United States Patent Office 3,712,891

Patented Jan. 23, 1973

2
action to approach completion and therefore the reactors
3,712,891 must be relatively large in order to obtain sufficient hold
CHILORINATION OF CYANURCACD up time.
Sidney Berkowitz, Highland Park, and Raymond N. SUMMARY OF THE INVENTION
Mesiah, Somerset, N.J., assignors to FMC Corpora 5
tion, New York, N.Y. Chloroisocyanuric acids, especially very pure dichloro
No Drawing. Filed July 21, 1971, Ser. No. 164,948 isocyanuric and trichloroisocyanuric acid, are produced
Int, C. COT d 55/40 by the process of this invention by reacting cyanuric acid
U.S. C. 260-248 C 4 Claims
and hypochlorous acid in an aqueous medium at a tem
10 perature of 0° to 50° C., and preferably below about
ABSTRACT OF THE DISCLOSURE 25 C. The molar ratio of cyanuric acid to hypochlorous
acid is preselected to yield a product having the desired
This invention provides a process for producing chlo degree of chlorination. This process eliminates the large
roisocyanuric acids by reacting cyanuric acid and hypo multiple-stage reactors and the heat removal and shut
chlorous acid in an aqueous medium at a temperature 5 down problems associated with the prior art process. Fur
of 0° C. to 50° C. The process is capable of producing thermore, high yields of chloroisocyanuric acids can be
chloroisocyanuric acids without producing a salt as a continuously obtained in commercial quantities employ
co-product of chlorination. ing only a relatively small, single stage reactor because
the chlorination reaction is relatively fast in comparison
20 to the prior art process, thereby eliminating the need for
BACKGROUND OF THE INVENTION long hold-up times for the reactants.
(A) Field of the invention The chloroisocyanuric acid produced by this process is
The chloroisocyanuric acids, sometimes referred to as obtained as a precipitate in a mother liquor while some
chlorocyanuric acids, are chemicals having many known chloroisocyanuric acid remains dissolved in the mother
uses. This invention provides a novel process for chlorinat 25 liquor. This dissolved chloroisocyanuric acid can be con
ing cyanuric acid to produce these useful chemicals. veniently recovered by recycling the mother liquor with
out interfering with the chlorination reaction because the
(B) Description of the prior art mother liquor need not contain sodium chloride or other
Dichloroisocyanuric acid and trichloroisocyanuric acid salts which interfere with chlorination since salts are not
have been produced by mixing cyanuric acid with sodium 30 formed as co-products of the chlorination reaction. This
hydroxide and then chlorinating by the addition of chlo is a significant advantage over prior art processes which
le. employ an alkali as a reactant with the result that a cor
Specifically, dichloroisocyanuric acid has been pro responding salt is produced in the mother liquor.
duced by mixing cyanuric acid with sodium hydroxide in 35
DETAILED DESCRIPTION OF THE INVENTION
a mole ratio of 1 part cyanuric acid to 2 parts sodium This invention provides a novel process for producing
hydroxide and then chlorinating by the addition of chlo chloroisocyanuric acids by reacting cyanuric acid and
rine, usually in two stages, until the pH is between 1.7 hypochlorous acid. The process obtains high yields em
and 3.5. After chlorination a slurry containing dichloro ploying a single stage reactor, requires relatively short
isocyanuric acid as a precipitate is filtered and the di 40 reaction times and can produce the chloroisocyanuric
chloroisocyanuric acid filter cake is usually washed and acid product in a mother liquor without the presence of
dried.
All prior art processes for chlorinating cyanuric acid sodium chloride or similar salts. Furthermore, the amount
employ a base, usually sodium hydroxide, which results of heat evolved from this chlorination reaction is sig
in the chloroisocyanuric acid product being obtained as a nificantly less than the amount of heat evolved by the
solid precipitate in the mother liquor which also con 45 prior process of reacting cyanuric acid, sodium hydroxide
tains a salt, usually sodium chloride, as a product. The and chlorine. These significant process advantages over
the prior art permit the process to continuously obtain
presence of salt in the mother liquor interferes with re high yields in commercial quantities employing a single
covering the chloroisocyanuric acid values by recycling small reactor with direct recycling of the mother liquor
the mother liquor. 50 after product separation.
