36
Soap, Fatty Acids, and
Synthetic Detergents
Janine Chupa, * Steve Misner, * Amit Sachdev,*
and George A. Smith**
SOAP AND FATTY ACIDS
Introduction
The origin of the word "soap" is traced to sac-
rificial Mount Sapo of ancient Roman legend.
The mixture of fat and wood ashes that
reacted to form soap was carried by rain to the
banks of the Tiber River and was found as a
clay deposit useful for cleaning clothes. 1
The boiling of fats with ashes was recorded
as early as 2500 B.C. Commercial soap-making
was a widespread art in the Middle Ages in
Europe. The invention of the soda ash process
by LeBlanc in 1791, and the discovery by
Chevreul in 1811 that soap was composed of a
mixture of fatty acids paved the way to mod-
em soap-manufacturing processess.F
Chemistry
The modem definition of soap relates to
cleansing agents derived from fats, oils, and
other fatty derivatives: the soaps are alkali
*Colgate Palmolive Company, Piscataway, NJ-Soap
and Fatty Acids.
**Huntsman performance products, Austin, TX-
Synthetic Detergents.
1694
and ammonium salts of fatty acids containing
from 8 to 22 carbon atoms. These fatty acids
are generally a mixture of saturated, unsatu-
rated, and polyunsaturated moieties:
CH 3(CH2)lOCOOM: saturated soap
CH3(CH2)6CH2CH =CHCHz(CHz)6COOM:
mono-unsaturated soap
CH3(CH2MCH2CH=CH)2CHiCH2)6COOM:
di-unsaturated soap
CH 3(CH2CH=CH)3CHz(CH2)6COOM:
poly-unsaturated soap
[M = Na, K, (HOCH2CH2)3NH+]
In general, two types of chemical reactions
are utilized in the manufacture of soap: the
saponification of triglycerides (fats and oils)
and the neutralization of fatty acids (which
themselves are produced from the triglyc-
erides by a variety of methods, most notably
splitting or hydrolysis of fats and oils with
steam under high pressure). Sodium hydrox-
ide (the predominant alkali employed in the
manufacture of soaps), potassium hydroxide,
sodium carbonate, and triethanolamine are
 SOAP, FATTY ACIDS, AND SYNTHETIC DETERGENTS 1695

saponification
3 RCOONa + Glycerin
(NaOH) Neutral Fat
(Soap) saponification
process

RCO-OCH 2
RCO-OCH
RCO-OCH 2
Triglyceride
Fat
splitting
RCOOH + Glycerin
>3
Fatty Acid

Neutralization

3
1
RCOONa
(NaOH)

Fatty Acid
Neutralization
(Soap) Process
Fig. 36.1. The chemistry of soap manufacture.

Methanol
Triglyceride --------------~~ RCOOMe + Glycerin
Catalyst
Fatty Methyl Ester

1 Saponification
(NaOH)
RCOONa + MeOH
(Soap)
Fig. 36.2. Fatty methyl ester process for soap manufacture.

the most commonly utilized alkaline moieties
in these processes (Fig. 36.1)Y
In recent years, soap manufacture by an
alternate route, the saponification of fatty
methyl esters, has been under development,
most notably in Japan (Lion Corporation)
and Italy (Ballestra). The fatty methyl esters
are obtained from the methanolysis of
triglycerides; inorganic alkali, quaternary
ammonium salts, and enzymes (lipase)
have been used as catalysts for methanol-
ysis in commercially practiced processes
(Fig. 36.2). The methyl ester process for soap
manufacture is typically more capital and
cost intensive versus the more traditional
fats/oils saponification and fatty acid neutral-
ization processes.
Manufacturing Technology
Several designs of commercial equipment,
based on the two processes described in
Fig. 36.1, are available for the manufacture
of soap.