CA1090926A

CA1090926A - Sodium hypochlorite treatment for removal of cyanurate compounds from aqueous waste streams

Info

Publication number: CA1090926A
Application number: CA293,550A
Authority: CA
Inventors: Ronald H. Carlson
Original assignee: FMC Corp
Current assignee: FMC Corp
Priority date: 1977-12-21
Filing date: 1977-12-21
Publication date: 1980-12-02

Abstract

ABSTRACT: Aqueous waste streams from the production of chlorinated isocyanurates are oxidized with sodium hypo-chlorite to remove therefrom dissolved cyanurate compounds.

Description

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This invention relates to the purification of aqueous waste streams containing triazines such as cyanuric acid and ammelide.
Chlorinated isocyanuric acids and their alkali metal salts are familiar chemical entities which are useful as a source of active chlorine. Especially important members are sodium dichloroisocyanurate and trichloroisocyanuric acid. These are high-purity, white crystalline solids, available in a variety of mesh sizes. Although active oxidizers, they can be handled and transported with rela-tive ease and safety. One of the important commercial applications of these products is in the area of water treatment where they have proved effective and convenient for controlling algae and pathogenic bacteria. The water in swimming pools, for example, is readily maintained in a clean and sanitary condition by the addition of chlori-nated cyanuric acid derivatives. Other volume uses are as a dry bleach in cleansing, laundering and sanitizing com-positions and the like.
Alkali metal dichloroisocyanurates and trichloroiso-cyanuric acid are produced commercially by the chlori-nation in aqueous media of alkali metal cyanurates. The process is well known and documented exclusively in the technical and patent literature and in this connection llJ~O~

reference is made to U.S. Patent Nos. 3,299,060 (British Patent No. 1,083,404), 2,969,`360 (British Patent No. 902,539), and 3,035,056. The principal reactions involved, omitting intermediate stages and species, can be depicted by the following simplified chemical equation in which the alkali metal is sodium:
ICl O=IC ~ C-ONa + 2Cl2 ~ o=f/ ~f=o + 2NaCl \C~ ~ C~N Cl Na O
Dichloroisocyanuric Acid NaOH

fl NaO-C~ \C=O
I ~ bl / -Cl 2C1 2 o N~Sodium Dichloroisocyanurate C~ N Cl ONa 3Cl2O=IC C=O + 3NaCl ~C~
o Trichloroisocyanuric Acid The chlorination can be carried out by passing chlorine through an aqueous slurry of the di- or trisodium - - , 013~

cyanurate thereby forming the corresponding di- or trichloroisocyanuric acid. These are filtered from the reaction mixture and the resulting filtrate, which con-tains up to about 2.0 percent dissolved chlorinated iso-cyanuric acids, constitutes an acid waste stream having a pH range of about 0.5 to 5Ø The dichloroisocyanuric acid is neutralized with base, for example aqueous sodium hydroxide and the so-formed sodium dichloroisocyanurate filtered off. The filtrate from the neutralization con-tains up to about 25 percent dissolved chlorinated sodium isocyanurate and constitutes a near neutral waste stream having a pH range of about 6.5 to 7Ø
Alternatively, the sodium dichloroisocyanurate can be realized directly by selective chlorination of trisodium cyanurate wherein two of the sodiums are replaced with chlorine while the third sodium remains attached to the cyanurate ring. The waste stream from this operation exhibits a pH in the vicinity of 5.0 to 7.5. In general, the pH of chlorinated isocyanurate waste streams will run from about 0.5 to 7.5. Where a neutral and an acid waste stream are produced these may be combined to yield a single waste stream.
Of all the chlorinated isocyanurate derivatives, sodium dichloroisocyanurate en~oys the greatest commercial usage since it possesses such desirable attributes as stability, water solubility and high available chlorine content. Although essentially water-insolublè, trichloro-isocyanuric acid has the highest available chlorine and lV~

