Vol. 99, No.
11 F I F T Y Y E A R S OF I N D U S T R I A L
A History of the Hydrogen Peroxide Industry
M. E. Bretschger a n d Edward Shanley t
Hydrogen peroxide was discovered in 1818 by the French
chemist Thenard. His preparations were made by reacting
barium peroxide with acids. Little or no use of this discovery
was made for over 50 years. In 1866 the French chemist Tesse
De Moray is said to have suggested the use of hydrogen
peroxide as a bleaching agent. By this time chlorine had been
in general use for textile bleaching for over 60 years.
The first commercial manufacturing of hydrogen peroxide
seems to have been carried out by the barium process at the
plant of Schering in Berlin starting in 1873. Following this,
hydrogen peroxide came into use for pharmaceutical purposes
and for the bleaching of straw and silk, as well as for certain
cotton, wool, and rayon specialties. Some bleaeheries operated
small scale plants for the conversion of barium peroxide to
hydrogen peroxide.
The electrolytic method for making hydrogen peroxide nmy
be traced back to the research of Faraday who observed in
1832 that sulfate solutions could be oxidized at a platinum
anode. After many years of effort on the part of B,'odie,
Berthelot, Traube, and others, the products of this oxidation
were found to he the anions (SOs =) or (S._,O~=)depending upan
the conditions. Marshall isolated the potassimn salt KeS2Os,
commonly called potassium persulfate, in 1891.
Teichner, working at the Consortium fur Elektrochemische
Industrie in 1905 first proposed the ktea of manufacturing
hydrogen peroxide by hydrolysis of persuffates and subse-
quent recovery of the peroxide by distillation. About 1910 the
Osterreichische Chemische Werke in Weissenstein set up the
first commercial plant for this purpose. Sulfuric acid was
oxidized to H~S20s on platinum anodes, after which hydrogen
peroxide was recovered as proposed by Teichner. This process
was a commercial success and is still operated on a large scale.
In 1909, the German chemists Pietzsch and Adolph ob-
tained a patent on an alternative way to synthesize hydrogen
peroxide via electrolytic persulfate. This process, operated
since 1912 by the Elektrochemische Werke Munchen, consists
of anodically oxidizing an ammonium bisulfate solution to
yield ammonium persulfate. This oxidation can be carried out
at very high current yields. The ammonium persulfate solu-
tion is treated with potassium bisulfate whereby the sparingly
soluble potassium persulfate separates out. This salt is mixed
with 50~ sulfuric acid and heated under vacuum, whereby
hydrogen peroxide is formed and immediately distilled from
the reaction mixture. Because of the recrystallization step
this process is capable of making exceptionally pure and
stable hydrogen peroxide. It was the basis for much of the
German supply during both World Wars.
The Riedel and Lowenstein process for making hydrogen
peroxide combines the high current yields of ammonium bi-
sulfate electrolysis with the convenience of all-liquid opera-
tion, the ammonium persulfate solution being taken directly
from the electrolysis to the hydrolysis and distillation stage.
This process, first used by J. D. Riedel E. De Haen A. G. is
also exploited on a large scale at the present time.
Hydrogen peroxide from the various electrolytic processes
proved to be purer and more stable than that from the barium
process, and in addition was readily prepared at higher con-
eentrations, such as 27.5 per cent, 35 per cent, and 50 per
cent. As a result of these factors the electrolytic processes
Buffalo Electro-Chemical Company, Inc., Division of Food
Machinery and Chemical Corporation, Buffalo, New York.
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ELECTROLYSIS 311C
quickly attained a dominating position in peroxide manu-
facture.
Electrolytic hydrogen peroxide was first made in the U.S.A.
in 1926. Since that time American producers have made great
strides in improving the product, its shipping containers, and
the manufacturing processes. Regarding the product, the
most important improvements have been in the storage
stability. Hydrogen peroxide solutions tend to break down
into water and oxygen, a process which is accelerated by
most metals, almost all impurities such as heavy metal ions,
dust and dirt, and many other materials. The work of Reichert
and collaborators exemplifies successful research into means
for improving the stability of commercial hydrogen peroxide.
