Patented Sept.

5, 1950 2,520,915

UNITED STATES PATENT OFFICE

2,520,915
PREPARATION OF SODUM CEORTE
George L. Cunningham, New York, N. Y., and
Frank Pretka, St. Paul, Minn, assignors to Dia
mond Alkali Company, Cleveland, Ohio, a cor
poration of Delaware
No Drawing. Application April 26, 1945,
Serial No. 590,514
S 3 Cairns. (C. 23-85)
2
The present invention relates in general to the flow of chlorine dioxide into said Solution is
the art of preparing oxidizing bleaching agents discontinued as also is the agitation of the so
and in particular to a new and improved method lution Set up by Suitable mechanical means be
of preparing sodium chlorite. fore the gas and liquid were first contacted. Then,
Heretofore it has not, to the best of our to recover the thus prepared sodium chlorite as
knowledge, been possible to produce Sodium chlo a premium grade product having a maximum of
rite by the simple, direct method of contacting bleaching power, the resulting aqueous mixture
sodium hydroxide with chlorine dioxide without of sodium chlorite and potassium chlorate is de
an equivalent quantity of Sodium chlorate re hydrated by evaporation until Substantially all
sulting. Consequently, because of the difficulty O the potassium chlorate is precipitated, and a
encountered in separating sodium chlorite from solid-liquid separation is effected through filtra
sodium chlorate and the low theoretical yield tion. The solid phase consisting of potassiuri
of Sodium chlorite on the basis of the quantity chlorate and substantially no sodium chlorite is
reacted, this process has not been generally a C desirably dehydrated and stored, while the liquid
cepted for commercial production - and indirect 5 phase containing Sodium chlorite is further con
and more complicated substitutes have been de centrated to obtain Solid Sodium chlorite which
Wised and employed. is preferably dried and stored out of contact with
As a result of our invention, it is now possible air containing moisture, chlorine, carbon dioxide
to double the sodium efficiency So that theoreti and like contaminants.
cally all the sodium employed can be recovered as Although sodium chlorite, unlike SOdin hy
sodium chlorite. Moreover, because of our dis pochlorite, is relatively stable in aqueous Solu
covery, it is possible to produce Sodium chlorite tion at temperatures up to the normal boiling
directly in a single step using chlorine dioxide, point of water, provided that the Solution is
While realizing maximum sodium efficiency. alkaline and is not exposed to actinic light, We
Briefly, the process of the present invention in prefer to treat and evaporate Such Solutions and
a preferred embodiment comprises the steps of dehydrate solid sodium chlorite under partial
contacting chlorine dioxide gas With Water Con vacuum at temperatures below about 70° C. Such
taining hydroxides of sodium and potassium. practice results in a consistently Small percentage
According to our invention as we prefer to of decomposition and loss of chlorite although
practice it to produce premium grade sodium ideal pH and light conditions do not prevail, and
chlorite, gaseous chlorine dioxide prepared in it possesses the further advantage that. Sodium
any convenient manner and substantially free of chlorite solubility is maintained at a minimum
contaminants such as carbon dioxide or chlorine, and product recovery and process efficiency is
is passed into a sodium hydroxide-water solution maximized.
containing potassium hydroxide in quantity ap 35 It Will be understood that without either de
proximately equimolar to said sodium hydroxide parting from the spirit of our invention or going
whereupon the reaction expressed in chemical beyond the scope of the appended claims, pro
language as follows takes place: cedures differing from the above described, ex
O cept in the important ultimate results, may be
2CO -- NaOH -- KOH - NaClO -- KClO3 - HO 40 employed. It is the fundamental concept of si
By way of comparison, the following would be multaneously producing Sodium chlorite and po
tassium chlorate which our invention embraces
the reaction if, as taught by the art, aforesaid and which we are claiming as novel and patent
solution consisted of Water and Sodium hydrox able. To illustrate, in addition to the method
ide: 45 of the foregoing detailed description we contem
O
2CO - 2NaOH - NaClO -- NaClO3 + H2O plate the preparation of sodium chlorite and
potassium chlorate by contacting Sodium chlorate
Since the water of the Sodium hydroxide SO and potassium chlorite in an aqueous medium,
lution in the foregoing reactions is merely the or by passing in contact with an aqueous me