because of this may be preferred for certain applications.
Generally speaking, however, both derivatives are important industrial chemicals.
While entirely satisfactory from a purely technical aspect, the manufacture of sodium dichloroisocyanurate and trichloroiso-cyanuric acid is accompanied by the production of aqueous waste streams containing dissolved cyanurates, the pollution-free dis-posal of which presents a special problem. A practical solution to this difficulty is a requirement for a commercially success-ful operation.
The increasing public concern over the pollution of our lakes and streams, coupled with the adoption of Federal, State, and local regulations governing the discharge of waste materials has occasioned increased effort in developing new and improved processes and systems for treating waste streams prior to dis-charge.
One approach to the problem is to heat the aqueous waste stream in a pressure vessel at about 225C to 275C to hydrolyze and decompose the cyanurate compounds, as described in Belgian Patent No. 840,817 issued October 15, 1976, in the name of Sidney Berkowitz and Charles V. Juelke and assigned to the assignee of the instant application. Although this process is highly effective in eliminating from the waste stream all traces of cyanurate compounds, it is costly in terms of energy input. In addition, the ammonia that is formed by decomposition of the cyanurate compounds is in itself a pollutant.

1~ ~ O ~ 2ti Another approach to the problem is to treat the aqueous waste stream with active carbon powder. The active carbon was found to exhibit a strong affinity for dissolved cyanurate compounds so that they were removed from the waste streams upon contact. Although this pro-cess effectively cleans up the waste stream, the need to purchase and handle large quantities of active carbon powder increases operating costs. The disadvantage is partially off-set by recycling cyanurate values recovered from the exhausted carbon. Even so, the process is not as economically attractive as might be desired and further improvements in the treatment of chlorinated isocyanurate waste streams are being actively pursued.
Yet another method for removing dissolved chlori-nated cyanurate compounds from aqueous waste streams is described in British Patent No. 1,450,003. That patent discloses a method of dechlorinating the waste stream by treatment with hydrogen peroxide. It is an advantage of this process that the cyanuric acid (or its sodium salt) precipitates from the waste stream and may be recycled back to the chlorination zone. Approximately 65 to 98%
of the cyanurate compounds dissolved in the waste streams are recovered in this manner. However the waste stream, after the solid cyanurate values have been precipitated, retains in solution a low level of organic matter - of the order of 200 to 3,000 parts per million (ppm).
The present invention provides a means for reducing the levels of cyanurate compounds present in lU~O~

the chlorinator waste stream to less than 15 ppm by reaction of the waste stream with sodium hypochlorite in either a batch or continuous process, and has particular application to the treatment of such waste streams that have been dechlorinated with hydrogen peroxide to reduce soluble cyanuric acid levels from 2 percent to 200-3,000 ppm. Further oxidization of such waste streams, con-taining as much as 3,000 ppm of cyanurate compounds with sodium hypochlorite can result in an effluent that meets zero nitrogen discharge requirements. The reaction rate is related to such variables as pH, temperature, initial concentration of cyanurate compounds and initial sodium hypochlorite concentration. Excess sodium hypochlorite can be subsequently destroyed by reaction with hydrogen peroxide.
In accordance with the present invention ammelide and cyanurate compounds such as cyanuric acid can be removed from aqueous waste streams by treatment with sodium hypo-chlorite solution. The amount of sodium hypochlorite used, the temperature and the pH at which the waste stream is maintained during contact with the sodium hypochlorite solution are critical for maximum process performance.
In carrying out the invention, sufficient sodium hypochlorite is added to the waste stream liquor to chemically oxidize the cyanuric acid or its sodium salt to carbon dioxide. The chemistry of the reaction of sodium hypochlorite with cyanuric acid may be represented by the following equation indicating a 4.5 to 1 molar 30.~

