Europaisches P a t e n t a m t

European Patent Office © Publication number: 0 049 4 2 9

Office europeen des brevets A1

EUROPEAN PATENT APPLICATION

© Application number: 81107628.0 ©Int CI.3: C 07 C 5 1 / 4 8

C 07 C 59/08, C 07 C 5 9 / 2 4 5
@ Date of filing: 25.09.81 C 07 C 5 9 / 2 6 5
//C1 2P7/42, C1 2P7/46, C1 2 P 7 / 4 8

© Priority: 06.10.80 US 194555 © Applicant: MILES LABORATORIES INC.

1127 Myrtle Street
Elkhart Indiana 46514IUS)
© Date of publication of application:
14.04.82 Bulletin 82/15 © Inventor: Baniel, Avraham Matitiahu
P.O. Box 8070
© Designated Contracting States: Jerusalem(IL)
AT CH DE FR GB IT U
© Representative: Adrian, Albert, Or. et al,
BAYER AG c/o Zentralbereich Patente Marken und
I Lizenzen
D-5090 Leverkusen 1, Bayerwerk(DE)

© Process for the extraction of organic acids from aqueous solution.

Organic acids, such as citric acid, malic acid and lactic

acid. can be extracted from aqueous solutions thereof by
contacting such solutions with a mixture of a water immisci-
ble amine and a water immiscible organic acid dissolved in a
suitable water immiscible solvent.
 Various organic acids, such as c i t r i c acid, malic acid,

lactic acid and the like, are produced by v a r i o u s techniques

and are available in a q u e o u s solutions from w h i c h it is d e -

sired to r e c o v e r such acids in a p u r i f i e d and c o n c e n t r a t e d

form.

Citric acid has b e e n commercially removed from aqueous

solutions thereof, such as f e r m e n t a t i o n beer, by the p r o c e d u r e
of a d d i n g l i m e to f o r m a precipitate of c a l c i u m citrate and

then reacting the c a l c i u m citrate with a q u e o u s sulfuric acid

to f o r m a citric acid s o l u t i o n and i n s o l u b l e calcium sulfate.

This procedure has the d i s a d v a n t a g e s of r e q u i r i n g expendable

lime and s u l f u r i c acid as w e l l as d i s p o s a l of c a l c i u m sulfate.

Liquid-liquid extraction procedures have also b e e n p r o -

posed in the p r i o r art. The use of long c h a i n aliphatic amines

dissolved in an a p p r o p r i a t e solvent to e x t r a c t organic acids is

discussed in J. Soc. C h e m . Ind. 67, 48 (1948). U. S. Patent

No.2, 539, 472 d i s c l o s e s use of an a m i n e - s o l v e n t mixture to

extract citric acid, lactic acid, or t a r t a r i c acid. The r e -

sulting complex requires steam distillation to r e c o v e r the

citric acid, lactic acid or t a r t a r i c acid t h e r e f r o m however.

The use of a m i x t u r e of a m i n e s and h y d r o c a r b o n s to e x t r a c t

citric acid, lactic acid or o x a l i c acid is d i s c l o s e d in B r i t i s h

Patent No. 1,426,018. The r e c o v e r y of c i t r a t e salts using an

amine-organic solvent mixture for e x t r a c t i o n of c i t r i c acid i s

also disclosed in U. S.. P a t e n t N o . 3 , 944, 606. None of t h e

above prior art discloses or s u g g e s t s the c o m b i n a t i o n of a

water immiscible amine and a w a t e r immiscible organic acid

to e x t r a c t organic acids, s u c h as c i t r i c acid.

In a c c o r d a n c e with the p r e s e n t invention, a process f o r

the extraction of an organic acid f r o m an a q u e o u s solution

thereof is p r o v i d e d w h i c h c o m p r i s e s contacting such solution

with a mixture of a w a t e r immiscible amine and a w a t e r im-

miscible organic acid d i s s o l v e d in a s u i t a b l e water immiscible

solvent. This process is e s p e c i a l l y useful for the e x t r a c t i o n

of c i t r i c acid.

The aqueous organic acid s o l u t i o n s used as s t a r t i n g ma-

terial for the p r o c e s s of the p r e s e n t invention are well k n o w n .
In the c a s e of c i t r i c acid, they c a n be f e r m e n t o r beers pro-
d u c e d by the f e r m e n t a t i o n of v a r i o u s cultures, such as

Aspergillus niger on c a r b o h y d r a t e s , or t h e y can be c i t r i c acid

solutions obtained from any o t h e r source. The concentration

of c i t r i c acid is not c r i t i c a l . The present i n v e n t i o n has been

u s e d to e x t r a c t citric acid f r o m aqueous solutions thereof con-
taining as low as 1 percent and as high as 20 p e r c e n t (weight/
volume basis) citric acid.
 The w a t e r immiscible amines useful in the p r e s e n t in-

vention m a y be primary, secondary, tertiary or q u a t e r n a r y

containing at l e a s t 12 c a r b o n atoms in a g g r e g a t e . The pre-

ferred amines contain at l e a s t 20 c a r b o n atoms in a g g r e g a t e .

