United States Patent Office 3,278,447 Patented Oct. 11, 1966 1 3278447 PROCESS FOR STABILIZING CHLORINE, DIOXIDE SOLUTION ‘Thomas P. MeNicholas, Greenville, Ry, sssgnor (0 ‘Cloro-Bae Produets, Ise, Esmond, Tl a comporation of Delaware ‘No Drawing. Filed Bee, 2, 1963, Sr. No. 327,500 6 Clalms. (Cl 282-187) ‘The present invention relates to compositions contain: ing chlorine dioxide, useful as disinfecting, cleaning and bleaching agents, ofc, and to methods for making the same; more particulary it relates to novel stabilized solo- tions of chlorine dioxide and methods for making the ‘Chlorine dioxide, which is normally a gs, is a well Iknovin germicide, a2 well 2s » disinfecting, cleaning and Dleaching agent. For most applications, it is not practical to use the ‘gaseous chlorine dioxide a3 such for & numberof ressons, ‘Therefore, itis available and used in aqueous solution. One method of making soch solution is to bubble the gaseous chlorine dioxide through water to produce a Seturated chlorine dioxide solution, A serious problem with such solutions is that only a zelaively small amount of the chlorine dioxide gas remains in solution after Dreparation thereof, sich amount being too small or prac- fical purposes except for water purifeation. ‘The reasons for this are (1) the amount of chlorine dioxide capable of teing dissoived is small and (2) upon standing the Ehlorine dioxide, except for small amounts, is given off Put in another way, chlorine dioxide solutions per © ‘which are sufficiently concentrated for most purposes are {oo unstable, Sodium perborate has been used to increase the concentration of chlorine dioxide which ean be placed in stable solution, the chiorine dioxide being bubbled into Water containing sodium perborate. ‘However, thero has been a need fo further increase the stuble chlorine dloxide concentration, one reason be- jing. reduction of shipping costs and another being the desirability of providing. stronger solutions for certain purposes. it isan object of the present invention to fll this need, jie. to ineresse the stable chlorino dioxide concentration fn aqueous solutions thereat. tvhas been discovered that the use of alkali metal (sodium) percerhonste instead of sodium perborate in- creases the amount of chlorine dioxide which can be hreld in stable solution as much as three huodred percent Tt is believed that the sodium percarbonate ‘becomes Chemicelly bonded in some way through the peroxy radical to. the chlorine dioxide to thereby hold the thlotine dioxide in solution until i comes into contact with a media which changes tho pH factor during use ‘upon ‘which the chlorine dioxide is released. In eny rent, tests have proved that the chlorine dioxide is not present in the form of a chlorite or chlorous weld. Pref- erably, an amount of sodium percarbonate is used which ‘will produce a saturated sofution thereof inthe final prod- uct. im practice, about two parts by weight of percar- Donate for each part of chlorine dioxide has been found { provide optimum stable C10, concentrations. TE lesser mounts are used, stability of the same chlorine dioxide Concentration is decreased. However, such lesser amounts provide sable solutions of lesser ClO, concentrations. Example 1 17 Ibs. of chlorine dioxide were bubbled into 90 gal- Tons of water at room temperature while adding 100 Tbs. ‘of sodium perborate, The chlorine dioxide concenir= tion was 2% based on total Weight of the resulting mix ‘The ClO, conventration did not decreases upon standing 20 a 30 40 o 5 70 2 {for a period of five months. Increasing the amount of chorine dioxide did mot result in eny increase in, solu- tion concentration. Instead, the excess chlorine dioxide tscaped from the solution, Adjustment of the amount ff perborate did not increase the maximum CIO; concen tration. Example 2 50 Ibs, of chlorine dioxide were bubbled into 90 gal. tons of water at room temperature over a period of twenty four hours while adding 100 Tbs, of sodium per- tatbonate containing 70% by weight esbonate snd 30% hydrogen peroxide. The chlorine dioxiée concentration was 69% by weight of the resulting mix and did not de- Crease upon standing for a period of five months. In frecsing the amount of chlorine dioxide did not result increase in solution concentration. Instead the ‘excess chlorine dioxide escaped from the solution. Ad Justment of the amount of percarbonate did not appre~ Clably increase the maximum chlorine dioxide concentra- tion. "Although the use of percarbonate substantially in- crenses the maximum stable chlorine dioxide concentra. tion, the cost of the product, even though less then with the ive of perborate because Of inereased ClO, concentra tion, is ll relatively high because of the high cost of percarbonate, It