stoichiometry of sodium hypochlorite to cyanuric acid.
H

O ~ N~C O

2 f I + 9NaOCl + 3N2 + 6CO2+9NaCl+3H20 HN~ ~NH
li On a weight basis, this reaction requires a ratio of 259.5 parts by weight of sodium hypochlorite to 100 parts by weight of cyanuric acid. At least 90 percent of the cyanuric acid nitrogen is oxidized to nitrogen gas, the balance being oxidized mostly to nitrates. The reaction of sodium hypochlorite with cyanuric acid proceeds most rapidly at pH 9.0 to 10 and increases in rate 2-3 times for every 10C increase in temperature. The effect of the initial concentration of cyanuric acid and sodium hypo-chlorite on the reaction rate will be discussed below.
The residence time for destruction of 95 percent of the cyanuric acid present in the waste stream can range from more than 200 hours to less than 5 minutes depending upon the reaction conditions.
Cyanurate compounds that may be removed from aqueous waste streams by the process of this invention include cyanuric acid, alkali metal salts of cyanuric acid, and amide derivatives of cyanuric acid such as ammelide.
The waste streams that may be advantageously treated by the process of this invention may contain up to about 2 percent of dissolved cyanurate compounds. Typical solutions will contain from 200 to 3,000 ppm of cyanurate compounds. Other soluble compounds may also be present lS)~O~Ztj in the waste stream such as sodium chloride (up to 10 percent by weight), sodium bicarbonate, ammonium dihydrogen orthophosphate, ammonium bisulfate, sodium nitrate, hydro-chloric acid, sulfuric acid and orthophosphoric acid.
The process of the present invention has application to solutions ranging in pH from essentially zero to 12.
However, the waste stream should be adjusted to a pH
of from 8 to 12 prior to contact with the sodium hypo-chlorite solution. The preferred operating range of the process of the present invention is between about 9 and 11.
Particularly preferred is an operating pH in the range of 9.0 to 10.
The amount of sodium hypochlorite reacted with the waste stream may range from a low of about 2 moles of sodium hypochlorite per mole of cyanurate compound present in the waste stream to as much as 9 moles of sodium hypo-chlorite per mole of cyanurate compound present in the waste stream. Preferred operating conditions require a molar stoichiometry of sodium hypochlorite to cyanurate between 6 to 1 and 8 to 1. The source of the sodium hypo-chlorite reactant may be either sodium hypochlorite added as such, gaseous or liquid chlorine, hypochlorous acid, or nitrogen chlorinated isocyanuric acid derivatives.
In addition to cyanuric acid, other triazines such as ammelide may be destroyed by the process of this invention.
The chemistry of the reaction of sodium hypochlorite with ammelide may be represented by the following equation indicating a 6 to 1 molar stoichiometry of sodium lV~

hypochlorite to ammelide.
H

H 2 N-Ç ç=o 2 ¦ ¦ + 12NaOC1 ~ 4N2 + 12NaCl + 6CO2 + 4H2O
~NH

o The benefits and advantages of the present invention will become apparent upon a reading of the description of the preferred embodiments taken in conjunction with the accompanying drawings, wherein:
Figure 1 is a graph that illustrates the effect of pH
on the rate of cyanuric acid decomposition in the presence of sodium hypochlorite.
Figure 2 illustrates a continuous process for treating a waste stream containing cyanurate compounds in accordance with the process of the present invention.
The invention is illustrated in greater detail by the following examples in which all percentages are by weight unless specified otherwise.
EXAMPLE I
One hundred parts by weight of a simulated waste effluent composition containing 0.3 percent cyanuric acid, 6 percent sodium chloride and 0.5 percent hydrochloric acid is mixed with 12.4 parts by weight of 5.25 percent sodium hypochlorite solution and the pH is adjusted to 10.5. The weight ratio of the sodium hypochlorite to the cyanuric acid present in solution is 217:100. This mix-ture is stirred at room temperature for a period of two hours, during which time extensive gassing is observed due to the elimination of nitrogen. During this reaction l~90~Z~

the pH of the mixture decreases to 10.0-10.1 due to decom-position of the cyanuric acid to form carbon dioxide and conversion of the carbon dioxide to sodium carbonate and sodium bicarbonate. The pH of the effluent is periodically readjusted during the reaction to pH 10.5 by addition of 10 percent sodium hydroxide solution. After the simulated waste effluent composition had been stirred for two hours, it is treated with hydrogen peroxide to destroy residual sodium hypochlorite and subsequently acidified and heated at pH 2 to dispel carbon dioxide.
The solution following this treatment is analyzed for cyanuric acid and found to contain 0.113 percent indi-cating that about 63 percent of the cyanuric acid present in the simulated waste solution was degraded. No ammonia or chloramine odors are detected in the solution during the two hour reaction.
EXAMPLE II
A number of batch experiments are conducted with a simulated waste effluent containing 480 ppm cyanuric acid and 6 percent sodium chloride. One hundred parts by weight of this simulated waste effluent is reacted with 1.19 parts by weight of 10.8 percent sodium hypochlorite solution at room temperature under varying conditions of pH and reactor residence time. The pH of the simulated waste effluent is maintained at the desired level by the addition of 10 percent sodium hydroxide solution as described above in Example I. The data from this Example appear in Table I below and show a good correlation ~go~

