MUCIC ACID FROM ARABINOGALACTAN

GEORGE T . A U S T I N
College of Engineering Research Division, Washington State University, Pullman, Wash. 99163

Mucic acid was prepared by oxidizing commercially produced arabinogalactan

with nitric acid. Optimum yields of 5 8 grams of mucic acid per 100 grams
of arabinogalactan fed were obtained using 3 hours' heating a t 93OC. starting
with 60% "01. The distribution of H N O i as evolved oxides and residual mother
liquor was determined. Chromatographic studies of impurities were made. Cost
estimates for raw materials for commercial production are included.

MUCIC,
acid, the six-carbon dibasic tetrahydroxy acid
obtained by the oxidation of lactose, galactose, or
galactans with nitric acid, was discovered and studied
a t a very early date. Liebig (1847) describes prior work
done by Berzelius, Hagen, and Guckelberger. Because
of the wide range of usefulness of similar dibasic acids
such as oxalic and tartaric, it seems that mucic should
be a commercially valuable substance, but the high cost
of the lactose and galactose used for its manufacture has
OHH OH
I / I tion was always controllable. The vessel was held a t con-
HOOC-C-C-C-C-COOH
I I I I
H OHOHH
kept it too expensive to be industrially interesting. Acree
(1921) and Schorger (1921, 1929) patented methods for
manufacturing mucic acid from larch sawdust, which is
high in arabinogalactan and can be oxidized to mucic
acid with nitric acid, but nitration-oxidation in the pres-
ence of cellulosic materials is most hazardous. Whittier
(1924) studied the catalyzed oxidation of galactose to
mucic acid and found that 3570 nitric acid a t 85" C. pro-
duced optimum yields. Tollens (1885) describes purification
methods.
Arabinogalactan has recently appeared as a commercial
product (STRactan, St. Regis Corp., Libby, Mont.),
available in large quantity a t prices that have been
estimated (Adams, 1967) as low as 20 cents per pound,
which makes it an interesting raw material for mucic
acid production. Attempts t o oxidize arabinogalactan to
mucic acid using bromate, iodate, hypochlorite, per-
manganate, chromate, and air with catalysts were all
unsuccessful. Conversion by oxidation with nitric acid is
extremely simple.
The effects of time, temperature, and concentration of
nitric acid on the oxidation of arabinogalactan were
studied. Because a considerable amount of nitric acid
is lost in the mother liquor and as fumes, attempts to
devise satisfactory methods to recover part of the nitric
values thus lost are also reported. Methods of purifying
the crude mucic acid obtained are described and a thin-
layer chromatographic study of the contents of the mother
liquor and precipitates was made.
Apparatus and Procedure
Arabinogalactan used for these studies was commercial
STRactan-10 obtained from the St. Regis Corp. This mate-
rial is approximately 98% arabinogalactan, with some
minor brown colored impurities of tsnnin-like substances.
Twenty-five grams of arabinogalactan were added t o a
1-liter, three-necked flask equipped with a reflux conden-
ser, the requisite quantity of water was added, and the
mixture was heated in a constant temperature bath in
a fume hood. Concentrated nitric acid (7OCc) was added
to the solution in one installment and 2 to 4 drops of
Dow-Corning antifoam B were added to control persistent
foaming. Vigorous evolution of oxides of nitrogen began
quickly, but had largely subsided in about 1 hour. The
induction period rarely exceeded 5 minutes and the reac-
stant temperature for the reaction time noted, allowed
to sit overnight a t room temperature, then the product
was filtered through a medium porosity sintered glass
crucible, washed with $0 to 80 ml. of iced distilled water
and 20 ml. of alcohol, dried for 24 hours a t 90°C., and
weighed.
Mucic acid is only slightly water-soluble (0.33 gram
per 100 grams of H,O), so very little should be lost in
washing. An experimental wash of 15 grams of dried prod-
uct with 70 ml. of water a t room temperature produced
a loss in weight under l ' c . A similar wash with 95'c
ethanol produced a negligible weight loss, indicating the
almost complete absence of oxalic acid in the product.
Expected impurities in the acid included oxalic, saccharic,
a b - and t a b mucic acids, etc., but these substances are
water- and/or alcohol-soluble and should be reduced to
low values by the simple wash purification.
A sample of the product was converted to sodium
mucate, recrystallized several times from hot water, then
reconverted to mucic acid by acidification. The melting
point remained constant a t 205" to 210°C. (with
decomposition), the infrared absorption spectrum re-
mained unaltered, and the thin-layer chromatograms of
the precipitate remained substantially identical. Melting
point is not a good criterion for purity of mucic acid,
but the once-washed material has a neutral equivalent
of 105 (theoretical, 105) and is believed to be pure. Figure
1 shows TLC chromatograms of the washed mucic acid
solid, recrystallized washed mucic acid solid, oxalic acid,
and the mother liquor from oxidations of arabinogalactan,
arabinose, and galactose with nitric acid under similar
conditions.
Small samples of D-arabinose (Mann), L(+)-arabinose
(Fisher), D(-)-arabinose (Eastman), D(+)-galactose (East-
man), lactose, and commercial arabinogalactan were
oxidized with nitric acid under identical conditions. D ( + ) -
galactose, lactose, and arabinogalactan reaction products

