Patented Sept.

2, 1952
2,609,391

UNITED STATE s PATENT OFFICE

2,609,391
STABILIZATION oF PERACIDs wiTH
DIPICOLINIC ACID
Frank P. Greenspan, Buffalo, and Donald G.
MacKellar, Kenmore, N.Y., assignors to Buf
falo Electro-Chemical Company, Inc., Tona-.
wanda, N.Y.
No Drawing. Application September 13, 1950,
Serial No. 184,710
12 Claims. (CI. 260-502)
1. 2
This invention relates to the stabilization of aliphatic acid by replacement of the hydroxyl
aqueous solutions of peracids. It is particularly group OH by the perhydroxyl group OOH.
concerned with the stabilization of aqueous Solu AS has been recognized by investigators in this
tions of peracetic acid by the employment of di field, the peracids differ very materially from
picolinic acid as a stabilizer. 5 peroxides and, stabilizers heretofore employed
Peracetic acid and its salts are employed prin- ; and recognized as stabilizers of hydrogen peroxide
cipally. in dilute solution as bleaching, washing are not effective as stabilizers for peracetic acid.
and germicidal baths. See article of Frank P. See Reichert et al., 2,347,434.
Greenspan and Donald C. MacKellar presented Therefore, the stabilization of aqueous solu
May 24, 1950 at the Tenth Annual Convention O tions of a peracid is concerned not merely with
F. I. T., Chicago, Illinois. Baths for this pur arresting or retarding the breakdown into oxygen
pose normally contain a low percentage of the and the aliphatic acid; rather, the decomposi
active ingredient, the peracid, and such baths tion of aqueous solutions of the acids involves a
may be prepared from a peracid of higher con relatively complicated series of the decomposition
centration. Since concentrated peracetic acid is 5 reactions, each of which yields a different de
most effective and economically prepared from composition product. - Exemplifying such decom
glacial acetic acid and high-strength hydrogen position by the employment of peracetic acid,
peroxide as, for instance, 90% H2O2, in the there appear to be several distinct mechanisms
presence of about 1% Sulfuric acid to catalyze of decomposition and these appear to proceed
the formation of peracetic acid, Such high con 20 principally in accordance with the following
centration products are diluted for Such com equations:
mercial uses. It will be understood, however, that
peracetic acid may be prepared by the reaction 1. CH3COOOH-4-HO-H2O2+CH3COOH
between acetic acid, acetic anhydride and hydro 2. CH3COOOH->O--CH3COOH
gen peroxide of Various strengths and in various 25
ways, reference being made to U. S. Patent 3. CH3COOOH-CH4+CO2+
2,490,800. It has been found generally desirable Small quantity of other products
to increase the resistance of the peracids to de The above reaction mechanisms appear to de
composition, i.e., to stabilize them. pend upon the temperature and the concentra
It is a principal object of the present invention 30 tion of the peracetic acid as well as the pH of the
to provide an effective stabilizer for peracetic Solution undergoing decomposition. For instance,
acid of Substantially any strength but particu the gas being evolved from a carboy of 40%
larly peracetic acid solutions containing substan peracetic acid, at room temperature, when ana
tial amounts of peracetic acid whereby the same lyzed was found to contain the following:
may be prepared and stored in concentrations 35 Per cent
greater than about 10%, prior to dilution and Sub CO2 ------------------------------------- 24.0
Sequent use, although the invention is applicable O? -------------------------------------- 75.6
to the stabilization of peracids of any strength. CO ------------------------------------- 0:0
It is also an object of the invention to provide
Stabilized Solutions of peracetic acid resistant to 40 Remainder ------------------------------ 0.4
decomposition at elevated temperatures, that is, A Sample of gas evolved from 1% peracetic acid
temperatures of 25° C. and above. at a pH 6.5 and at 80° C. was collected arid ana
The invention is applicable to the stabilization lyzed with the following results:
of the aliphatic peracids of which the lowest Per cent
member is performic acid HCOOOH, the next 45 CO2 ------------------------------------- 3.2
succeeding homolog differing by the radical CH2. O -------------------------------------- 95.8
The most important member of this series is CO ------------------------------------- 0.0
peracetic acid and the invention will be generally Remainder ------------------------------ 1.0
described and its particular application exempli Whatever the mechanism of the decomposi
fied with peracetic acid, CH3COOOH. The 50 tion may be, it is more greatly complicated than
peracids may be regarded as derived from the the simple. decomposition of hydrogen peroxide
 2,609,391
3 4.
into water and oxygen and, furthermore, it has the per cent loss in performic acid, at room ten
been found that the usual stabilizers for hydro perature, was reduced from 43% in 24 hours,
gen peroxide are not effective as stabilizers for to 20% in 24 hours. Results of similar type are
the peracids. Thus, whereas Sodium stannate is obtained with other peracids, for instance the
an excellent stabilizer for hydrogen peroxide, it 5 aliphatic peracids, even if solid at normal ten
is not particularly effective upon peracetic acid, perature show increased stability by inclusion
for instance as shown by the following: of dipicolinic acid. Perlauric acid unstabilized
showed a loss at room temperature (20° C.) Of
Per Cent Active 5.6% peracid per month. However, this loSS WaS
Concen-
tration
Oxygen LOSS O reduced by more than half when 500 parts per
Stabilizer parts per million dipicolinic acid was included as a stabi
nil. 5 Days 29 Days lizer, namely, to 2.1% per month. Similar re
Sults are obtainable With perbenzoic acid, per
Sodium Stannate------------------. 9.0 4. 4.
... 3
phthalic acid, percamphoric acid and a host of
. . . . .. . . . . . . . . . ... --> -- a -- was a -w- - -a as a a a saw aw 5.5
5 Others, including the Substituted aliphatic per
acids Such as perchloracetic acid.
A sample of relatively concentrated peracetic In general, the greater the amount of the
acid was prepared from standard grade acetic dipicolinic acid added, the greater the stabiliz
acid and 90% hydrogen peroxide in the presence ing effect. This is shown by the results of the
of 1% sulfuric acid. The resultant product con 20 following test when a very unstable commercial
tained 40% peracetic acid. To a sample of this Sample of 41.5% peracetic acid was treated with
peracetic acid was added 500 parts per million of Various amounts of the stabilizer and the
dipicolinic acid. The samples so treated, as well samples covered and stored at 30° C. The per
as a similar sample of the original peracetic acid loSS WaS determined after two weeks:
acid, not so treated, were stored at 30° C. in glass 25
stoppered Pyrex flasks for one month whereupon Percid
the loss of the peracetic acid concentration was Amount of 9SS
determined with the following results: w aw
Samples Peracetic Acid Strength, Pereent Acidin Parts
iSipiconi After
Two
Per Cent 30
SFNiii. Wils
Percent
Peracid
Sarnple w
Sibiiser Loss in
i. Noise 17.3
Month 2. O
3. 100 2.8
4. 1,000 1, G
40%peracetic acid------- N9ne.-------------------- 56.0 35
40%pera Cetic acid------- Dipicolinic Acid 500 p.p.m. 4.9
40% peracetic acid------- Dipicolinic Acid 1,000 p.p.m. 3. A Sample of 40% peracetic acid of somewhat
better initial stability was treated with 250 parts
The amount of stabilizes to be employed may per million of dipicolinic acid and stored in
vary considerably and may be from about 5 covered containers, and the peracid loss per
parts per million to 1000 parts per million, de 40 month determined at four-week and eight-week
pending upon the stability desired in the product intervals.
and the concentration of peracid in the Solu w