These amines m a y be a l i p h a t i c , araliphatic, aromatic, or

mixtures or c o m b i n a t i o n s thereof. Examples of u s e f u l amines

are t r i l a u r y l a m i n e , tricaprylylamine, tritridecylamine, tri-

octylamine, dilaurylamine, dilaurylbenzylamine, a secondary

amine h a v i n g two h i g h l y b r a n c h e d aliphatic groups attached

to the n i t r o g e n atom and with a molecular weight of about 351

to 393, primary aliphatic amines wherein the a l i p h a t i c group

is t e r t i a r y hydrocarbyl having 18 to 22 c a r b o n atoms, and t h e

like.

The w a t e r immiscible organic acids useful in the p r e s e n t

i n v e n t i o n m a y be c a r b o x y l i c acids, alkylphosphoric .acids,

alkylphosphonic acids, halogen substituted derivatives thereof

and m i x t u r e s thereof. Such a c i d s should contain at l e a s t 12

carbon atoms in a g g r e g a t e and p r e f e r a b l y at l e a s t 18 c a r b o n

atoms in a g g r e g a t e . The h a l o g e n a t e d derivatives may con-

. tain l e s s t h a n 12 c a r b o n atoms so long as the m a t e r i a l is w a t e r

immiscible. Examples of u s e f u l acids are oleic acid, di-

ethylhexyl phosphoric acid, 2-bromohexanoic acid, linoleic

acid, octanoic acid, 2-bromolauric acid, an a l i p h a t i c sub-

stituted cyclopentyl carboxylic acid and the l i k e .

The w a t e r immiscible solvents useful in the p r e s e n t in-

v e n t i o n m a y be a l i p h a t i c hydrocarbons, aromatic hydro-

carbons, petroleum fractions, hydrocarbons carrying nitro

or halo s u b s t i t u e n t s , alcohols, ketones and m i x t u r e s thereof.

Examples of u s e f u l solvents are an a l i p h a t i c naphtha (petro-

leum fraction) having a boiling point range of 17.9. 4 - 2 0 4 . 4° C .
and an a v e r a g e specific gravity of 0. 752 measured at 25° C . ,

xylene, a petroleum fraction having a boiling point range of

140-210° C. , a petroleum fraction having a b o i l i n g point r a n g e

of 1 8 0 - 2 1 0 ° C., n-octanol, nitrobenzene, a hydrocarbon

fraction having a boiling point r a n g e of 6 0 - 9 0 ° C . , n-octane,

and the l i k e .

The water immiscible amines and w a t e r immiscible

organic acids are preferably employed in the m o l a r p r o -

portion of a m i n e : o r g a n i c acid f r o m about 0. 8:1 to about 1. 2:1.

Higher proportions of a m i n e are not d e s i r a b l e since the excess

of a m i n e will f o r m a complex with c i t r i c acid, for example,

from w h i c h the c i t r i c a c i d c o u l d not be c o n v e n i e n t l y recovered

at the s a m e temperature as the extraction. Higher pro--

portions of acid m a y be n e c e s s a r y in c e r t a i n combinations of

amines and a c i d s in o r d e r to o b t a i n the d e s i r e d eventual r e -

covery of ci-tric acid.

The extraction temperature is not n a r r o w l y critical and .

can be f r o m a b o u t 20° C. to about 80° C. The desired acid,

such as c i t r i c acid, can be c o n v e n i e n t l y r e c o v e r e d from the

amine-acid-solvent p h a s e by b a c k - e x t r a c t i o n with w a t e r at

the same temperature as the i n i t i a l extraction step.

The c o m b i n a t i o n of a m i n e and acid employed in t h e

process of the p r e s e n t i n v e n t i o n to e x t r a c t water soluble or-

ganic acids, such as c i t r i c acid, is u n e x p e c t e d when c o m p a r e d

to the known p r i o r art. In a c o n v e n t i o n a l extraction process

the amine, w h i c h is b a s i c , reacts with the c i t r i c acid to f o r m

a complex salt. This complex salt is t h e n d i s s o c i a t e d chem-

ically or at e l e v a t e d temperature so that the c i t r i c acid c a n

be r e c o v e r e d in a b a c k - e x t r a c t i n g step. If one i n i t i a l l y added

an acid to the a m i n e , this acid w o u l d be e x p e c t e d to r e a c t

with the amine and t h u s reduce the c a p a c i t y of the amine to

react with and e x t r a c t citric acid. It is thus unobvious and

unexpected to e m p l o y an a m i n e - a c i d combination and s t i l l h a v e

a desirably high e x t r a c t i o n capacity. It is f u r t h e r unexpected

that this extraction process enables the c i t r i c acid to be r e -

covered by b a c k - e x t r a c t i o n at the s a m e temperature as t h e

extraction step.

