Concentrated aqueous bromine solutions and their preparation and use

Abstract

Described is a process of producing a concentrated liquid biocide formulation. Mixed together are (a) bromine chloride or bromine and (b) an aqueous solution of alkali metal salt of sulfamic acid having a pH of at least about 7, in amounts such that (i) the active bromine content of the solution is at least about 100,000 ppm (wt/wt), and (ii) the atom ratio of nitrogen to active bromine from (a) and (b) is greater than 1 when bromine is used and is greater than 0.93 when bromine chloride is used. Use of bromine chloride as the source of the active bromine in the process is preferred because in the resulting aqueous compositions, all of the bromine of the bromine chloride is made available as active bromine in solution. In other words, the chlorine of the bromine chloride is converted in the process to dissolved alkali metal chloride salt, thereby liberating all of the bromine in the biocidal composition as active bromine capable of providing biocidal activity.

1 . An unpurified aqueous biocide composition having a pH of at least 7 and that comprises water having in solution therein (i) an active bromine content of at least about 100,000 ppm (wt/wt) up to about 180,000 ppm (wt/wt), and (ii) a content of nitrogen provided by sulfamic acid or a salt thereof in an amount such that the atom ratio of nitrogen to active bromine in said biocide composition is greater than 0.93, and wherein said composition is devoid or essentially devoid of bromate.  
     
     
         2 . A composition according to  claim 1  wherein said atom ratio is greater than 1.  
     
     
         3 . A composition according to  claim 1  wherein said pH is in the range of from 12 to about 13.5.  
     
     
         4 . A composition according to  claim 1  wherein the active bromine content of the solution is in the range of about 145,000 ppm (wt/wt) to about 160,000 ppm (wt/wt).  
     
     
         5 . A composition according to  claim 1  wherein said atom ratio is greater than 1, and wherein said pH is in the range of about 12 to about 13.5.  
     
     
         6 . A composition according to  claim 1  wherein said atom ratio is greater than 1, wherein the active bromine content of the solution is in the range of about 145,000 ppm (wt/wt) to about 160,000 ppm (wt/wt).  
     
     
         7 . A composition according to  claim 1  wherein said pH is in the range of from 12 to about 13.5, and wherein the active bromine content of the solution is in the range of about 145,000 ppm (wt/wt) to about 160,000 ppm (wt/wt).  
     
     
         8 . A composition according to  claim 1  wherein said atom ratio is greater than 1, wherein said pH is in the range of from 12 to about 13.5, and wherein the active bromine content of the solution is in the range of about 145,000 ppm (wt/wt) to about 160,000 ppm (wt/wt).  
     
     
         9 . A composition according to  claim 1  wherein said composition further comprises chloride ion in solution therein.  
     
     
         10 . A composition according to  claim 9  wherein the active bromine content of the solution is in the range of about 145,000 ppm (wt/wt) to about 160,000 ppm (wt/wt).  
     
     
         11 . A composition according to  claim 9  wherein said atom ratio is greater than 1, and wherein said pH is in the range of about 12 to about 13.5.  
     
     
         12 . A composition according to  claim 9  wherein said atom ratio is greater than 1, wherein the active bromine content of the solution is in the range of about 145,000 ppm (wt/wt) to about 160,000 ppm (wt/wt).  
     
     
         13 . An aqueous biocide composition having a pH of at least 7 and that comprises water having in solution (i) an active bromine content of at least about 100,000 ppm (wt/wt) up to about 180,000 ppm (wt/wt), and (ii) an atom ratio of nitrogen to active bromine of greater than 1, the nitrogen originating from sulfamic acid and/or an alkali metal salt thereof, and wherein said composition is devoid or essentially devoid of bromate, and since its inception has been devoid or essentially devoid of bromate.  
     
     
         14 . A composition according to  claim 13  wherein said pH is 13 or above.  
     
     
         15 . A composition according to  claim 13  wherein said pH is in the range of from 12 to about 13.5.  
     
     
         16 . A composition according to  claim 13  wherein the active bromine content of the solution is at least about 145,000 ppm (wt/wt).  
     
     
         17 . A composition according to  claim 16  wherein said pH is in the range of about 12 to about 13.5.  
     
     
         18 . A composition according to  claim 13  wherein the active bromine content of the solution is in the range of about 145,000 ppm (wt/wt) to about 160,000 ppm (wt/wt).  
     
     
         19 . A composition according to  claim 18  wherein said pH is in the range of from 12 to about 13.5.  
     
     
         20 . A composition according to  claim 13  wherein said active bromine content originates from bromine chloride or a combination of bromine chloride and bromine, and wherein said pH is 13 or above, and wherein the active bromine content of the solution is at least about 145,000 ppm (wt/wt).  
     
     
         21 . A composition according to any of claims  13 - 19  wherein said composition further comprises chloride ion in solution therein.  
     