tion, with the average quantity required to Sta Amount of Percent

bilize being in the neighborhood of 250 to 750 --

Peracid 40%. Peracetic Acid AEE, I.Evil

- - - - - Peracid

g
parts per million of dipicolinic acid. - - 45 a e
The dipicolinic acid may be added to the ma per Million onth
terial subsequent to its formation or may be
added to the ingredients prior to their reaction (1) Control--------------------- None
seeks
4. 8.
in the presence of the catalyst. No material 2 Contigl-------------------- None 8 8.4
difference in effectiveness of stabilization ap (3) Stabilized 250 4. 0.6
50 (4) Stabilized 250 8 1.4
pears to result from the employment of these (5) Stabilized 1,000 4 O. :
Variations. (6) Stabilized--------- 1,000 8 0.9
As stated, the dipicolinic acid appears to be
effective as a stabilizer in substantially any dilu Generally, the amount of dipicolinic acid en
tion of the peracid. A sample of 40% peractic 55 ployed will depend upon the initial instability
acid was diluted to 1% peracid and the pH of the of the per'acid and the degree of stability desired
Solution adjusted to 7 by the addition of dilute in the final product, the greater the amount of
chemically pure caustic SOda, Solution. This So Stabilizer, the greater the stabilizing action.
lution was divided into a number of Samples, and However, 250 to 500 parts per million of the
dipicolinic acid added. The samples were left O Stabilizer is usually Sufficient in the average case.
at 80 C. and stabilities determined after a pe The following results were obtained in samples
riod of a hour. Those samples containing of 40% peracetic acid stored in covered con
dipicolinic acid Were much more resistant to de tainers at room temperature:
composition than the blank containing no di
picolinic acid. 35 Percent
Dipicolinic Acid in Parts Per Million Peracetic
Loss Per
Month
fEE
PSE Per Cent
Time. In Fe
Acid in Loss of
Parts Per EOTS Peracid
Million
--ee-or-i-------- 70
None -6 1.9
00 -6 61
3. 44.1