The invention which is particularly useful for the

extraction of citric acid, lactic acid and malic acid

is described in further detail in the following examples:

EXAMPLE

A s o l u t i o n of t r i l a u r y l a m i n e and o l e i c a c i d in a h y d r o -

carbon solvent was prepared by m i x i n g 12. 5 g. trilauryl-

amine and 5. 64 g. oleic acid in s u f f i c i e n t amount of a l i q u i d

hydrocarbon to p r o d u c e 100 ml. of s o l u t i o n . The l i q u i d

hydrocarbon was an a l i p h a t i c naphtha (petroleum fraction)

having a b o i l i n g point r a n g e of 1 7 9 . 4 - 2 0 4 . 4 ° C. and a n

average specific gravity of 0. 752 m e a s u r e d at 25° C. The

resulting s o l u t i o n had a m o l a r ratio of t r i l a u r y l a m i n e : o l e i c

a c i d of 1. 2:1. Similar solutions were produced having m o l a r

ratios of t r i l a u r y l a m i n e : o l e i c acid of 1:1 and 0. 8:1. Separate

aqueous solutions containing 1 percent, 10 p e r c e n t and 20 p e r -

cent, respectively, (weight/volume basis) of c i t r i c acid w e r e

also p r e p a r e d .

A 40 ml. portion of e a c h of the above t h r e e separate

citric acid s o l u t i o n s was placed into t h r e e separate 100 m l .

containers (a t o t a l of nine containers). A 10 ml. portion of

each of the above t h r e e separate trilaurylamine-oleic acid

solutions was p l a c e d into t h r e e of the above citric acid

solution containers so that e a c h of the separate trilaurylamine

-oleic acid s o l u t i o n s was contacted with e a c h of the s e p a r a t e

citric acid solutions. All of the nine containers were then

placed in a 20° C. water bath for about 15 min. to e q u i l i b r a t e ,

were shaken twice, left o v e r n i g h t at 20° C . , shaken again and

centrifuged for 15 min. at about 2800 R P M . The o r g a n i c

phase of the contents of e a c h of the c o n t a i n e r s was then

analyzed for citric acid. The r e s u l t s are shown below in

Table 1.

It can be s e e n f r o m the a b o v e d a t a that a mixture of t r i - .

laurylamine and o l e i c acid in v a r i o u s concentrations in a

hydrocarbon solvent can e x t r a c t citric acid f r o m aqueous

solutions having various concentrations thereof.

EXAMPLE 2

A solution of t r i l a u r y l a m i n e and d i e t h y l h e x y l phosphoric

acid in a h y d r o c a r b o n solvent was prepared by m i x i n g 12. 5 g.

trilaurylamine and 6. 44 g. diethylhexyl phosphoric acid i n

sufficient amount of the l i q u i d hydrocarbon described in E x -

ample 1 to p r o d u c e 100 ml. of s o l u t i o n having a molar ratio

of t r i l a u r y l a m i n e : d i e t h y l h e x y l phosphoric acid of 1. 2 : 1 .

Similar solutions were produced having molar ratios of t r i -

laurylamine: diethylhexyl phosphoric acid of 1:1a n d 0. 8 : 1 .

 A 40 ml. portion of e a c h of the t h r e e separate citric
acid solutions described in E x a m p l e 1 was placed into t h r e e

separate 100 ml. containers (a t o t a l of nine containers). A

5 ml p o r t i o n of each of the above three separate trilauryl-
amine-diethylhexyl phosphoric acid solutions was placed into
each of the t h r e e containers containing the 1 percent citric
acid s o l u t i o n s . A 10 ml. portion of each of the above t h r e e

separate amine-acid solutions was placed into six of t h e

above containers containing respectively, the 10 and 20 p e r -

cent c i t r i c acid s o l u t i o n s . All of the nine containers were

then s h a k e n and p l a c e d in a 20° C. water b a t h for about 15

min. They were then c e n t r i f u g e d for about 15 m i n . at a b o u t

2800 R P M . The o r g a n i c phase of the contents of e a c h of t h e

containers was analyzed for c i t r i c acid. The r e s u l t s are

s h o w n below in T a b l e 2.

It can be s e e n f r o m the above data that a mixture of t r i -

laurylamine and d i e t h y l h e x y l phosphoric acid in v a r i o u s con-

centrations in a h y d r o c a r b o n solvent can e x t r a c t citric acid

from aqueous solutions having various concentrations thereof.

 EXAMPLE 3

A solution of t r i l a u r y l a m i n e and 2 - b r o m o h e x a n o i c acid

in a h y d r o c a r b o n solvent was prepared by m i x i n g appropriate

quantities of t r i l a u r y l a m i n e and 2 - b r o m o h e x a n o i c a c i d in s u f -

ficient amount of the l i q u i d hydrocarbon described in E x -

ample 1 to p r o d u c e 100 ml. of s o l u t i o n h a v i n g a molar ratio

of t r i l a u r y l a m i n e : 2 - b r o m o h e x a n o i c acid of 1. 2:1. Similar

solutions were produced having molar ratios of t r i l a u r y l -

amine:2-bromohexanoic a c i d of 1:1 and 0 . 8 : 1 .