In a series of patents issued during the 1930's and assigned
to the Du Pont Company, these men disclosed the tin process
for peroxide stabilization, furnishing one means for making
commercial hydrogen peroxide so stable that only one or two
per cent of the active oxygen is lost during 24 hours at 100~
FIG. 1. Early batch-type distillation
and less than this amount in a year of normal storage. Simi-
larly and subsequent to the above, many other stabilizing
reagents have been developed and particularly has the de-
velopment of processes for very high purity peroxide furthered
such program.
Hydrogen peroxide was originally shipped only in glass
bottles and carboys. In 1931 the Buffalo Electro-Chemical
Company pioneered the use of aluminum tank cars for ship-
ping concentrated hydrogen peroxide. Suitable aluminum
drums were developed a little later and today ahnost all
peroxide shipments are made in one or another of these con-
tainers. Aluminum storage tanks are also commonly employed
at the point of use. The peroxide industry could not have
reached its present size without the development of these
safe, inexpensive and convenient shipping and storage con-
tainers.
Great strides have also been made in manufacturing opera-
tions. Modern peroxide stills have about eight times the
throughput of the original European counterparts. Fig. 1
and 2 show the contrast between the older batch4ype dis-
tillation and a modern still room. Fig. 3 shows a modern
battery room, the cells of which are operated at about three
times the current input of early models.
Improvements in peroxide technology are also apparent
in the range of available concentrations of peroxide. The
standard commercial concentration was 27.5 per cent H202
 312C J O U R N A L OF T H E E L E C T R O C H E M I C A L S O C I E T Y
in the 1930's. Today most deliveries are made at 35 per cent
or 50 per cent, and 90 per cent H202 is readily available.
Perhaps the most tangible evidence for improvement in
manufacturing methods is furnished by price comparisons.
In a time of rapid inflation the price of hydrogen peroxide
has shown a downward trend as illustrated in Fig. 4. This
record has been achieved by continual refinements in process-
ing, permitting a steady reduction in costs.
FIG. 2. A modern peroxide still room
FIG. 3. A modern battery room
Following the introduction of the electrolytic hydrogen
peroxide into the U.S.A., large-scale application research was
undertaken in this country. From 1925 to the present time
American peroxide producers have invested a total of about
1000 man years in such research. The industrial applications
of the product have followed a sharply rising curve, due in
large measure to this factor. The growth curve is illustrated
in Fig. 5. A few of the important uses, most of which were
fostered and developed in large part by the hydrogen peroxide
industry, are outlined below.
An early use for hydrogen peroxide was in the bleaching of
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November 1952
cotton goods, and by the early 1930's hydrogen peroxide was
being used for specialty bleaching in several American cotton
mills. The original impetus was furnished by the fact that
cotton goods containing vat-dyed portions could be peroxide
bleached without damage to the colors. The reliability and
safety of the peroxide bleaching process, and the excellence
of the results led to a great swing toward the use of this re
FIG. 4. Price of hydrogen peroxide
Fit. 5. Production of hydrogen peroxide
agent in all cotton processing. During the 1930's this trend
carried hydrogen peroxide into the bleaching of all types of
cotton yarns, knit goods, and woven goods, both colored and
all white. The continuous bleaching system for use in process-
ing cotton piece goods appeared in 1940. Having the usual
merits of continuous operations, such as faster processing,
greater uniformity, and low cost, this process was an imme-
diate success. Its adoption was delayed by material shortages
during the war years, but by 1948 most large scale cotton piece
 Vol. 99, No. II F I F T Y Y E A R S OF I N D U S T R I A L E L E C T R O L Y S I S
goods bleaching in the U.S. was being carried out in con-
tinuous peroxide equipment. In addition, the process has been
adopted by many bleaeheries abroad, and continuous peroxide
bleaching equipment is now coming into use all over the world.