between the decomposition of cyanuric acid and sodium hypochlorite, thus substantiating the 4.5 to 1 sodium hypochlorite to cyanuric acid molar stoichiometry.

~V9092ti .
O Q

c a W o ~ J

æ o a) o C
~J
H '~1 _ 1~ t~ .~
~: C C ~ O O O O O O O
O O
~0 ~ t~
o o&
.,, a ~
~ OoD C ~
'.L~ ~ rl U~ Il~ 21 J~
a 5~
a ~ ~ ~ ~ ~ ~ ~ O O O
~ O ~: h ~ ~ ~ ~ ~ ~ t~
,~ ~ ~1 ~ a~
o ~ Q, _1 ~ z ~
~C~ u~- C E~
O ~ H ~ ~ t~
R u~ u~ o u~ o o o o C ~ ~ O ~
Zl ~
o C ~
~C

~U5~0~32~i The data in the abo~Te table are plotted in Figure 1 and suggest that under stoichiometric operating conditions at about 20C the reaction rate reaches a maximum at a pH
value between 9 and 10.

EXAMPLE I I I
A simulated waste effluent containing 1,714 milli-grams per liter of cyanuric acid and about 6 percent by weight of sodium chloride is treated with a solution con-taining 4,804 milligrams of sodium hypochlorite. The molar ratio of sodium hypochlorite to cyanuric acid is 4.86:1 (an 8 percent excess of sodium hypochlorite). The decom-position rate (25C) is measured at pH 8.5, 9.5 and 10.5.
The residual undecomposed cyanuric acid present in the simulated waste solution is measured by total Kjeldahl nitrogen analysis. These data are listed in Table II
below which shows the advantage of close pH control at about pH 9.5 for maximum rate at a temperature of 25C.

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TABLE II

Effect of pH on Rate of Decomposition of Cyanuric Acld Wlt Sodlum Hypochlorlte Conditions: 25C
NaOCl/CA mole ratio 4.86/1 Initial CA 1,714 mg/l Elapsed Time % CA Decomposition 10 (Hours) pH .5 pH 9.5 pH .5

4 36 85 21.5 55.5 96.5 EXAMPLE IV
A simulated waste effluent containing 1,714 milli-grams per liter of cyanuric acid and about 6 percent by weight of sodium chloride is treated with a solution con-taining 4,804 milligrams of sodium hypochlorite ~an 8 per-cent excess). The decomposition rate is measured at temperatures of 12, 25 and 35C while maintaining the operating pH of the solution at 9.5. The data listed in Table III below show that the reaction rate increases markedly between 12 and 35C.

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TABLE III

Effect of Temperature on Rate of Decomposition o Cyanuric Acl Wlth Sodium Hypochlori~te Conditions: pH 9.5 NaOCl/CA mole ratio 4.86/1 Initial CA 1,714 mg/l Elapsed Time % CA Decomposition (Hours) 12C 25C 35C

4 46.5 85 8 64.5 95 72 96.5 EXAMPLE V
To evaluate the effect of changing the initial molar ratio of sodium hypochlorite added to the cyanuric acid waste stream, a simulated waste effluent containing 1,714 milligrams per liter of cyanuric acid and about 6 percent by weight sodium chloride is treated with a solution con-taining 2,175 milligrams of sodium hypochlorite. The molar ratio of sodium hypochlorite to cyanuric acid is 2.2:1. The mixture is agitated for 4 hours while main-taining the temperature at 25C and the pH at 9.5. Fifty-one percent of the cyanuric acid is decomposed.
This experiment is repeated increasing the amount of sodium hypochlorite from 2,175 milligrams to 9,390 milli-grams. The molar ratio of sodium hypochlorite to cyanuric acid is 9.5:1. The mixture is agitated for 4 hours while 1~90~

