EP1744631A1 - Préparation de solutions de brome concentré et de solides de brome à forte activité - Google Patents

Préparation de solutions de brome concentré et de solides de brome à forte activité

Info

Publication number
EP1744631A1
EP1744631A1 EP04822042A EP04822042A EP1744631A1 EP 1744631 A1 EP1744631 A1 EP 1744631A1 EP 04822042 A EP04822042 A EP 04822042A EP 04822042 A EP04822042 A EP 04822042A EP 1744631 A1 EP1744631 A1 EP 1744631A1
Authority
EP
European Patent Office
Prior art keywords
alkali metal
bromine
solid
sulfamic acid
earth alkali
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP04822042A
Other languages
German (de)
English (en)
Inventor
Jonathan N. Howarth
Michael S. Harvey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Enviro Tech Chemical Services Inc
Original Assignee
Enviro Tech Chemical Services Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Enviro Tech Chemical Services Inc filed Critical Enviro Tech Chemical Services Inc
Priority to EP10158856.4A priority Critical patent/EP2236034B1/fr
Priority to EP11157553.6A priority patent/EP2359694B1/fr
Priority to EP10158859A priority patent/EP2236035A2/fr
Priority to EP10158861A priority patent/EP2236036A2/fr
Publication of EP1744631A1 publication Critical patent/EP1744631A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds

