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2,872,293

United States atent 0 Q? Patented Feb. 3, 1959

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It is a further object ofthis invention to provide a
method of preparing a stannate type stabilizer free of
2,872,293 adjuncts apt to reduce stabilizer e?iciency.
Another object of this invention is to prepare a stan
STABIIJZING HYDRUGEN PEROXIDE nate type stabilizer which will prevent objectionable in
Edward M. Roth, .Iia, Kenmore, N. Y., assignor, by mesne teraction between the stabilized hydrogen peroxide solu
assignments, to Food Machinery and Chemical Corpo tion and an aluminum container.
ration, San Jose, Caii?, a corporation of Deiaware Still another object of this invention is to prepare a
No Drawing. Application March 18, 1953 stannate type stabilizer which will maintain the original
Serial No. 343,245 stability level of a so stabilized'hydrogen peroxide solu
tion upon long term storage in aluminum containers.
1 Claim. (Cl. 23-2075) A further object of this invention is to prepare a stan
nate type stabilizer which will maintain the original
stability level of a so stabilized hydrogen peroxide solu
This invention pertains to the preparation of a stabilizer 15 tion even after diluting the hydrogen peroxide solution to
for solutions containing hydrogen peroxide, to a method a substantially lower concentration.
of stabilizing hydrogen peroxide and, more particularly, It is also an object of this invention to prepare a stan
to the preparation of a stannate stabilizer for such solu nate type stabilizer suitable for stabilization of alkaline
tions. 7 ' hydrogen peroxide process solutions.
The need to stabilize solutions containing hydrogen 20 It is also an object to provide a method of stabilizing
peroxide to prevent active oxygen loss during processing, hydrogen peroxide against the adverse in?uences of dilu
shipping and storing, has been recognized for. many years. tion with water. .
.Although numerous organic and inorganic stabilizers and I have now found that these and other objects of my
various stabilizing methods have become known to the invention are accomplished if a relatively concentrated
art, modern practice has come to recognize the pyrophos 25 stannate type stabilizer solution is prepared by dissolving
phate and stannate, or stannate containing stabilizers, as a stannate first in relatively concentrated hydrogen per
among the most efficient stabilizer types. Indeed, sta oxide and then adjusting the pH of the resulting stabilizer
bilizers of this type, as described by Reichert 1,958,204, solution with acid to substantially pH 5. This solution,
Gilbert 2,004,809, Gilbert 2,091,178 and Reichert 2,426, when added to unstabilized hydrogen peroxide, produces
, 154, as well as the stabilizing methods disclosed by these 30 better stabilities per unit of tin than addition of an
' patents, perform very well under ordinary conditions en aqueous stannate solution directly to the peroxide to be
countered in handling solutions containing hydrogen stabilized.
peroxide. The performance data given in the subsequent Tables 1
However, presently available stannate type stabilizers to 4 make it very clear that the stabilizing properties of
are not completely satisfactory in some respects. If a 35 a stannate type stabilizer are profoundly in?uenced by
stannate solution is added to solutions containing hy the chemical nature of the solvent medium in which the
drogen peroxide to serve as the sole stabilizing agent, stabilizer is prepared. The complex physico-chemical
clouding of the solution due to formation of insoluble properties of tin compounds are responsible for the fact
precipitates is very apt to occur. If pyrophosphates, that, depending on conditions, solutions of these com
which have a stabilizing effect of their own, are added to pounds may contain the tin compound in molecular,
prevent formation of precipitates, as vdescribed by Reichert colloidal or macro-disperse form. This last form is
1,958,204, the. stabilizing e?iciency of the stannate is clearly undesirable because, quite aside from its ordinarily
found to decrease. Hydrogen peroxide solutions sta low stabilizing e?iciency, macro-disperse particles produce
bilized in this manner, upon prolonged storage in the more or less pronounced turbidity or even precipitate in
commonly used aluminum containers, are found to exert, 45 the, solvent medium; in the present case, the stabilizer
on occasion, a corrosive effect on the container. This is containing hydrogenperoxide solution. Relatively low
evidenced not only in pitting of the container wall, but 7 stabilizing effects are observed in the non-turbid hydrogen
also results in reduced stability of the hydrogen peroxide peroxide solutions containing the tin compound in mo
solution thus stored. Although the exact mechanism of lecular dispersion, as results from the use of water as
this corrosive attack is not known, it is a familiar phe the solvent medium for the tin compound. .The sur
nomenon well known to the hydrogen peroxide manu prisingly high efficiency of the stannate-peroxide type sta
facturers. bilizer of this invention is presumably due to the particular
_ Another disadvantage of presently available stannate and critical micelle size obtained by reducing the water
type stabilizers is the fact that if they be used to stabilize activity in the solvent medium by substituting hydrogen
a more concentrated hydrogen peroxide solution and this 55 peroxide for the water ordinarily employed. That re
solution be subsequently diluted with water, the resulting duction of water activtiy is an important factor is borne
' dilute hydrogen peroxide solution will be less stable than out by the ?nding that the hydrogen peroxide concen
the original, more highly concentrated solution. This tration in the solvent medium has to be at least of the
fact might be due to stabilizer dilution or to introduction order of 20%, in order to obtain the desired effects.
of catalytically active impurities during the dilution step, 60 In short, there is reason to_believe that the tin com
but regardless of its mechanism, it requires addition of pound involved in preparing stannate type stabilizers is
further amounts of stabilizer properly to protect the obtained in different physical form and diiierent stabiliz
dilute hydrogen peroxide solution from objectionable de ing properties depending on whether water or hydrogen
composition. This is of considerable'practical interest
because large quantities of concentrated hydrogen peroxide peroxide solutions are used as the solvent medium.
are purchased and subsequently diluted and bottled for In the preparation of the concentrated stannate-per
resale. Such diluted product must possess an acceptable oxide stabilizer solution of my invention, I prefer to use
shelf life even though storage conditions thereof be ad sodium stannate trihydrate as the tin compound, for rea
verse. . sons of availability, purity and solubility.
It istherefore an object of this invention to provide a 70 The relatively concentrated hydrogen peroxide solution
method of preparing an efficient stannate type stabilizer used in my invention, as the solvent medium for the
for hydrogen peroxide solutions. stannate, may have an H202 content of between about
2,872,298
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20% and 50% by weight, although higher concentra~ Table 1
tions may be used. For convenience sake, ,the use of [Percent loss per year at room temperature of hydrogen per
commercial hydrogen peroxide solutions of 27.5% or oxide solutions before and after dilution, kept in glass]
35% concentration by weight islpreferred, and I prefer
to use the hydrogen peroxide solution as produced; that mg. Percent
Sample Sodium Type of Solution H202
is to say, not yet containing any stabilizing agents, so as Stannate Loss per
to avoid unnecessary, and possibly objectionably high per liter year
residues in the hydrogen peroxide solutions as stabilized
with the stabilizer of my invention. A _______ __ 100.0 H202 35%, water solution of stannate 1.0
stabilizer added.
The usual acids found suitable for adjusting the pH B _______ __ 15. 5 H202 35%, stabilized as in A and 40.3
of hydrogen peroxide solutions may be used to adjust diluted to 6% H202.
C _______ ._ 95.5 H202 35%, stannate-peroxide solution 1.0
:the pH of the solution resulting from dissolving sodium of stabilizer added.
stannate trihydrate in hydrogen peroxide of 20 to 50% D ______ __ 15.0 Sample 0 after dilution to 6% H202 2.2
concentration.
concentration. Examples of such acids are citric, lactic,
malic, gluconic, glycolic and phosphoric acid. For rea 15
The superior stabilizing effect of the stabilizer of this
sons of cost and availability I prefer to use phosphoric
acid. '
invention is clearly shown by the critical and much im
The following is an example of the exceedingly simple proved stabilizing effect after dilution of the stabilized
procedure required to prepare the stannate type stabilizer concentrated hydrogen peroxide solution, as shown in
of this invention, the most critical and distinguishing fea 20 samples C and -D above.
ture of that procedure being the dissolution of the tin Peroxide stability is also a?ected by possible inter
action between the solution and aluminum upon com
compound used in a relatively concentrated hydrogen mercial storage in the commonly used aluminum drums.
peroxide solution which serves as the solvent medium.
Here, again, the stabilizer of this invention gives im
EXAMPLE 1 25 proved results as shown in the following Table 2.
Table 2
100 grams of sodium stannate trihydrate [Percent loss per year at room temperature of hydrogen per
oxide solutions before and after dilution, the concentrated
solution having been stored in aluminum containers for at
Na2SHO33H2O least two weeks]
of C. P. grade was dissolved at room temperature and mg. Percent
with slight stirring in approximately 900 grams of a 35% Sample Sodium Type of Solution H202
solution of unstabilized hydrogen peroxide to give about Stannate Loss per
per liter Year
1000 grams of an approximately 10% sodium stannate
The pH of the resulting solution was found
. solution.
E _______ __ 100.0 H202 35%, water solution of stannate 1.8
to be about 7.5 to 8.0 and was adjusted by adding slowly stabilizer added. -
and with constant stirring, the required amount of con F ....... __ 15.5 Sample E after dilution to 6% H202 47.1
concentration.
centrated phosphoric acid, to result in a solution having G _______ ._ 96. 5 H202 35%, stannate-peroxide solution 1.0
a pH of about 5.0. The solution thus preparedis im of stabilizer added.
H _______ __ 15.0 Sample G after dilution to 6% H202 2.2
rnediately ready for use as stabilizer for a hydrogen per 40 concentration.