maintaining the temperature at 25C and the pH at 9.5.
Ninety-one percent of the cyanuric acid is decomposed.
EXAMPLE VI
This Example and Figure 2 describe a continuous process for treating a waste effluent containing cyanuric acid compounds with sodium hypochlorite. Referring now to Figure 2 containers 11, 12 and 13 are 2-1/2 gallon (9.46 liters) battery iars, each of which contains 8 liters of 6 percent sodium chloride splution. Vessel 11 contains 100 ppm of cyanuric acid and 0.02 moles per liter of sodium hypochlorite. Vessel 12 contains 40 ppm of cyanuric acid, and 0.017 moles per liter of sodium hypochlorite. Vessel 13 contains 15 ppm cyanuric acid and 0.014 moles per liter of sodium hypochlorite.
The levels of cyanuric acid and sodium hypochlorite present in containers 11, 12 and 13 represent typical concentrations obtained under continuous steady-state operating conditions.
The contents 14, 15 and 16 of each of the three vessels 11, 12 and 13 are maintained at 45C with gentle stirring and the pumps (P-l through P-5) are started.
The pump P-l is adjusted to deliver 63 ml per minute of a 6 percent sodium chloride solution containing 660 ppm of cyanuric acid to the container 11. The pump P-2 is adjusted to deliver 4 ml per minute of an aqueous 0.64 molar sodium hypochlorite solution to the container 11. The pumps P-3, P-4 and P-5 are adjusted to maintain 8 liters of 11)9~

solution in each of the vessels 11, 12 and 13. The pH in each of the reactor vessels 14, 15 and 16 is maintained at 9.5 + 0.2 for 12 hours. After six hours of operation the total Kjeldahl nitrogen in the three vessels is determined.
The residual cyanuric acid and the amount of cyanuric acid decomposed in each of the vessels is described in Table IV.
TABLE IV
VesselCyanuric Acid Present Decomposed (%) 11147 ppm 92 1231 ppm 98 13 6 ppm 99 Operation of the three-vessel continuous system described above reduces the organic nitrogen content (as cyanuric acid) from 200 ppm to less than 5 ppm in 6 hours at 45C, in 3 hours at 55C, or in 1/2 hour at 85C.
The pH is an important variation and should be control-led to 9.5 + 0.5 when operating in the temperature range of 45 to 85DC. The amount of sodium hypochlorite most effective in the continuous process described by this Example is between 6.8 and 9.0 moles of sodium hypo-chlorite per mole of cyanuric acid (a 50 percent to 100 percent excess).
EXAMPLE VII
To 4,240 parts of 6 percent sodium chloride solution is added 2.4 parts of ammelide and the pH is adjusted to 9.5. Seventy parts of a 14.3 percent sodium hypochlorite solution is added and the temperature is increased to ~090~

45C with gentle agitation while maintaining the pH at 9.5. After 15 minutes a sample of solution is removed and analyzed for ammelide content by U.V. spectroscopy.
The analysis indicated 106 ppm of residual ammelide corresponding to 81 percent decomposition during the 15 minute interval.
Pursuant to the requirements of the patent statutes, the principle of this invention has been explained and exemplified in a manner so that it can be readily practiced by those skilled in the art, such exemplifi-cation including what is considered to represent the best embodiment of the invention. However, it should be clearly understood that, within the scope of the appended claims, the invention may be practiced by those skilled in the art, and having the benefit of this disclosure otherwise than as specifically described and exemplified herein. In the following claims, the term "cyanurate compounds" shall include but not be limited to ammelide and water soluble salts thereof.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process of eliminating dissolved cyanurate com-pounds from aqueous waste liquors characterized by con-tacting the waste liquors with an aqueous solution of sodium hypochlorite under conditions such that the major portion of said cyanurate compounds are oxidized to form nitrogen, carbon dioxide and sodium chloride.

2. The process according to claim 1 characterized in that the cyanurate compounds are cyanuric acid and water soluble salts thereof.

3. The process according to claim 1 characterized in that the cyanurate compounds are ammelide and water soluble salts thereof.