A 25 ml. portion of e a c h of the t h r e e separate citric acid

solutions described in E x a m p l e 1 was p l a c e d into t h r e e

separate 100 ml. containers (a t o t a l of nine c o n t a i n e r s ) . A

5 ml. portion of e a c h of the above t h r e e separate amine-acid

solutions was placed into t h r e e of the above c i t r i c acid

solutions containers so that each of the s e p a r a t e amine-acid

solutions was c o n t a c t e d with e a c h of the s e p a r a t e citric acid

solutions. All of the nine containers were then p l a c e d in a

20° C. water b a t h for about 15 m i n . , shaken and t h e n r e -

p l a c e d into the w a t e r bath for about 15 m i n . , shaken again

and c e n t r i f u g e d for about 15 m i n . at 2800 R P M . The organic

phase of the c o n t e n t s of e a c h of the c o n t a i n e r s was analyzed

for citric acid. The results are s h o w n below in T a b l e 3.
 It c a n be s e e n f r o m the above data that a m i x t u r e of t r i -

laurylamine and 2 - b r o m o h e x a n o i c a c i d in v a r i o u s concentra-

tions in a h y d r o c a r b o n solvent can e x t r a c t citric acid f r o m

various aqueous solutions having various concentrations

thereof.

EXAMPLE 4

A 200 ml. quantity of a s o l u t i o n of t r i l a u r y l a m i n e and

oleic a c i d in a h y d r o c a r b o n solvent having a molar ratio of

trilaurylamine:oleic acid of 1. 2:1 was prepared as d e s c r i b e d

in E x a m p l e 1. A 50 ml. portion of this s o l u t i o n was placed
into e a c h of four c e n t r i f u g e tubes. Into e a c h centrifuge tube

was also placed a 75 ml, portion of an a q u e o u s fermentor

beer containing 17 p e r c e n t citric acid (weight/volume basis).

The fermentor beer also contained 1889 ppm sulfate ions.

All the c e n t r i f u g e tubes were placed in a 40° C. water bath

for 15 min. , were shaken for 5 min. on a s h a k e r and t h e n

centrifuged for 20 m i n . at 2800 R P M . The organic phases

of all the tubes w e r e then r e m o v e d and pooled. Analysis of

the organic phase i n d i c a t e d that it c o n t a i n e d 5. 6 p e r c e n t

citric acid ( w e i g h t / v o l u m e basis).

 The 200 ml. of o r g a n i c phase was d i v i d e d into t w o

100 ml. portions. One p o r t i o n was m i x e d with 20 ml. water

at 40° C. for 15 m i n . , shaken and then c e n t r i f u g e d for 20 m i n .

at 2800 R P M . The aqueous and o r g a n i c phases were separated

and the a q u e o u s phase was then c o n t a c t e d with the o t h e r 100

ml. portion of the i n i t i a l organic phase and t r e a t e d as d e -

scribed above. The aqueous and o r g a n i c phases were then

separated and the a q u e o u s phase was analyzed to c o n t a i n 8. 12

percent (weight/volume basis) citric acid and 24 p p m sulfate

ions.

This example shows t h a t the p r o c e s s of the p r e s e n t in-

vention can c o n v e n i e n t l y extract citric acid f r o m impure so-

lutions thereof and that the extracted acid can be e a s i l y re-
covered in a p u r i f i e d state by b a c k - e x t r a c t i o n with w a t e r at

the s a m e temperature as the i n i t i a l extraction.

Carbonizables in c i t r i c acid solutions are measured by

contacting 10 ml. concentrated sulfuric acid at 0° C. with 1 m l .

of s a m p l e (prediluted to o b t a i n a f i n a l O. D. in the r a n g e of

0. 1-0. 3) in a t e s t t u b e · i n an ice b a t h . The m i x t u r e is s h a k e n ,

then heated for 1 hour at 90° C. It is' c o o l e d to r o o m tempera-

ture and the O. D. measured at 497 nm. The above citric

acid-containing fermentor beer had a c a r b o n i z a b l e content

represented by an O. D. of 24. 4. The b a c k - e x t r a c t aqueous

citric a c i d had an O. D. of 0. 33. This also s h o w s that the

process of the present invention also purifies citric acid

solutions by r e m o v i n g undesirable carbonizables.

The process of the p r e s e n t i n v e n t i o n is c o m p a r e d to t h e

prior art in the following example.