is an object of the present invention to produce stable chlorine dioxide solutions of concentra~ tions af least as high as shose achieved with percarbonate at only a fraction, as Ite as about Y of the cost and to produce such solutions with other materials. ‘This is achieved by virtue of the discovery that it is the active oxygen of the hydrogen peroxide of the per carbonate In combination with the carbonate thereof ‘hich increases the stable ClO, concentration and that substantially Tess (5096 ess) active oxygen is required fo do this than is present in the percarbonate coataining the necessary amount of carbonste. ‘Thus, with perea bonate, of necessity, twice as much hydrogen peroxide being used than is necessary 10 stabilize the chlorine di oxide, Therefore, by using an alkali metal (Sodium) car- Bonate or bicarbonate (both are inexpensive) and a refered quantity of hydrogen peroxide, or some other ource of active oxygen sich as ozone, substantially Jess than the quantity present in percarbonate containing the same amount of carbonate, the same stable concentra tion of chlorine dioxide can bo achieved at only fraction (about 114) of the cost using the relatively expensive porcarbonute. ‘The present invention also contemplates using the ex ‘ess peroxide or active oxygen in the percarbonate by ‘tddtion of sodium carbonate or bicarbonate to the per- Carbonate in sufficient amount to utilize all the available active oxygen. “Although it is believed that the active oxygen of the hydrogen peroxide, added as such or present in the per= acbonate, causes the chlorine dioxide to become bound fn some way to earbonate of bicarbonate to thereby hold it in solution, the resulting composition does not contain ‘any hydrogen peroxide or active oxygen. ‘Commercially svailable sodium percarbonate, eg. that sold by Food Machinery Company, contsins seventy per= tent by weight sodium carbonate and 30% hydrogen peroxide.” OF the 30% hydrogen peroxide about 47% by weight i active oxygen 80 that the percarbonate con- tains about 146 of active oxygen and 70% cerbonate. However, only about half of this amount of setive oxygen. js required for the amount of sodium carbonate present Jn the percarbonate for optinum stable ClO, concentra tions s0 that sbout 7% active oxygen or 15% hydrogen peroxide, is being wasted. Not only does this result in A waste of the hydrogen peroxide but the cost of combin«3,278,447 3 ing such unused hydrogen peroxide with the carbonate also wasted. Put in another way, the ratio of hydro- igen peroxide to sodium carbonate in the percarbonate Is higher than that required to achieve equally as good re- sulls, The present invention, by supplying the active oxygen soparately from the carbonate permits the proper amount of active oxygen to be added with substantial ‘savings. ‘The active oxygen can be supplied as ozone, hydrogen peroxide or any other peroxy compound sich as ealeium, ‘miggnesium, sodium or urea peroxide, alkali metal, per- Dorate, persulphate or perphosphate snd other peroxides and peracid sats. ‘A preferred ratio by weight of carbonate or bicarbonate to chlorine dioxide is between about 1.5 to 1 and 12 to 1 but this may vary considerably with good resulis, If the ratio is decreased much Tess than 1.2 to 1 the maxi- ‘mum concentration of chlotine dioxide which can be held in sable solution fs docreased but so long as there is some carbonate or biearbonste together with active oxygen, an increased stable concentration is achieved compared ¢0 the use of no carbonate. Saturated carbonate or bicar- ‘bonate solutions are preferred. Tho ratio of carbonate or bicarbonate to chlorine dioxide can be greater than 1.5 to 1.0 but litle improvement results so that the i cTeased expense is not warranted. For optimum results, the amount of hydrogen peroxide should not be much less than IM or 15¢e by. weight, ‘based on carbonate and/or bicarbonate and hydrogen peroxide, or about 0.20 part by weight per part of car Donate and/or Bicarbonate. In terms of active oxygen {about 47% of hydrogen peroxide is active oxygen) this is about 0.1 part active oxygen per part of carbonate and/or bicarbonate. Thus, where active oxygen is used ‘8 such, eg. ozone, oplimum results are achieved with 0.1 part active oxygen per part of carbonate and/or bicarbonate. No’ noticeable improvement re- sulis by increasing the bydrogen. peroxide or active ‘oxygen beyond this amount so that the increase in cost jn doing so is not warranted and the main advantage of cost saving is not achived. As aforesaid, with the per- carbonate, the amount of active oxygen comprises 0.2 part pet part carbonate so that ify in the present invention, itis much more than 0.15 past per part carbonate, ale though there is e cost savings of 