The prior art process of mixing cyanuric acid with The reaction temperature can vary between 0 and 50°
sodium hydroxide to produce disodium cyanurate and and preferably is maintained below 25 C. The best mode
then reacting the latter with chlorine results in an exo contemplated for practicing this invention, which provides
thermic reaction and produces a slurry from which large the highest yields, is with a reaction temperature of be
quantities of heat must be removed. Removing this heat 55 tween 10' and 15 C.
presents difficult process engineering problems when the The hypochlorous acid reactant is preferably intro
process is operated continuously to produce commercial duced as an aqueous hypochlorous acid solution having
quantities. Because of the nature of the slurry involved, a pH between about 4 and about 4.5. Hypochlorous acid
heat exchangers used to control temperatures in the re solutions having pH's outside the preferred range of 4
actor frequently plug during operation and require nu to 4.5 can be used. However, their commercial usefulness
merous shutdowns for cleaning. During these shutdowns, decreases as the pH of the hypochlorous acid deviates
some of the cyanuric acid values present in the slurry from the preferred range. This is due to the decrease in
hydrolyze forming ammonia and carbon dioxide. The hypochlorous acid stability and concentration as the pH
presence of ammonia in the slurry cannot be permitted of the hypochlorous acid solution deviates from the pre
because it leads to formation of highly explosive nitrogen ferred range of 4 to 4.5. Hypochlorous acid solutions
trichloride during subsequent chlorination. As a result, having a pH higher than 5.0 or lower than 3.5 tend to
all of the slurry must be discarded if a prolonged shut be uneconomical although they are operable.
down (several hours) takes place and such discarding of A significant characteristic of this process not provided
reactants and products represents not only an undue eco by any of the prior art processes, is that the residence
nomic loss but also a difficult disposal problem. 70 time in the reactor required for the reaction to reach sub
In addition to the operating difficulties, the prior proc stantial completion is very short. High, commercially valu
esses require long hold-up times for the chlorination re able yields are obtained with residence times in the
 8,712,891
3 4.
reactor between about 1 to 10 minutes. The best mode filtrate which resulted in an overall yield of 95% based
contemplated for practicing this invention is with resi on the weight of cyanuric acid feed.
dence times of less than about 10 minutes, preferably
1 to 3 minutes. The combination of high yields, short EXAMPLE 3
residence times and the ability to operate with a single 5 A reactor was used consisting of a 600 ml. beaker
stage process results in a commercial process which can equipped with a Teflon paddle stirrer, thermometer, gas
employ a single, small, pipe-like reactor with high sparger and pH electrodes. The reactor was cooled by
throughput (short residence times). This eliminates most means of a brine bath. A solution of 16.85 g. (0.42 mole)
of the heat removal and operating problems of the prior of sodium hydroxide in 200 ml. of water was added to
processes along with a substantial reduction in the amount O the reactor, cooled to 10° C. and chlorinated to a pH of
of capital equipment needed. 10.1 which resulted in the conversion of the sodium
The mole ratio of cyanuric acid to hypochlorous acid hydroxide into sodium hypochlorite. A 20% by weight
fed into the reaction zone determines the degree of chlori sulfuric acid solution was then rapidly added with cooling
nation of the chloroisocyanuric acid product. A mole ratio to the sodium hypochlorite solution in the reactor until
of cyanuric acid to hypochlorous acid of about 1:2 gives 5 the pH dropped to 4.1. This resulted in the formation of
high yields of essentially pure dichloroisocyanuric acid hypochlorous acid. A slurry of 12.9 g, of cyanuric acid
while a mole ratio of about 1:3 gives high yields of essen and 35 ml. of water was then added to the reactor. This
tially pure trichloroisocyanuric acid. Mole ratios of be caused the pH to fall from 4.1 to 2.6. With the reaction
tween about 1:2 and about 1:3 yield a product mixture of mixture being stirred, the pH remained constant at 2.6
di- and tri-chloroisocyanuric acids. 20 after about 1 minute. After 2-3 minutes with the reactor
The basic process provided by this invention employs contents at a pH of 2.6, the contents were filtered and the
hypochlorous acid directly as a reactant. However, the solids recovered, washed and dried. The solid product
process can be modified and improved for certain uses by amounted to 17.8 g. (0.0893 mole) of dichloroisocyanuric
preparing hypochlorous acid in situ. This is accomplished acid having 70.9% by weight available chlorine. The fil
by replacing the hypochlorous acid solution with reactants 25 trate contained an additional 1.5 g. (0.0076 mole) of di
which will produce a hypochlorous acid solution. Exam chloroisocyanuric acid resulting in an overall yield of
ples of reactions and their associated reactants that will 97% by weight dichloroisocyanuric acid based upon the
produce hypochlorous acid in situ are: amount of cyanuric acid feed.