424 I & E C PRODUCT RESEARCH A N D DEVELOPMENT

 Nitric Acid Consumption. The nitric acid used is either
evolved as oxides of nitrogen or remains behind as nitric
acid in the mother liquor; only a small amount is des-
troyed.
Figure 4 shows the apparatus used to determine the
evolved oxides of nitrogen by absorption in sodium hydrox-
ide, reoxidation with air, and hack titration. The nitrate
in the spent liquor was determined gravimetrically by
precipitation with nitron following removal of interfering
organic substances by oxidation with permanganate. Nitric
acid balances obtained in this manner check within 670,
which can he taken as the upper limit of the loss to
Figure 1. Thin-layer chromatogram of oxidation product solids he expected.
and mother liquors
R,Voluer

1 . Mother liquor-D-arabinose oxidized wilh HNOl 0.65,0.52.0.43

2. Mother liquor-L(+)-orabinore oxidized with "Os 0.66,0.48, 0.43
3. Mother liqu~r-D(-)-orobinore oxidized with "08 0.67,0.49, 0.42
4. Mother liquor-D(+)-galoaore oxidized with HN03 0.67,0.53, 0.46
5. Mother liquor-lactose 0.67,0.53,0.45
6. Mother liquor-STRoOon-2 0.67,0.52, 0.43
7. Precipitole-D(+)-saloctore 0.45
8. Precipitole-loclore 0.40
9. Piecipitote-STRocton-2 0.50
10. Oxalic acid 0.43
1 I . TEA and woter only 0.44

contained solid mucic acid; the other materials yielded

clear solutions only. These small samples were used for
the chromatographic studies. The chromatographic Fig
medium used was Mallinckrodt CHRomar-500 silica- mu
containing sheet. Two-microliter spots of triethylamine
salt solutions were used with the composition 0.1 gram
of salt plus 4 ml. of H,O plus 1 ml. of triethylamine. These 0.c
were developed ascending with 60/20/20 v./v./v. 1-
~_____.
hntinol-olsrii m-ot.ir
lll". erirl-arat.er
l mirtnre
.^...._I_and
_ viu~alizod
._I
with ninhydrin.
0 0.:
Q
I t has not proved possible to separate oxaiic from mucitc m
acid chromatographically, but several unidentified impu '
Q
040
rities, a t least part of them oxidation products from arahin
ose, exist in the mother liquor and are absent from th,e
z
washed precipitate. Reaction products from arabinose ani1 lsi 0 30
n
galactose afe shown to he similar, with impurity levelS A
W
:.. 'L^ I_--1 ---,.:..:L"L"" C_^_-. -
.
.:
J
"&
:
-.
. ^C -","-a,."-
6dl"L.'VUZ,
111 Ll't: WLIbIICU pIwApLLILGh llV'll "AluaLlVII "I
020
lactose, and arabinogalactan all low and similar. Oxidation 70 75 80 85 90 95 100
of arabinose [D, L(+), and D(-)] produced no precipitate,
while o(+)-galactose, lactose, and arahinogalactan all gave
precipitates of a similar nature, but in varying quantity
as shown by melting point, infrared spectrum, and neutral
equivalent.
Effect of Time of Redion.. Arahinogalactan was oxidized
starting with 41.1 and 54.6% nitric acid a t 9 2 C . and
with 41.1% acid a t 9YC. for varying periods (Figure
2). Periods beyond 3 hours bring decreased yields in all
cases, probably due to continued oxidation of the products
formed. All later studies were made with 3 hours' heating
I AIR PUMP

time.
Effect of Initial Acid Concentration and Temperature. A
comprehensive series of tests with initial nitric acid concen-
trations of 30, 40, 50, and 60% resulted in the values
shown in Figure 3. These tests show that optimum yields J
of 58 grams of mucic acid per 100 grams of arahinogalactan OIL B A T H
charged occur when, the initial nitric acid concentration
is 60% and the reaction is allowed to run 3 hours a t Figure 4. Apparatus for oxidation of arabinogalactan
94°C. with nitric aicd