About 80 per cent of all cotton bleaching in the U.S. is
now carried out with hydrogen peroxide, and this for some
years was the largest single use for H20~.
The bleaching of wool with hydrogen peroxide has been
practiced, at least on a small scale, for a great many years.
However, until the early 1920's peroxide wool bleaching was
a specialty operation in the U.S. With the availability of
domestic hydrogen peroxide, wool bleachers have turned in-
creasingly to the use of this chemical in place of the various
reducing bleaches. Starting in 1928, hydrogen peroxide proc-
essing was adapted to the continuous wool scouring machine.
Since that time peroxide bleaching has been applied to a
constantly increasing proportion of the wool produced in this
country.
The bleaching of groundwood pulp has become a major
outlet for peroxide during the past few years. Interest in
peroxide for this purpose was fostered by the desire to use
groundwood pulp as a partial replacement for chemical pulp
in book and magazine papers. Groundwood pulping yields
approach 100 per cent based on the wood, while chemical
pulping by its very nature discards about half the wood
weight, retaining only the cellulose for paper making. How-
ever, groundwood pulp is dark in color and is not bleaehable
by standard chlorine pulp bleaching teehniques. The develop-
ment of peroxide bleaching methods for groundwood pulps
has fostered the use of this cheaper pulp on a very large
scale, and most nationally circulated magazines are eurrently
printed on groundwood content paper.
The newest big use for peroxygen chemicals is in the field
of organic synthesis. The current availability of concentrated
hydrogen peroxide makes it convenient and economical to
synthesize performie, peraeetie, and other peracids. This in
turn makes it possible to carry out numerous organic oxida-
tion reactions. Examples are the synthesis of epoxy and hy-
droxy stearie acids from oleie add. The epoxy compounds
are especially valuable as stabilizers and plastieizers for
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313C
chlorinated polymers and for the production of new resins
and surface active materia}~. Other valuable new reactions
of the same type include the synthesis of an epoxidized in-
secticide, Dieldrin, and the preparation of 17 hydroxy stear-
oids, such as cortisone.
Drug and cosmetie uses, longtime standby of the peroxide
industry, continue to thrive, although now constituting a
minor part of total peroxide consumption. Some millions of
small bottles of hydrogen peroxide are sold annually for use
in hair dyeing, hail" bleaehing, in cold waving, and for various
pharmaceutical uses. Most of this material is bottled at a per
cent or 6 per cent H=O~ by firms purchasing 35 per cent in
bulk containers.
Before World War II the Germans carried on secret large-
scale developments looking toward the production of very
highly eoneentrated hydrogen peroxide and its use in weapons
of war. Large facilities were set up for making 80-85 per cent
hydrogen peroxide. As it turned out, these developments were
not completed in time t~ have a decisive effect. Some, like
the high speed submarine and the long range rocket might
have changed the course of the war.
The American peroxide industry, when appraised of the
need, was able to outdo European praetiee. In reeord time
the Armed Forces were provided with a supply of 90 per cent
hydrogen peroxide, purer and more concentrated than that
available in Germany- The military research conducted on
the basis of this material is largely under security restric-
tions, but it is safe to assume that our country will not lag
in the exploitation of this compact and extremely powerful
energy source.
To supply the expanding demands outlined above has re-
quired continuous expansion of the hydrogen peroxide pro-
ducing facilities. Hydrogen peroxide has been in very tight
supply in this country many times in the past ten years, yet
essential demands have always been met. Because of the in-
evitable lag between a decision to expand and the completion
of a plant, continued approximate balance of supply and
demand is evidence of foresight on the part of management.
At the present time and for the immediate future it is indi-
cated that all demands for this chemical can be fully met.