 EXAMPLE 5

A solution of t r i l a u r y l a m i n e and o l e i c acid in a h y d r o -

carbon solvent having a molar ratio of t r i l a u r y l a m i n e : o l e i c

a c i d of 1. 2:1 w a s prepared as d e s c r i b e d in E x a m p l e 1. A

comparison solution r e p r e s e n t i n g the p r i o r art was prepared

by mixing trilaurylamine, octanol and the l i q u i d h y d r o c a r b o n

u s e d in E x a m p l e 1 in the r a t i o s of 36 g. trilaurylamine, 5 g.

octanol and 57 g. liquid h y d r o c a r b o n . Separate 55 ml. portions

of a q u e o u s citric acid s o l u t i o n s containing either 1 percent or

20 p e r c e n t (weight/volume basis) citric acid w e r e separately

contacted w i t h 10 ml. portions of the a b o v e trilaurylamine
-oleic a c i d or t r i l a u r y l a m i n e - o c t a n o l solutions at e i t h e r 20° C .

or 70° C. After temperature equilibration for about 15 m i n . ,

they w e r e shaken three times and c e n t r i f u g e d for 5 min. at

10, 000 R P M . There was clean phase separation with n o

emulsion formation. The o r g a n i c phase of e a c h sample was

analyzed for c i t r i c acid c o n t e n t . The r e s u l t s are shown i n

Table 4 b e l o w :
 It c a n be s e e n from the a b o v e d a t a that the p r o c e s s of t h e

present i n v e n t i o n is l e s s temperature sensitive than is a

related prior art p r o c e s s . The amount of c i t r i c acid ex-

tracted by the p r i o r art p r o c e s s from a 1 percent citric acid

s o l u t i o n was reduced by 84 p e r c e n t w h e n the e x t r a c t i o n tem-

perature was i n c r e a s e d from 20° C. to 70° C. In c o n t r a s t to

this, the amount of c i t r i c acid extracted by the p r o c e s s of t h e

present i n v e n t i o n was r e d u c e d by only 72 p e r c e n t under the

same conditions. The amount of c i t r i c acid e x t r a c t e d by t h e

prior art process from a 20 p e r c e n t citric acid s o l u t i o n was

reduced by 15 p e r c e n t when the e x t r a c t i o n temperature was in-

creased from 20° C. to 70° C. In c o n t r a s t to this, the a m o u n t

of c i t r i c acid e x t r a c t e d by the p r o c e s s of the p r e s e n t invention

was reduced by only 10 p e r c e n t under the s a m e conditions.

 EXAMPLE 6

A solution in a h y d r o c a r b o n solvent of oleic acid and a

primary aliphatic amine consisting of a m i x t u r e of p r i m a r y

amines wherein the aliphatic group is t e r t i a r y hydrocarbyl

having 18 to 22 c a r b o n atoms (Primene JM-T) was prepared

by m i x i n g sufficient amounts of the amine and acid in t h e

liquid h y d r o c a r b o n described in E x a m p l e 1 to p r o d u c e a con-

centration of 0. 5 M a m i n e and 0. 5 M acid (molar ratio of

amine:acid of 1:1). An a q u e o u s solution of c i t r i c acid c o n -

taining 20 p e r c e n t citric acid ( w e i g h t / v o l u m e basis) was

mixed with the above amine-acid-hydrocarbon mixture in a

volume ratio of 8:30 (organic phase:aqueous phase) in a 50 m l .

centrifuge tube. The mixture was placed in a 40° C. water

b a t h for about 30 m i n . It was then shaken four t i m e s . Each

shaking p e r i o d was about 1 min. with a s e p a r a t i o n of a b o u t

15 m i n . between periods. W h e n the m i x t u r e was not b e i n g

shaken, it r e m a i n e d in the w a t e r bath. It t h e n s t o o d o v e r -

night in the w a t e r bath. The organic phase was analyzed to

contain 0. 303 m o l e s / l i t e r citric acid. This procedure was

repeated with f r e s h solutions at 80° C. , and the organic phase

contained 0. 304 m o l e s / l i t e r citric acid.

EXAMPLE 7

A solution in a hydrocarbon solvent of l i n o l e i c a c i d and

a secondary amine having two h i g h l y b r a n c h e d aliphatic groups

attached to the n i t r o g e n atom and with a m o l e c u l a r weight of

about 351 to 393 ( A m b e r l i t e LA-1) was prepared by m i x i n g

sufficient amounts of the a m i n e and acid in the l i q u i d h y d r o -

carbon described in E x a m p l e 1 to p r o d u c e a concentration of

0. 4 M a m i n e and 0. 5 M acid (molar ratio of a m i n e : a c i d of

0. 8 : 1 ) . A n aqueous solution of c i t r i c acid h a v i n g the same
concentration as E x a m p l e 6 was m i x e d with the amine-acid

hydrocarbon mixture in the same way as d e s c r i b e d in E x -

ample 6. The organic phase from the 40° C. extraction con-

tained 0. 174 m o l e s / l i t e r citric acid and the o r g a n i c phase

from the 80° C. extraction contained 0.195 moles/liter citric

acid.