25%, its not nearly 25 ‘marked. If the amount of hydrogen’ peroxide or active oxygen is decreased much below this amount, Le. O.1 Patt per part carbonate and/or bicarbonate, the maximum, Stable ClO, concentration achievable is decreased bit 80 long as there is some active oxygen in the presence of the carbonate and/or biearbonate improved results are achieved. ‘Where active oxygen is supplied in the form of ozone of liguid hydrogen peroxide, ther basic alkali metal sats ‘of inorganie acids containing oxyzen but no chlorine in the acid radical can be used, a8 for example, sodium oF ppolassium borate, sulphate, phosphate, ete.” However, metal carbonate and/or bicarbonate are preferred. Tn preparing the chlorine dioxige solutions ofthe present invention, the carbonate, bicarbonate or other basic salt and the hydrogen peroxide or active oxygen are con- imuously fed into the water at uniform metered Tates ependent on the rate of addition of ehloride dioxide, ‘which is also added at a uniform rate. In this way, the ‘BH of the solution remains about the samo over the entire period of compounding. The rate of chlorine dioxide ad- ‘ition depends upon the outpot of the CIO, generator ince a preferred form of the invention contemplates Adding the CIO; to the water as itis generated, e.g. from Chlorate and acid. ‘In compounding the solutions of the present invent ‘they ate maintained at a neutral or baste DH. Example 3 Seventy pounds of sodium carbonate and fifteen pounds pf liquid hydrogen peroxide in the fozm of a 35% aqueous 75 10 15 20 0 0 46 50 oo 5 4 solution (forty five Ibs, solution) were continuously added at metered rates to 90 gals. of water at room tempera- ture over a period of 24 hours. At the same time, chlo Fine dioxide gas generated from sodium chlorate and sulfuric acid was bubbled continuously up into the water ‘over the same period of twentj-four hours, after which time fifty-two pounds had been added to provide a stable chlorine dioxide concentration of 6% by weight of the total mix, which did not decrease upon standing for & ‘petiod of five months, Example 4 Example 3 was repeated except that sodium bicarbonate ‘was used instead of sodium carbonate with equally good results. ‘Where percarbonate (70% carbonate and 30% hydro- sen peroxide) Is used, 100 Ibs, is necessary to provide the ‘same 70 Ibs. of carbonate, which requires 20 Tbs. of hy= ‘drogen peroxide, whereas in Examples 3 and 4 only 15 ls, of hydrogen peroxide were used with equally good resills, ‘The 100'Ibs. of percarbonate costs forty cents per Ibs. (market price) or $40.00 whereas 70 Ibs. of Sodium carbonate at $0.04 per Tb, (market price) costs $2.80 and fifteen bs, of liquid hydrogen peroxide at cbout $0.60 per Io, (actually sich peroxide ie bought in the form of a 35% solution at a market price of $0.20 per pound) costs $9.00, the carbonate and hydrogen peroxide together costing $11.80 compated to a cost of $40.00 using percarbonate, most four times more. ‘This is indeed quite remarkable, Example 3 100 ths. of sodium percarbonate, containing 70% by weight of carbonate and 30% by’ weight of hydrogen, peroxide, and 70 Tbs. of sodium eatbonate (a total of 140 Ibs, of carbonate to 30 Ibs. of hydrogen peroxide) were Added at uniform metered rates to 180 gals. of water at oom temperature over 48 hour period white atthe same time bubbling 104 Ibs. of ClO, into the water to provide 8 stable 6% CIO, solution which did not decrease in ‘oncentration after standing for five months. Examples 6 and 7 ‘These examples were the same as Examples 3 and 4, except that instead of hydrogen peroxide, 7 Ibs, of ozone generated between a pair of electrode plates was used ‘with good resuls, Example § Same as Example 3 except twenty Ibs. of sodium per- ‘oxide was wsed instead of the hydrogen peroxide, ‘The results were a8 good as Example 3 except that the end produst contained adltonal sodium which i not pre ferred. Example 9 ‘Same as Example 3 except seventy Ths, of sodium pyro- phosphate was used isead of the carbonate with goed results. Example 10 Same as Example 3 except seventy Ibs. of sodium borate was used instead of the carbonate with good re sults," However, borate is not preferred where the prod- uct is to be used with food or food handling equipment ‘because it is more toxic than carbonate, In all the above examples, the resulting solution con- tained no hydrogen peroxide or active oxygen a8 such, Evidently, in whatever way the peroxy or active oxygen ‘causes the ClO, to bond to the basic sally i disappears in the process. ' The ClO, exists as such in the solution because it ean be removed from the solution as ClO, and and not Cis and oxygen. ‘Also, in all the examples, the solution was neutral or basic during and after compounding. ‘tis