VOL. 8 N O , 4 DECEMBER 1 9 6 9 425

 Table 1. Distribution and Consumption of Nitric Acid

Initial HNO, "0, Evolved, "03 Mother, icHXO', in Grams HNOI" Grams HiVOID
Run No. Con.cn., 5; Grams Grams Mother Liquor G r a m M.4 Grams M A
Temperature 88' C.
1 35.3 22.8 24.6 50 3.89 2.10
2 38.0 25.8 22.4 45 3.91 1.88
3 44.8 27.0 17.3 35 3.60 1.64
4 49.3 29.2 17.4 35 3.68 1.52
0 61.5 36.5 9.3 29 3.45 0.91
Temperature 93s C.
6 29.1 20.0 29.7' 61 4.24 2.53
7 35.3 22.5 27.2' 55 3.92 2.15
8 41.2 30.2 19.jc 39 3.63 1.42
9 44.8 28.8 20.9' 42 3.63 1.52
10 49.3 30.3 19.4 39 3.60 1.41
11 54.8 33.8 15.9' 32 3.50 1.12
12 61.5 33.8 15.9 32 3.64 1.16
Assumes no HiVO, recover?., acid fed M A produced. 'Assumes all HNO, vapors evolved recocerable, (acid fed-acid evolved) M A produced
Estimated by difference.

Taking a price of 20 cents per pound for arabinogalactan

I I
0.5 L I I I I 1
20 30 40 50 60
I N I T I A L C O N C E N T R A T I O N OF
N I T R I C A C I D - O/o
Figure 5 . Effect of initial nitric acid concentration on
nitric acid utilization
U p p e r . 88°C.
Lower. 93°C.
The absorption of the evolved oxides of nitrogen in
fresh arabinogalactan solutions has been tried and found
feasible, although foaming is a persistent problem. T h e
concentration of nitric acid in the mother liquor is between
10 and 24% and represents nearly half of the acid fed,
so this material cannot be wasted if the process is to
be economic. A small amount can be utilized as dilution
water in making up reactant solutions and tests have
shown that the impurities do not build up in the system,
causing difficulties. The remainder must be recovered by
distillation, but no experiments on the recovery problems
have been made. Table I and Figure 5 summarize the
results obtained from a series of experiments designed
to study nitric acid distribution and consumption.
and technical 6 8 5 nitric acid a t 5 cents per pound, the
raw material costs for mucic acid, made under optimum
observed conditions, are: if evolved gases are wasted,
$0.60; if evolved gases are recovered, $0.43; if evolved
gases and HNOi in mother liquor are recovered ( 6 5 loss),
$0.36.
I In view of the extra equipment required for the recovery
of the mother liquor, this step would probably be economi-
cally unsound unless a waste-disposal problem made it
essential.
Optimum conditions for manufacture thus appear to
be 3 hours' reaction time a t 94°C. with an initial 6 0 5
70 concentration of nitric acid. High temperatures (90" to
l0O'C.) are also essential if the precipitate obtained is
to be filterable. At temperatures below 90'C. the acid
lives up to its German name, "Schleimsaure." Product
color is also much improved by high temperature oxidation.
Acknowledgment
S. M. Jain made most of the oxidation runs as part
of an M. S.thesis problem at Washington State University
(1961). Other students contributing significantly to this
work include: Maurice Hedlund, Donald Bea, Karl
Berntsen, Don Ennis, Dave Larsen, and Ibrahim Kellizy.
Literature Cited
Acree, S.F., Brit. Patent 160,777 (March 18, 1921).
Adams, M. F., Washington State University, Pullman,
Wash., private correspondence, 1967.t
Liebig, J., Ann. 63, 347 (1847).
Schorger, A. W., Can. Patent 213,175 (Aug. 30, 1921);
U. S. Patent 1,718,837 (June 25, 1929).
Tollens, G., Ann. 227, 222 (1885).
Whittier, E. O., Ind. Eng. Chem. 16, 745 (1924).
RECEIVED
for review March 17, 1969
ACCEPTED July 22, 1969

426 I & E C PRODUCT RESEARCH A N D DEVELOPMENT