 7 1 % t e r t i a r y

b u t y l

h y d r o p e r o x i d e , t h e r e

was

s l o w l y

addedpver

a

two- ho ur

period 50 c . c . o f 65% s u l f u r i c

a c i d

w h i l e

maintaining t h e temperature

below about

7

C . After allowing the mixture t o stand over

n i g h t , a n additional 50 c . c . o f 75% s u l f u r i c acid

wa s added in

8 0

minutes time

a t a temperature

below

0

C .

Thereafter with

the

r e a c t i o n

v e s s e l

placed

i n a c o l d

water bath t o s t a r t , t h e tempera

ture w a s permi-ttedto warm t o r o om v t e m p e r a t u r e .

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

o f p h a s e s ,

the

( u p p e r l a y e r wa s

w a s h e d

free . o f l h y d r o p e r o x i d e with s e v e ra l 1 0

c . 0 . portions

of 40% c a u s t i c . After

a ? n a l water

wash, 5 5 c . c . of d i ~ l ( . t e r t i a r y

b u t y l ) peroxide

w a s

obtained.

This product wa s determined

t o

' b e

f a i r l y

pure y i i ' t s

l a c k

o f oxygen

f a c t o r

and meas

urement

o f

d e n s i t y , b o i l i n g

p o i n t

and r e f r a c t i v e

index 7 ~

Example

3 . - - A number

o f i n d i v i d u a l hydro~

carbons o f

approximately

98%

o r

b e t t e r

p u r i t y

were

?rst oxygenated bypla c i n g a sample of each

35

6 . 0

65

7 1 0

7 5

hydrocarbon i n a

v e s s e l

? t t e d w i t h a n a i r i n l e t ,

a sampling d e v i c e ,

a

w a t e r

t r a p ,

a n d a re?ux

condenser. This

apparatus

wa s immer sed

in

a

constant temperature o i l

bath maintained

a t p e r

. o x i d a t i o n

t e m p e r a t u r e .

A f t e r s u ? i c i e n t t i m e

f o r

the contents t o

reach

the bath temperature, a i r

w a s passed through

the

hyd ro carbon v i a . a d i s

t r i b u t i n g p l a t e i n t h e bottom o f t h e

o x i d i z e r

v e s

s e l .

Samples were w ith dra w n

from the m a i n

b o d y

o f

t h e hydrocarbon a t p e r i o d i c i n t e r v a l s .

The oxygen f a c t o r ( i n d i c a t i n g

t h e

hydroperoxide

content)

of

the

s am ple and a c i d content were

determined.

When the o x ygen f a c t o r

reached

a

maximum o r s h o rt l y t h e r e a f t e r , v

the

stock wa s

removed

from the

a p p a r a t u s ,

c o o l e d

a n d

neu

t r a l i z e d with 5 0%

by Volume

o f

5%

sodium b i

carbonate

t o

remove a c i d s . The peroxidized

.ma

t e r i a l w a s then a dded i n 2.5%

a n d

10% c o n cen

t r a t i o n s t o a . Diesel f u e l base (derived from w a x y

C a l i f o r n i a crude)

a n d

the

cetane

n um be r

o f

the

blend determined.

The

r e s u l t s obtained

i n

t h i s

m a n n e r

. a r e given

i n

the Table H e l o w , wherein

t h e peak

oxygen

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

o b t a i n e d

by

determination

o n w ith dra w n

samples

whereas

the

blending o x ygen factor i s the ?nal o x ygen

f a c e

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

t o

b l e n d i n g . ( T h e l a t t e r

v a l u e

i s

u s u a l l y

lower

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

r e d u c e s t h e p e r o x i d e

content

approximately

10%

a nd

a i r

v b l o w i n g was g e n e r a l l y not stopped

u n t i l

the p e a k h a d been p a s s e d , r e s u l t i n g i n a

lower

p e r o x i d e c o n t e n t . )

The

o c t a n e

number

i n c r e a s e

f o r the unperoxidized

material

w a s

obtained

i n

o r d e r

t o

s h o w

t h e t r u e

e f f e c t

o f t h e p e r o x i d e

s i n c e

o n l y 5 t o 20% o f

the'unconcentrated

blown ma

t e r i a l w a s

peroxides;

h e n c e

cetane number i n s

crease w a s corrected

in

a c cordan ce with su ch

blanks. The

relative

e? ectivenes s of the d i f f e r

ent hydroperoxides i s g i v e n a s the i n c r e a s e

i n

octane

n u m b e r

per 1000 o x ygen f a c t o r , i n order

t o bring the e f f e c t i v e n e s s o f the p e r o x i d e s t o a

common asis.


9/11

TABLE I

R e s u l t s o f

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

pure

h y d r o c a r b o n s

C e t a n e Number I n c r e a s e

_ Relative Ei

P e r o x i -

Blend:

f e c t i v e n e s s ,

C o m p o u n d

g g o l g r i 5 2 3 % P e i - o x i d i z e d U r g g g x l

C o r r e c t e d

S O N / 1 0 0 0 0 F

2 . 5 % 1 0 % 2 . 5 %

1 0 %

2 . 5 % 1 0 % 2 . 5 %

1 0 %

n-Decane

_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

- _ 2 7 5 7 1 9 5 9 0

8 .

6 1 5 .

7

+0.

5

+3. 1 8 . 1 1 2 .

6

1 3 . 8 2 1 .

3

n -D o de ca n e -_ . 300 529 302

3 .

2 1 0 . 6

_

1

( 1 0 .

6) 1 ( 3 3 . 1 )

O c t e n e - 1 . _ _ _ _

_

2 4 0 1 , 1 4 2 9 0 2 7 . 5

1 4 .

6 +0. 1 +0. 4 7 . 4

1 4 .

2 8 . 2

1 6 .

7

Decen e- l- -

_ _ _ _ 250 849 614 5. 1 1 0 . l +0.1 +0.6 5.0 9 . 5 8.2

1 5 .

4

Ethylcyclohexane

_ 2 6 5

1 l , 4 8 4 1 , 2 5 0

7 . 0 1 3 . 3

O.

6 ~1.

3 7 .

6 1 4 . 6

6 . 1

l 1 .

7

Iso-Propylcyolohexane _

3 0 0

1 ,

4 2 2 9 5 6 5 . 6 1 2 .

0

0 . 7 l.

5 6 .

3 1 3 .

5 6 . 6

1 4 . l

t h y l b e n z e n e u n s n u - _ 2 6 5 a 2 , 0 5 0 1 , 8 6 8 5 . 5 8 . 3 -1.4 3.5 6 .

9

1 1 . 8 3.7 6 . 3

o-Xylc ne.

_ _

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Di-Organo Peroxide