EXAMPLE 8

A solution of t r i l a u r y l a m i n e and o c t a n o i c a c i d in a h y d r o -

carbon solvent was prepared by m i x i n g sufficient amounts of

the amine and acid in the l i q u i d h y d r o c a r b o n described in E x -

ample 1 to p r o d u c e a concentration of 0. 5 M a m i n e and 0 . 5 M

acid (molar ratio of a m i n e : a c i d of 1:1). An a q u e o u s solution

of c i t r i c acid h a v i n g the same concentration as in E x a m p l e 6

was mixed with the amine-acid-hydrocarbon mixture in the

same w a y as d e s c r i b e d in E x a m p l e 6. The organic phase

f r o m the 40° C. extraction contained 0. 269 m o l e s / l i t e r citric

acid, and the o r g a n i c phase from the 80° C. extraction con-

tained 0.197 moles /liter citric acid.

EXAMPLE 9

A solution in a h y d r o c a r b o n solvent of t r i l a u r y l a m i n e

and an a l i p h a t i c substituted cyclopentyl carboxylic acid c o m -

prising a mixture of c o m p o u n d s h a v i n g the g e n e r a l formula:

wherein R is one or m o r e aliphatic groups and "n'' is an

integer from 0 to 4 and having an a v e r a g e molecular weight

of 200 to 300 was prepared by m i x i n g sufficient amounts of t h e

amine and acid in the l i q u i d hydrocarbon described in E x -

ample 1 to p r o d u c e a concentration of 0. 5 M a m i n e and 0. 5 M

acid (molar ratio of a m i n e : a c i d of 1:1). An a q u e o u s solution

of c i t r i c acid h a v i n g the s a m e concentration as in E x a m p l e 6

was m i x e d with the a m i n e - a c i d - h y d r o c a r b o n mixture in t h e

same w a y as d e s c r i b e d in E x a m p l e 6.. The organic phase -

from the 40° C. extraction contained 0. 246 m o l e s / . l i t e r citric

acid and the o r g a n i c phase f r o m the 80° C. extraction con-

tained 0. 177 m o l e s / l i t e r citric acid.

EXAMPLE 10

A solution of t r i l a u r y l a m i n e and 2 - b r o m o l a u r i c acid i n

a hydrocarbon s o l v e n t was prepared by m i x i n g sufficient

amounts of the a m i n e and acid in the l i q u i d hydrocarbon

described in E x a m p l e 1 to p r o d u c e a concentration of 0. 5 M

amine and 0. 5 M acid (molar ratio of a m i n e : a c i d of 1:1). An

aqueous s o l u t i o n of c i t r i c acid h a v i n g the same concentration

as in E x a m p l e 6 was mixed with the a m i n e - a c i d - h y d r o c a r b o n

mixture in the s a m e way as d e s c r i b e d in E x a m p l e 6. The

organic phase from the 40° C. extraction contained 0.145

moles /liter citric acid, and the o r g a n i c phase f r o m the 80° C .

extraction contained 0. 145 m o l e s / l i t e r citric acid.

It is noted that the r e s u l t s in E x a m p l e s 6-10 above show

that t h e r e is s u b s t a n t i a l l y no t e m p e r a t u r e effect on the e x -

traction process of the p r e s e n t invention when extractions at

40° C. and 80° C. are compared.

 EXAMPLE 11
A 200 ml. solution of 0. 6 M t r i l a u r y l a m i n e and 0. 5 M

oleic acid in the l i q u i d hydrocarbon described in E x a m p l e 1

was prepared having a concentration of 0. 6 M a m i n e and 0. 5 M

a c i d . ( a m i n e : acid m o l a r ratio of 1. 2:1). This solution was

then m i x e d with 300 ml. of an a q u e o u s solution of 20 p e r c e n t

citric acid (weight/volume basis). The r e s u l t i n g mixture was

shaken, p l a c e d in a 40° C. water bath for about 15 m i n . ,

centrifuged for about 15 m i n . at 2800 R PM, and the o r g a n i c

and a q u e o u s phases were separated and a n a l y z e d to c o n t a i n

respectively, 0.278 moles/liter citric acid and 16. 1 p e r c e n t

citric acid ( w e i g h t / v o l u m e basis). This organic phase w a s

then s p l i t into two s e p a r a t e 85 ml. portions. The first

portion was m i x e d with 20 ml. water, shaken, p l a c e d in a

40° C. water b a t h for about 15 min. , centrifuged for about

15 m i n . at 2800 R P M , and the organic and a q u e o u s phases

were separated and a n a l y z e d to c o n t a i n r e s p e c t i v e l y , 0. 2 2 7

moles /liter citric acid and 6. 4 p e r c e n t citric acid. This

organic phase was then m i x e d with 40 ml. of an a q u e o u s

solution containing 20 p e r c e n t trisodium citrate, shaken,

placed in a 40° C. water b a t h for about 15 m i n . , centrifuged

for about 15 m i n . at 2800 R P M , and the o r g a n i c phase w a s

separated and analyzed to c o n t a i n 0. 06 m o l e s / l i t e r citric acid.