In the presence of 1000 p.p.m. dipicolinic acid, 75 action under conditions where the Sample of
The dipicolinic acid also shows good stabilizing
 2,609,391
5 6
peracid is deliberately contaminated. Samples
of 40% peracetic acid were exposed in uncovered
containers placed on the desktop at room tem
perature for the exposure times noted. They
were then transferred to clean glass stoppered
flasks and stored at 30° C. The stability of these
stored samples was then determined and is ex
pressed in the following table as per cent loss per
month. It will be seen that excellent resistance
to decomposition was inherent in the stabilized
samples:
Exposure SEPercent
is
Month
Houts
0.
A Unstabilized 40%. Peracetic Acid.------
. . . 24
s 0
B-Peracetic Acid 40% containing 250
p.p.m., Dipicolinic Acid---------------- 4.
- 24
C. Peracid Acid 40% Containing 500
0.
1.
00
0.8
p.p.m. Dipicolinic Acid---------------- 2 3.
Dipicolinic acid is generally recommended as a
stabilizer as the pure acid; however, the soluble
salts such as the alkali metal salts, may also be
employed to this end, as can certain double salts,
such as the double Salt With potassium nitrate.
It is believed that in Solution in the peracid di
picolinic acid itself is produced and functions
as the stabilizer.
By means of the present invention, it is possible 35
to obtain better stabilities in glass for the per
acids generally, and a stability not obtainable
with any known peroxygen stabilizer. It is fur
ther possible to employ standard grade chemicals
in the preparation of the peracid and by addition 40
of dipicolinic acid thereto, form a peracid of ex
cellent stability and one which possesses a re
serve stability against deliberate contamination.
From the practical view point, the invention
will find wide applicability for the stabilization
of peracetic acid as prepared from acetic acid
and the commercial strength of hydrogen per
oxide, i. e., aqueous solutions of peracetic acid
from about 10% to 55% strength. It will be un
derstood, however, that the invention is suitable 50
for stabilizing peracetic acid and peracids gen
erally of any strength.
What is claimed is:
1. The method of stabilizing a carboxylic
peracid which comprises incorporating dipic
olinic acid therein.
2. The method of stabilizing a carboxylic per
acid which comprises incorporating at least 5
parts per million dipicolonic acid therein.
10 3. The method of stabilizing peracetic acid
which comprises incorporating, dipicolinic acid
therein. -
4. The method of stabilizing peracetic acid
which comprises incorporating in stabilizing
5 amounts dipicolinic acid therein.
5. The method of stabilizing peracetic acid
which comprises incorporating at least 5 parts
0.9 per million dipicolinic acid therein.
E8 6. A stabilized carboxylic peracid containing
20.0 20
0.6 the peracid and a Small amount of dipicolinic
0.6
.7 acid as a stabilizer.
2.3 7. A stabilized carboxylic peracid containing
the peracid and at least 5 parts per million of
dipicolinic acid as a stabilizer.
25 8. A stabilized carboxylic peracid containing
the peracid and from 250 to 750 parts per million
of dipicolinic acid as a stabilizer.
9. A stabilized peracetic acid containing per
acetic acid and a Small amount of dipicolinic
30 acid as a stabilizer,
10. A stabilized peracetic acid containing per
acetic acid and at least 5 parts per million of
dipicolinic acid as a stabilizer.
ill. A stabilized peracetic acid containing per
acetic acid and from 250 to 750 parts per million
of dipicolinic acid as a stabilizer.
12. A stabilized peracetic acid solution con
taining from 10 to 55% peracetic acid and at least
5 parts per million of dipicolinic acid.
FRANK P. GREENSPAN.
DONAL.D. G. MACKELLAR.
REFERENCEs CITED
The following references are of record in the
file of this patent:
UNITED STATES PATENTS
Number Name - Date
2,363,778 Pedersen ---------- Nov. 28, 1944