oxidesolution. '
If preferred, a somewhat more concentrated stabilizer These data clearly show that deleterious drum eifects
solution may be prepared. However, for ordinary prac on peroxide stability, particularly after dilution, are sub
tice, an approximately 10% stabilizer solution will be stantially reduced by the stabilizer of this invention, as
found to be convenient. - contrasted to a conventional type of stannate stabilizer.
Prior to adding the stabilizer solution to the hydro A conventional test for peroxide stability consists in
gen peroxide solution to be stabilized, I prefer to adjust keeping the sample under test for 24 hours at a tempera
the unstabilized hydrogen peroxide solution to about pH ture of 100 C. andthen determining the peroxide loss
2.5 to 2.7 by adding an alkali such as ammonium hy of the sample. The following Table 3 shows the supe
droxide. This pH adjustment serves to prevent precipita 50 rior performance of the stabilizer of this invention when
tion of any tin compound with ensuing cloudiness in the tested in accordance with that method.
stabilized hydrogen peroxide solution.
Following the pH adjustment, the stannate-peroxide Table 3
stabilized solution is added slowly and with stirring to [Percent loss in 24 hours at 100 C. of hydrogen peroxide solutions before
the hydrogen peroxide solution to be stabilized. After and after dilution, the concentrated solution having been stored in
aluminum containers for at least two weeks]
addition and uniform distribution of the stabilizer solu
.tion, the thus stabilized hydrogen peroxide solution may mg. Percent
then'be further adjusted, if desired, to the commonly Sample Sodium Type of Solution H202
preferred range of pH 3.5 to 4.0. Stannate Loss
per liter
The amount of stabilizer added is preferably about 10
mg. to 1000 mg. of sodium stannate per liter of resultant 100. 0 H202 35%, water solution of stannate 3.4
hydrogen peroxide solution. stabilizer added. _ t