The second portion of the above split o r g a n i c phase was m i x e d

w i t h the 20 ml. of w a t e r w h i c h had p r e v i o u s l y been mixed w i t h

the first portion of the split organic phase, shaken, placed i n

a 40° C. water bath for about 15 m i n . , centrifuged for about

15 min. at 2800 R P M , and the o r g a n i c and a q u e o u s phases

were separated. The aqueous phase was analyzed to c o n t a i n

9. 5 p e r c e n t (weight/volume basis) citric acid. The organic

phase was analyzed to c o n t a i n 0. 257 m o l e s / l i t e r citric acid.

 It can be s e e n f r o m the above data that c i t r i c a c i d can b e

easily extracted from an a q u e o u s solution t h e r e o f by a m i x -

ture of t r i l a u r y l a m i n e and oleic acid in. a h y d r o c a r b o n solvent

and t h a t the extracted citric acid can be e a s i l y recovered by

back-extraction with w a t e r at the same temperature as the e x -
traction. Residual citric acid in the o r g a n i c phase can be r e -

moved by b a c k - e x t r a c t i o n with t r i s o d i u m citrate. This a l s o

exemplifies b a c k - e x t r a c t i o n , with an a l k a l i s a l t to r e c o v e r the

extracted acid as an a l k a l i salt.

EXAMPLE 12

A 200 ml. solution of t r i l a u r y l a m i n e , oleic acid and t h e

liquid hydrocarbon d e s c r i b e d in E x a m p l e 1 was p r e p a r e d as

described in E x a m p l e 11. This s o l u t i o n was t h e n m i x e d w i t h

300 ml. of an a q u e o u s solution of 20 p e r c e n t malic acid

(weight/volume basis). The r e s u l t i n g mixture was shaken,

placed in a 40° C. water b a t h for about 15 m i n . , centrifuged

for about 15 m i n . at 2800 R P M , and the o r g a n i c and a q u e o u s

phases were separated and a n a l y z e d . The aqueous phase con-

tained 17. 0 p e r c e n t malic acid (weight/volume basis). The

organic phase,which contained 0. 400 M m a l i c acid, was then

s p l i t into two s e p a r a t e 85 ml. portions. The f i r s t portion

was m i x e d with 20 ml. water, shaken, p l a c e d in a 40° C .

water b a t h for about 15 m i n . , centrifuged for about 15 m i n .

at 2800 R P M , and the o r g a n i c phase was separated and

analyzed to c o n t a i n 0. 237 M m a l i c acid. The second portion

of the above split o r g a n i c phase was then m i x e d with the 20 m l .

of w a t e r w h i c h had p r e v i o u s l y been in c o n t a c t with the f i r s t

portion of the split organic phase. These materials were

shaken, p l a c e d in a 40° C. water bath for about 15 m i n . ,

centrifuged for about 15 min. at 2800 R P M , and the o r g a n i c

and a q u e o u s phases were separated and a n a l y z e d . The or-

ganic phase contained 0. 303 M m a l i c acid, and the a q u e o u s

phase contained 12.8 percent (weight/volume basis) malic

acid.

The above example shows that m a l i c a c i d can be e x t r a c t e d

by the amine-acid-hydrocarbon process of the p r e s e n t in-

vention and can be e a s i l y r e c o v e r e d by b a c k - e x t r a c t i o n with

water at the s a m e temperature as the e x t r a c t i o n .

EXAMPLE 13

A 200 ml. solution of t r i l a u r y l a m i n e , oleic acid and t h e

liquid h y d r o c a r b o n described in E x a m p l e 1 was prepared as

described in E x a m p l e 11. This solution was then mixed w i t h

300 ml. of an a q u e o u s solution of 20 p e r c e n t l a c t i c acid

(weight /volume basis). The r e s u l t i n g mixture was shaken,

p l a c e d in a 40° C. water b a t h for about 15 m i n . , centrifuged

for about 15 m i n . at 2800 R P M , and the o r g a n i c and a q u e o u s

phases were separated and a n a l y z e d . The aqueous phase con-

tained 16. 0 p e r c e n t lactic acid ( w e i g h t / v o l u m e basis). The

organic phase, which contained 0. 696 M l a c t i c acid, was then

s p l i t into two s e p a r a t e 85 ml. portions. The first portion w a s

m i x e d with 20 ml. water, shaken, p l a c e d in a 40° C. water

b a t h for about 15 m i n . , centrifuged for about 15 m i n . at 2 8 0 0

RPM, and the o r g a n i c p h a s e was separated and a n a l y z e d to

contain 0. 471 M l a c t i c acid. The second portion of the above

split organic phase was then m i x e d with the 20 ml. of w a t e r

which had p r e v i o u s l y b e e n in contact with the f i r s t portion of

the split organic phase. These materials were shaken, placed

in a 40° C. water bath for about 15 m i n . , centrifuged for about
15 min. at 2800 R P M , and the o r g a n i c and a q u e o u s phases

were separated and a n a l y z e d . The organic phase contained

0. 548 M l a c t i c acid, and the aqueous phase contained 14. 8

percent (weight/volume basis) lactic acid.