(a) acidification of sodium hypochlorite to a pH of 4.1 The best mode contemplated for practicing this inven
to 4.5 to produce hypochlorous acid tion comprises continuously reacting cyanuric acid and
(b) chlorination of water in the presence of mercuric hypochlorous acid under process conditions such that the
oxide (HgC) to produce hypochlorous acid reaction reaches substantial completion in less than 10
(c) addition of Cl2O to water to produce hypochlorous minutes, for example at a reaction temperature of between
acid. 35
10° C. and 15 C., reacting a hypochlorous acid solution
having a pH of between 4.1 and 4.5 with cyanuric acid and
The following examples are provided by way of illustra obtaining an aqueous mother liquor containing a chloro
tion only and are not intended to limit the scope of the isocyanuric acid product without the presence of salts, the
invention. All percentages used herein are weight per product is separated from the motor liquor and resulting
centages unless otherwise specified. 40 mother liquor is recycled back to the reaction according to
standard recycling techniques.
EXAMPLE 1. Pursuant to the requirements of the patent statutes,
A reactor consisting of a 250 ml. beaker equipped with the principle of this invention has been explained and
exemplified in a manner so that it can be readily practiced
a Teflon paddle stirrer, thermometer and pH electrodes by those skilled in the art, such exemplification including
was charged with 85 g. (0.062 mole) of an aqueous hypo what is considered to represent the best embodiment of
chlorous acid solution having a pH of 4.1. The acid the invention. However, it should be clearly understood
solution in the reactor was cooled to 10° C. and a slurry that, within the scope of the appended claims, the inven
containing 3.9 g. (0.0302 mole) of cyanuric acid in 10 ml. tion may be practiced by those skilled in the art, and
of water was added to the reactor. The pH in the reactor 50 having the benefit of this disclosure, otherwise than as
dropped from 4.1 to 2.6. The reaction mixture turned specifically described and exemplified herein.
clear and then a white precipitate formed. This occurred What is claimed is:
in about 1-2 minutes. The solids were filtered, washed 1. A process for producing chloroisocyanuric acids
with 10 ml. of water and dried at 90° C. and a pressure comprising reacting cyanuric acid and hypochlorous acid
of 20 mm. of mercury. The yield of precipitated product in an aqeous medium at a temperature of 0° to 50° C.
was 5.4 g (0.0273 mole) of dichloroisocyanuric acid hav 55
ing 71.6% by weight available chlorine (theory for di to produce a chloroisocyanuric acid precipitate in an aque
chloroisocyanuric acid is 71.6%). An additional 0.6 g. ous mother liquor.
(0.0025 mole) of dichloroisocyanuric acid was contained 2. The process of claim 1 in which the hypochlorous
in the filtrate which resulted in a total yield of 98.5% by acid is introduced as an aqueous solution having a pH
between 4.1 and 4.5.
weight based upon the amount of cyanuric acid feed. 60
3. The process of claim 1 in which the cyanuric acid
EXAMPLE 2 and hypochlorous acid are present in a mole ratio of
cyanuric acid to hypochlorous acid of from about 1:2
The same reactor was used as in Example 1. Seventy and dichloroisocyanuric acid is produced.
eight g. of an aqueous hypochlorous acid solution contain 65 4. The process of claim 1 in which the cyanuric acid
ing 0.0475 mole of hypochlorous acid was added to the and hypochlorous acid are present in a mole ratio of
reactor at a temperature of 10° C. A slurry containing cyanuric acid and hypochlorous acid of about 1:3 and
2.0 g. (0.0155 mole) of cyanuric acid in 10 ml. of water trichloroisocyanuric acid is produced.
was added to the hypochlorous acid solution. The pH References Cited
dropped from 4.1 to 2.6. After 1-2 minutes, the product 70
precipitated and was filtered, washed with 10 ml. of water UNITED STATES PATENTS
and dried, yielding 3.0 g (0.0130 mole) of trichloroiso 3,108,079 10/1963 Wixon ----- 260-248 X
cyanuric acid having 90.1% by weight available chlorine 3,178,429 4/1965 Vazopolos ---------- 260-248
(theory for trichloroisocyanuric acid is 91.5%). Another
0.04 g. of trichloroisocyanuric acid was contained in the 75 JOHN M. FORD, Primary Examiner