The following tables show the etfectiveness of my stan 15.5 Sample I after dilution to 6% H202 22.8
concentration.
nate type stabilizer under various test conditions and will 96. 5 H202 35%, stannate-peroxide solution 0.5
also show its superiority over a stannate type stabilizer of stabilizer added.
15.0 Sample K after dilution to 6% H202 0.6
which is introduced into the hydrogen peroxide solution concentration.
to be stabilized in form of a stannate solution in water,
as contrasted to my stabilizer, which is introduced in I These data clearly show the exceptionally high im
form of a solution in hydrogen peroxide. provement in the stability, particularly of the diluted
As pointed out above, one of the important require 70 hydrogen peroxide solutions obtained by using the sta
ments for a hydrogen peroxide stabilizer is that it will bilizer ofthis invention, by first preparing a relatively
permit substantial dilution of a hydrogen peroxide solu concentrated solution in hydrogen peroxide, as compared
tion thusistabilized, with production of a diluted solu to the preparation of water solution of sodium stannate
' tion-of substantially equal stability. This is demonstrated and addition of such solution to the peroxide to be
by the data of Table 1. 75 stabilized.
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The stabilizer of this invention is also suitable to process solutions containing 0.1 and 1 part per million
protect alkaline hydrogen peroxide process solutions from of iron respectively. Here the stability test consisted
objectionable decomposition. Such process solutions are of determining percent loss of active oxygen after keep
of importance, for example, in the manufacture of sodium ing the sample for two hours at 60 C.
perborate. A typical process solution from which so Where data are given herein of the pH of a solution,
dium perborate would be recovered by precipitation would such data were determined by direct immersion of the
be composed of about 137 liter of distilled water, 48 glass electrode of a pH meter in the solution, the pH
liter of a saturated solution of sodium metaborate and of which was to be determined.
15 liter of a 50% solution of hydrogen peroxide. To What is claimed is:
insure satisfactory yields of sodium perborate, that is, 10 In the method of stabilizing aqueous hydrogen per
to avoid hydrogen peroxide losses through decomposition oxide with sodium stannate the improvement which
in the course of processing, addition of a stabilizer is comprises adjusting the pH of the aqueous hydrogen
advisable, particularly to counteract the catalytic e?ects peroxide to be stabilized to about pH 2.5 to 2.7 and
of unavoidable traces of iron present in the solution. then adding thereto a solution of sodium stannate in
The following Table 4 shows the excellent effects ob 15 hydrogen peroxide the pH of which solution is about
tained by using the stabilizer of this invention with such pH 5, said solution containing about 10% of sodium
Table 4 stannate and prepared by dissolving the sodium stannate
in unstabilized hydrogen peroxide of at least 20% con
Amount 0! Sta- Percent loss
centration, the amount of said solution added being suf
Parts per million Fe in process bilizer added in in peroxide 20 ?cient to produce a concentration per liter in the result
Solution gram of sodium after 2 hours ant mixture of 10 milligrams to 1000 milligrams of so~
stannate per liter at 60 0.
01' solution dium stannate.

none 11.0 References Cited in the ?le of this patent


1. 0 4. 5
none
1. 0
96. 2
9. 5
UNITED STATES PATENTS
1,958,204 Reichert _____________ _- May 8, 1934