The above example shows that l a c t i c acid can be e x -

tracted by the a m i n e - a c i d - h y d r o c a r b o n process of t h e p r e s e n t

invention and can be e a s i l y recovered by b a c k - e x t r a c t i o n with

water at the s a m e temperature as the e x t r a c t i o n .

The following example describes the use of the extraction

process of the p r e s e n t i n v e n t i o n to e x t r a c t hydrochloric acid.

EXAMPLE 14 '

A 200 ml. solution of t r i l a u r y l a m i n e , oleic acid and t h e

liquid h y d r o c a r b o n described in E x a m p l e was p r e p a r e d as

described in E x a m p l e 11. This s o l u t i o n was then m i x e d w i t h

300 ml. of a 1N a q u e o u s solution of h y d r o c h l o r i c acid. The

resulting mixture was shaken, p l a c e d in a 40° C. water bath

for about 15 m i n . , centrifuged for about 15 m i n . at 2800 R P M ,

and the o r g a n i c and a q u e o u s phases were separated and

analyzed. The aqueous phase contained 0. 682 M hydrochloric

acid. The organic phase which contained 0. 539 M h y d r o -

chloric acid, was t h e n s p l i t into two s e p a r a t e 85 ml. portions.
The f i r s t p o r t i o n w a s m i x e d with 20 ml. water, shaken, placed
in a 40° C. water b a t h for about 15 m i n . , centrifuged for about
15 min. at 2800 R P M , and the o r g a n i c phase was separated
and a n a l y z e d to c o n t a i n 0. 520 M h y d r o c h l o r i c acid. The

second portion of the above split organic phase was then

m i x e d with the 20 ml. of w a t e r w h i c h had p r e v i o u s l y been in

c o n t a c t with the f i r s t portion of the split organic phase.

These materials were shaken, p l a c e d in a 40° C. water bath
for about 15 m i n . , centrifuged for about 15 min. at 2800 R P M ,
and the o r g a n i c and a q u e o u s phases were separated and

analyzed. The organic phase contained 0. 513 M h y d r o c h l o r i c

a c i d and the aqueous phase contained 0. 121 M h y d r o c h l o r i c

acid.

It can b e s e e n f r o m the above example that the amine in

the p r o c e s s of the p r e s e n t invention reacts with the s t r o n g

mineral hydrochloric acid. This resulting c o m p l e x is n o t

easily broken down by w a t e r in a b a c k - e x t r a c t i o n to e n a b l e

the h y d r o c h l o r i c acid to be r e c o v e r e d in an a q u e o u s solution.

 1. A process for the e x t r a c t i o n of an o r g a n i c acid from

an a q u e o u s solution thereof which comprises contacting such

s o l u t i o n with a mixture of a w a t e r immiscible amine and a

water immiscible organic acid d i s s o l v e d in a s u i t a b l e water

immiscible solvent.

2. A process according to C l a i m 1 wherein the w a t e r

immiscible amine contains at l e a s t 12 c a r b o n atoms in a g g r e -

gate.

3. A process according to C l a i m s 1-2 wherein the water

immiscible amine is t r i l a u r y l a m i n e .

4. A process according to C l a i m s 1-3 wherein the water

immiscible organic a c i d is s e l e c t e d f r o m the c l a s s consisting

of c a r b o x y l i c acids, alkylphosphoric acids, alkylphosphonic

acids, and h a l o g e n substituted derivatives thereof.

5. A process according to C l a i m s 1-4 wherein the water

immiscible organic a c i d is s e l e c t e d f r o m the c l a s s consisting

of o l e i c acid, diethylhexyl phosphoric acid, 2-bromohexanoic

acid, linoleic acid, octanoic acid, 2-bromolauric acid and a n

aliphatic substituted cyclopentyl carboxylic acid.

 6. A process according to C l a i m s 1-5 wherein the molar

proportion of a m i n e : o r g a n i c a c i d is f r o m about 0. 8:1 to a b o u t

1. 2:1.

7. A process according to C l a i m s 1-6 wherein the s.uitable

water immiscible solvent is s e l e c t e d f r o m the c l a s s con-

sisting of a l i p h a t i c hydrocarbons, aromatic hydrocarbons,

petroleum fractions, hydrocarbons carrying nitro or h a l o

substituents, alcohols, ketones and m i x t u r e s thereof.

8. A process according to C l a i m s 1-7 carried out at a

temperature from about 20° C. to about 80° C. -

9. A process according to C l a i m s 1-8 wherein the water

immiscible solvent m i x t u r e is then c o n t a c t e d with w a t e r to

back-extract and r e c o v e r the e x t r a c t e d organic a c i d at t h e

same temperature as the i n i t i a l extraction.

10. A process according to C l a i m s 1-9 wherein the organic

a c i d to be e x t r a c t e d is s e l e c t e d f r o m the c l a s s consisting of

citric acid, malic acid and l a c t i c acid.