medium and unaffected chemically by reagents 50 dium containing sodium hydroxide and potassium
or reaction products, its presence is indicated chlorite, chlorine dioxide. Certain refinements
above the arrow in each instance. of and controls over these processes not beyond
When the bases (potassium and Sodium hy ordinary skill are not detailed here but will be
droxides) are practically exhausted, that is, obvious to those versed in the art and will be
when the solution is neutral or slightly alkaline 55 employed to advantage by them.
 ---. - - - - -
2,520,915
v. 3 4.
The present invention will perhaps be better 2. In a process for preparing sodium chlorite
understood by those skilled in the art by the substantially uncontaminated with sodium chlo
following illustrative, but not limiting, example rate, the steps of forming a solution containing
of Our practice of it: in admixture sodium hydroxide and potassium
Eacample 5 ions derived from a compound selected from the
group consisting of potassium hydroxide and
To 1000 parts of water were added 40 parts of potassium chlorite, passing chlorine dioxide into
sodium hydroxide and 56.1 parts of potassium said solution until said solution reaches substan
hydroxide, and chlorine dioxide diluted. With air tial neutrality, evaporating the solution under
was passed into the resulting solution until 135 10 reduced pressure at a temperature below about
parts was absorbed and the solution was slightly 70° C. to obtain the precipitation of potassium
acidic. The solution was then subjected to a chlorate, separately recovering said potassium
vacuum of 28 inches of mercury and heated to chlorate, and then further evaporating said so
a temperature of about 70° C. until 936 parts of lution under reduced pressure and at a tempera
water was removed, at which time the vacuum 5 ture below about 70° C. to precipitate substan
was relieved and the temperature was adjusted tially anhydrous sodium chlorite.
to 30° C. and 109 parts, or about 88.9%, of the 3. In a process for preparing sodium chlorite
potassium chlorate was precipitated. Through substantially uncontaminated with sodium chlo
conventional filtration means, the solid potas- . . rate, the steps of forming a solution containing
sium chlorate was separated from the liquid 20 in admixture sodium chlorate and a quantity of
phase consisting essentially of water and Sodium potassium chlorite substantially equivalent to
chlorite, and was heated and dried. The liquid said sodium chlorate, evaporating the solution
phase again was heated under Vacuum according under reduced pressure at a temperature below
to the foregoing Conditions until Solid sodium about 70° C. to obtain the precipitation of po
chlorite containing substantially no chemically 25 tassium chlorate, separately recovering said po
uncombined water remained. tassium chlorate, and then further evaporating
In this specification and the appended claims said solution under reduced pressure and at a
the weight basis is meant and referred to wher temperature below about 70° C. to precipitate
ever parts, percentages or ratios of compositions substantially anhydrous sodium chlorite.
or reagents are stated. 30
Having thus described the present invention GEORGE: L. CUNNINGHAM.
So that others skilled in the art may be able FRANK PRETKA.
to understand and practice the same, we state
that What we desire to Secure by Letters Patent
is defined in what is claimed. . m 35 REFERENCES: CITED
We claim: The following references are of record in the
1. In a process for preparing sodium chlorite file of this patent:
substantially uncontaminated with sodium chlo
rate, the steps of forming a solution containing UNITED STATES PATENTS
in admixture sodium ions, chlorite ions, chlorate 40 Number Name Date,
ions, and potassium ions derived from a con 2,031,681. Vincent ------------ Feb. 25, 1936
pound Selected from the group consisting of po 2,169,066 Cunningham -------- Aug. 8, 1939
tassium hydroxide and potassium chlorite, evap OTHER REFERENCES
orating Said solution under reduced pressure at
a temperature below about 70° C. to obtain the 45 Mellor's "Comprehensive Treatise on Inorganic
precipitation of potassium chlorate, separately and Theoretical Chemistry,' vol. 2, 1922 ed., pp.
recovering said potassium chlorate, and then 282, 283.
further evaporating Said solution under reduced Seidell, 'Solubilities of Inorganic and Organic
pressure and at a temperature below about 70° Compounds,' Vol. 1, pp. 513 and 639, D. Wan
C. to precipitate substantially anhydrous sodium Nostrand & Co., New York city, 1919.
50
chlorite.