     
         22 . An aqueous biocide composition having a pH of at least 7 and that comprises water having in solution therein (i) an active bromine content of at least about 100,000 ppm (wt/wt) up to about 180,000 ppm (wt/wt), and (ii) a sulfamate content in an amount such that the atom ratio of nitrogen to active bromine in said biocide composition is greater than 0.93, and wherein said composition is devoid or essentially devoid of bromate, and since its inception has been devoid or essentially devoid of bromate.  
     
     
         23 . A composition according to  claim 22  wherein said atom ratio is greater than 1, and wherein said pH is in the range of from 12 to about 13.5.  
     
     
         24 . A composition comprising an aqueous solution containing a stable oxidizing bromine compound wherein the solution is free of detectable bromate, and wherein the aqueous solution has an active bromine content of at least about 100,000 ppm (wt/wt) up to about 180,000 ppm (wt/wt).  
     
     
         25 . A composition according to  claim 24  wherein from its inception said composition is free of detectable amounts of bromate.  
     
     
         26 . A concentrated biocidal composition containing a stabilized oxidizing halogen which may be obtained from bromine chloride or a combination of bromine chloride and bromine, and sulfamic acid or an alkali metal sulfamate, said composition being free of detectable amounts of bromate ion and having at least about 100,000 ppm (wt/wt) up to about 180,000 ppm (wt/wt) bromonium ion present, measured as Br 2 .  
     
     
         27 . A composition according to  claim 26  wherein said stabilized oxidizing halogen is obtainable from bromine chloride or a combination of bromine chloride and bromine, and sodium sulfamate.  
     
     
         28 . A composition according to  claim 26  wherein the amount of bromonium ion present, measured as Br 2 , is at least about 145,000 ppm (wt/wt).  
     
     
         29 . A composition according to  claim 26  wherein the amount of bromonium ion present, measured as Br 2 , is in the range of about 145,000 to about 160,000 ppm (wt/wt).  
     
     
         30 . A concentrated biocidal composition containing sulfamate-stabilized bromonium ion, said composition (i) from its inception, having a pH in excess of 8 and (ii) having greater than about 10 wt % up to about 18 wt % bromonium ion present, measured as Br 2 , said wt % being based on the total weight of the composition.  
     
     
         31 . A concentrated biocidal composition containing sulfamate-stabilized bromonium ion, said composition (i) containing greater than about 10 wt % up to about 16 wt % bromonium ion, measured as Br 2 , said wt % being based upon the total weight of the composition, (ii) from its inception, being free of detectable amounts of bromate ion, and (iii) from its inception, having a pH greater than 10.  
     
     
         32 . A concentrated biocidal composition containing sulfamate-stabilized bromonium ion, said composition (i) containing at least about 10 wt % up to about 18 wt % bromonium ion, measured as Br 2 , said wt % being based upon the total weight of the composition, (ii) having a pH greater than 10 and (iii) containing no detectable bromate ion.  
     
     
         33 . A concentrated biocidal composition containing stabilized oxidizing halogen obtained by the reaction of BrCl and  ⊖ SO 3 NH 2 , said composition (i) having at least about 10 wt % up to 16 wt % bromonium ion, measured as Br 2 , said wt % being based upon the total weight of the composition, and (ii) having a pH greater than 10.  
     
     
         34 . A concentrated biocidal composition containing stabilized oxidizing halogen obtained by the reaction of BrCl and  ⊖ SO 3 NH 2 , said composition having a pH greater than 10, and said composition having an active bromine content in the range of about 105,000 to about 120,000 ppm (wt/wt).  
     
     
         35 . A concentrated biocidal composition containing stabilized oxidizing halogen obtained by the reaction of BrCl and  ⊖ SO 3 NH 2 , said composition containing at least about 10 wt % up to about 18 wt % bromonium ion, measured as Br 2 , said wt % being based upon the total weight of the composition.  
     
     
         36 . A concentrated biocidal composition containing at least about 10 wt % up to about 18 wt %  ⊖ SO 3 NH 2  stabilized non-BrO ⊖ -oxidizing halogen.  
     
     
         37 . A concentrated biocidal composition containing stabilized non-BrO Θ -oxidizing halogen, said composition having a pH greater than 10, and said composition having an active bromine content of at least about 10 wt % up to about 16 wt %, said wt % being based upon the total weight of the composition.  
     
     
         38 . An aqueous mixture containing stabilized oxidizing halogen and having a pH between about 7 and about 8, and said composition having an active bromine content of at least 100,000 ppm (wt/wt) up to about 180,000 ppm (wt/wt).  
     
     
         39 . A composition according to any of claims  22 - 25 ,  30 - 32 , or  36 - 38  wherein said composition further comprises chloride ion in solution therein.