known to use perearbonate, hydrogen peroxide and perborate in chlorite solutions to’ suppress the formation3,978,447 5 of chlorine dioxide, However, the preseat composition is not a chlorite but rather a complex ofthe carbonate or bicarbonate and the chlorine dioxide and is tree from chlorine, Whereas, the object of using these peroxy com pounds in chlorite solutions is to insure agaist the pres- {nce of ClOs in the solution, the solution of the present Snvention cohtains ClO, as its active ingredient and does ‘ot contsin ebloite. Thus, when the solution of Example 3'is dried only a sodium carbonate residbe is left the eveous ClO, and water being driven off. No sodium Chlorte is in the residue. On the other hand, when a Sodium chlorite solution containing hydrogen peronide is ‘tied, the residue is sodium chlorite, With a sodium chlorite solution containing hydrogen peroxide and sodium ‘carbonate or sodium percarbonate, the residue resulting ftom drying also conte sodium chlorite. Also, oxalic, cid which changes calor when brought into contact with Chlorine of chlorite but not chlorine dioxide does not thange color when added to the composition of the present invention, Tt is pointed out that the use of hydrogen peroxide or setive onygen alone doesnot inrease the maximum stable concentration of chlorine dioxide in solution but that the ‘carbonate or bicarbonate or some other basic alkall metal Salt of an inorganie acid containing oxygen but not chlo- ine mvust also o present "ts also poited out that if there is any chlorine (whic is present in the reaction mix generated by reacting chlo- rae and acid to form chlorine dioxide and which is always present in commercial chlorite solutions) inthe C10, solu flons of the present invention they cannot be stabilized Evidently, under such conditions, the active oxygen does not tle the chlorine dioxide to the basic salt, In the present cate, a pure CIO, is stripped from the generated Teastion mintare and is added to water topether with the carbonate and hydrogen peroxide so that there is no thlorine or chloe present, It is known to add hydrogen peroxide and other peroxy compounds such 36 porearbonatss to the chlorate-2cid reactors in generating ClO, oz (o the reaction mix to Suppress the rate of evolution of the chlorine dioxide but, this does not give tho advantages of the present invention because af the presence of reaction products other than chlorine dioxide, e. chlorine, ebloric and chlorous acids fand chlorate, any or all of which prevent stabilization by the perearbonate. ‘The chlorine dioxide gas is usually Stripped from such reaction mix and added to water in Which case the percarbonate is lft behind or the eblorine 10 20 % 0 6 6 dionide is generated at the place where it is to be used tnd the generated reaction mix used immedietely, es such, eg. a bleach bath, so that stabilization is not a problem. “Allhough certain theories and examples have been set forth above, the invention is n0t limited thereto or thereby but only to the compositions and methods recited in the following claims and thelr equivalents Telaim: 1A method of making a stable chlorine dioxide solu- tion comprising adding separately to water (1) 2 source of active oxygen selected from the group consisting of ‘ozone, hxlrogen peroxide, calcium, magnesium, sodium fand urea peroxide and allali metal perborate, persulfate land perphosphate and (2) a salt of the group consisting fof alkali tal carbonate and bicarbonate and alkali metal borate stilfate and phosphate, and (3) chlorine dioxide ag substantially free {rom chlorine said ehlorine dioxide fgas being added by bubbling it through said solution, the Smiount of active oxygen in said source being substantially Tess than 0.2 patt by weight per pact of sad salt. 2. A method according 10 claim 1, said salt being selected fom the group consisting of Sediem carbonate ‘and bicarbonate, 3. A method according to claim 2, the source of said active oxygen comprising hydrogen peroxide. ‘4. A method according to claim 2, the source of said active oxygen comprising ozone. S.A method according (0 claim 1, said salt com- pound, said source of free oxygen and ssid chlorine dic Die being separately added to said water simultaneously fn adutly over an extended period at substantially ‘6. A method according to claim 1, the amount of ative oxygen in said source being not substantially less than (ut par by weiaht per part of sad salt. References Cited by the Examiner UNITED STATES PATENTS 2,150,926 3/1939 Krauflman et al. 31082146 3/1963 Wentworth etal, 3084995 4/1963 Grubitsch 253187 XR 3,123,521 3/1964 Wentworth etal. 252187 XR LEON D. ROSDOL, Primary Examiner. JULIUS GREENWALD, ALBERT T. MEYERS, Examiners. 1M, WEINBLATT, Assistant Examiner.