4. The process of claim 1 characterized in that the aqueous waste liquors are maintained at a pH in the range of 8.0 to 12Ø

5. The process of claim 1 characterized in that the aqueous waste liquors are maintained at a pH in the range of 9.0 to 10Ø

6. The process of claim 1 characterized in that the waste liquors are maintained at a temperature in the range of 20°-55°C.

7. The process of claim 1 characterized in that the waste liquors contain 200-3,000 ppm of cyanurate compounds prior to contact with the sodium hypochlorite solution.

8. The process of claim 1 characterized in that the waste liquors contain less than 15 ppm of cyanurate com-pounds after contact with the sodium hypochlorite solution.

9. The process according to claim 1 characterized in that the contact time is 2-6 hours.

10. The process according to claim 1 characterized in that the molar ratio of sodium hypochlorite to the cyanurate compounds present in the waste liquors is between 6:1 and 8:1.

11. The process of producing chlorinated isocyanurates by the chlorination in aqueous media of an alkali metal cyanurate to form the corresponding chlorinated cyanuric acid and aqueous waste liquors containing dissolved cyanurate compounds, characterized by contacting the waste liquors with an aqueous solution of sodium hypochlorite whereby the major portion of said cyanurate compounds are oxidized to form nitrogen, carbon dioxide and sodium chloride.

12. The process according to claim 11 characterized in that the cyanurate compounds are cyanuric acid and water soluble salts thereof.

13. The process according to claim 11 characterized in that the cyanurate compounds are ammelide and water soluble salts thereof.

14. The process of claim 11 characterized in that the aqueous waste liquors are maintained at a pH in the range of 8.0 to 12Ø

15. The process of claim 11 characterized in that the aqueous waste liquors are maintained at a pH in the range of 9.0 to 10Ø

16. The process of claim 11 characterized in that the waste liquors are maintained at a temperature in the range of 20°-55°C.

17. The process of claim 11 characterized in that the waste liquors contain 200-3,000 ppm of cyanurate compounds prior to contact with the sodium hypochlorite solution.

18. The process of claim 11 characterized in that the waste liquors contain less than 15 ppm of cyanurate compounds after contact with the sodium hypochlorite solution.

19. The process according to claim 11 characterized in that the contact time is 2-6 hours.

20. The process according to claim 11 characterized in that the molar ratio of sodium hypochlorite to the cyanurate compounds present in the waste liquors is between 6:1 and 8:1.

21. A process for removing dissolved chlorinated cyanurate compounds from aqueous waste liquors by con-tacting the waste liquors with hydrogen peroxide to pre-cipitate 65 to 98% of the cyanurate compounds dissolved therein and separating the precipitated cyanurate com-pounds from the waste liquors, characterized by subsequently contacting said waste liquors with an aqueous solution of sodium hypochlorite to oxidize residual cyanuric compounds present in the waste liquors to form nitrogen, carbon dioxide and sodium chloride.

22. The process according to claim 21 characterized in that the cyanurate compounds are cyanuric acid and water soluble salts thereof.

23. The process according to claim 21 characterized in that the cyanurate compounds are ammelide and water soluble salts thereof.

24. The process of claim 21 characterized in that the aqueous waste liquors are maintained at a pH in the range of 8.0 to 12.0 during contact with the sodium hypochlorite solution.

25. The process of claim 21 characterized in that the aqueous waste liquors are maintained at a pH in the range of 9.0 to 10.0 during contact with the sodium hypochlorite solution.

26. The process of claim 21 characterized in that the waste liquors are maintained at a temperature in the range of 20°-55°C during contact with the sodium hypochlorite solution.

27. The process of claim 21 characterized in that the waste liquors contain 200-3,000 ppm of cyanurate compounds prior to contact with the sodium hypochlorite solution.

28. The process of claim 21 characterized in that the waste liquors contain less than 15 ppm of cyanurate compounds after contact with the sodium hypochlorite solution.

29. The process according to claim 21 characterized in that the contact time of said waste liquors with the sodium hypochlorite solution is 2-6 hours.

30. The process according to claim 21 characterized in that the molar ratio of sodium hypochlorite to the cyanurate compounds present in the waste liquors is between 6:1 and 8:1.