Definitions

  • the invention relates to methods for the preparation of concentrated aqueous bromine solutions and high activity bromine-containing solids using elemental bromine or bromine chloride.
  • the products are used as microbiocides in water treatment.
  • 5,683,654, 5,795,487, 5,942,126, and 6,136,205 all describe a method to manufacture a single feed, liquid bromine biocide by mixing an aqueous hypochlorite solution with bromide ion sources followed by introduction of a stabilizer agent.
  • the method requires a complex two-vessel reaction. In the first step, NaBr and NaOCl solutions were mixed and sufficient time was allowed to permit the formation of a sodium hypobromite (NaOBr) solution. In the second step, this was then introduced to a solution of the stabilizer agent maintained at 50° C.
  • NaOBr sodium hypobromite
  • the disadvantage of this method is that the concentration of the stabilized bromine product is limited by the concentration of NaOCl bleach that is commercially available.
  • WO 03/093171 disclosed a method for preparing a stabilized bromine solution with a halogen content higher than any previously reported solution prepared from hypochlorite and sodium bromide.
  • Example 1 of WO 03/093171 described a cumbersome multi-step method.
  • an unstabilized solution of sodium hypobromite was made by adding elemental bromine to a sodium hydroxide solution and allowing the mixture to react.
  • Introducing a solution of sodium sulfamate prepared by reacting sulfamic acid with a solution of sodium hydroxide followed this.
  • the resulting product was determined to possess a halogen content of 19.6% as Br 2 (8.7% as Cl 2 ).
  • Example 4 of the same application disclosed an even more complex multi-step method for preparing a solution reported to have a halogen concentration of 21.6% as Br (9.6% as Cl ).
  • this concentration is erroneous because the maximum concentration that can be obtained from the stated quantities of the components (even assuming a 100% yield in every step), is calculated to be 19.7% as Br 2 (8.7% as Cl 2 ).
  • the concentration that was obtained was probably substantially less than 19.7% as Br 2 (8.7% as Cl 2 ), because it is well-known that the first step cannot proceed with a 100% yield.
  • the prior art also discloses that other methods also fail to yield satisfactory products in terms of higher active ingredient concentration, physical stability, and reaction efficiency.
  • bromine-releasing compounds that are sold commercially as biocidal products. They are generally available as heterocyclic organic compounds to which an oxidizing bromine atom is covalently bonded to a nitrogen atom on the ring. Examples include N,N ⁇ bromochloro-5,5-dimethylhydantoin, l,3-dibromo-5,5-dimethylhydantoin, and mixtures of these compounds with various other components. In water, these materials hydrolyze to release hypobromous acid, which is the biocidal agent. However, a major limitation of these solid compounds is that they are only sparingly soluble in water.
  • N,N" bromochloro-5,5-dimethylhydantoin has a water solubility of only 0.1% at 20° C.
  • bromine is released very slowly from these products as they dissolve.
  • the low solub* " of these products also precludes application where there is insufficient water available to dissolve enough of the solid to deliver a biocidally-effective dose. This invention addresses those needs.
  • the present invention is directed to convenient methods of preparing: (1) highly concentrated liquid bromine-containing solutions, (2) highly concentrated mixed halogen liquid bromine and chlorine-containing solutions, and (3) high-activity bromine- containing solids, all having excellent physical and chemical stability. Contrary to the teachings of the prior art, the present invention discloses methods in which elemental bromine or bromine chloride is introduced to a sulfamate solution to yield a final solution having a concentration of active ingredient in excess of 18% as Br 2 (8% as Cl 2 ). The methods of the present invention also yield a final solution having a mole ratio of hydroxide ion to hydrogen ion source (e.g.
  • the hydrogen ion source is defined as being the sum of the reagents that dissociate into strong acids in water, e.g. sulfamic acid or other acidic stabilizer plus Br or BrCl.
  • the present inventors have discovered that calculating this mole ratio is a more accurate way of determining the amount of hydroxide ion to use to obtain a final solution of high concentration, than the methods used by the prior art.
  • the prior art methods use a pH measurement, and teach that the amount of hydroxide ion that should be added is the amount necessary to raise the pH to about 13.
  • the present inventors have calculated the mole ratio for several of the solutions produced by introducing elemental bromine or BrCl to a solution of sodium su 1 ⁇ "- ite that have been disclosed in the prior art and found them all to be less than or equal to 1.62:1.
  • the method employed a hydroxide ion to hydrogen ion source (sulfamic acid plus Br 2 ) mole ratio of 1 : 1 and obtained a product that had a measured pH of 7.
  • Example 4 of the same patent described a solution containing 19.6% as Br 2 (8.7% as Cl 2 ) that utilized a hydroxide ion to hydrogen ion source (sulfamic acid plus Br 2 ) mole ratio of 1.62: 1.
  • This solution had a measured pH of 13.0. No elevated temperature, chemical, or physical stability data was reported for either of these solutions.
  • Example 2 of U.S. 6,506,418 described a method involving the addition of both Br 2 and Cl 2 to a solution of sodium sulfamate to a maximum strength solution of 14.8 % as Br (6.59 % as Cl 2 ). Again, this utilized a hydroxide ion to hydrogen ion source (sulfamic acid plus Br 2 plus Cl ) mole ratio of 1.62: 1.
  • solutions produced using the introduction of Br 2 or BrCl to a solution of sodium sulfamate that have a mole ratio of hydroxide ion to hydrogen ion source of greater than 1.62: 1 have not been previously reported. As will be subsequently demonstrated, such solutions display dramatically enhanced chemical and physical stability over those in which the mole ratio is less than or equal to 1.62: 1.
  • the products of the methods of this invention are sources of oxidizing bromine that are useful for microbiological control in aqueous systems. This is generally achieved by introducing the products into water requiring microbiological control in an amount sufficient to be biocidally effective.
  • the first embodiment of the invention is a method for preparing highly concentrated liquid bromine-containing solutions using elemental bromine or bromine chloride. The method yields solutions that have concentrations of bromine in excess of 18% as Br 2 (?
  • the second embodiment of the invention is a method for preparing highly concentrated liquid bromine-containing solutions using elemental bromine in conjunction with a solid organic or inorganic halogenating agent.
  • the method yields solutions that are chemically and physically stable and possess concentrations of bromine of at least 11.25%) as Br 2 (5% as Cl 2 ). Using this method, it is possible to prepare such solutions at concentrations greater than 22.9% as Br 2 (10.2% as Cl 2 ). Physical and chemical stabilization of the solutions is achieved using a hydroxide ion to hydrogen ion source (e.g. sulfamic acid plus Br 2 ) mole ratio of at least 1.9:1.
  • the third embodiment of the invention is a method for preparing highly concentrated mixed halogen solutions that contain both bromine and chlorine. The method utilizes elemental bromine in conjunction with a solid organic or inorganic chlorinating agent.
  • the method yields solutions that have excellent chemical and physical stability, and possess total halogen concentrations of at least 11.25% when expressed as Br 2 (5% when expressed as Cl 2 ). Using this method, it is possible to prepare such solutions having concentrations of total halogen that are greater than 22.7% when expressed as Br 2 (10.1% when expressed as Cl ). Physical and chemical stabilization of the solutions is achieved using a hydroxide ion to hydrogen ion source (e.g. sulfamic acid plus Br 2 ) mole ratio of at least 1.9:1.
  • the fourth embodiment of the invention is a method for preparing solid bromine- containing compositions. This method utilizes elemental bromine in conjunction with a solid organic or inorganic halogenating agent to prepare three end products.
  • the first is a saturated solution of the alkali metal or earth alkali metal salt of hydrated N- bromosulfamate.
  • the second and third are the solid alkali metal or earth alkali metal salt of hydrated N-bromosulfamate and the solid alkali metal or earth alkali metal salt of anhydrous N-bromosulfamate, respectively.
  • the stabilization is accomplished by employing a hydroxide ion to hydrogen ion source (e.g. sulfamic acid plus Br 2 or BrCl) mole ratio of at least 1.9:1.
  • a hydroxide ion to hydrogen ion source e.g. sulfamic acid plus Br 2 or BrCl
  • a major benefit of the methods of the second and third embodiments is that all of the Br moieties introduced to the reactor as elemental bromine materialize as active bromine in the final product. None of the Br moieties are wasted as by-product inactive bromide ion salts.
  • the solid organic or inorganic halogenating agents serve to reactivate the bromide ions to ensure that both bromine atoms of the Br 2 molecule are utilized as active forms in the products.
  • a noteworthy feature of the method of the second embodiment is that it provides stable, aqueous bromine-containing compositions that contain significantly lower amounts of contaminant halide ion salts than the methods of the prior art.
  • the method of the second embodiment results in an all-bromine liquid composition with a far lower level of halide ion contaminant per mole of active bromine than is possible using alternative methods.
  • this method yields a product in which halide ion-induced physical and chemical destabilization is significantly reduced.
  • Table I compares the ratio of inactive, soluble halide ion (X ' ) to active bromine in the final product when various alternative reagents are used. Table I
  • this method yields a product in which halide ion-induced physical and chemical destabilization is significantly reduced.
  • Table II compares the ratio of inactive, soluble halide ion (X " ) to active halogen in the final product when various alternative reagents are used.
  • these solid halogenating agents are generally high in available halogen and do not contain large amounts of extraneous salts or inactive ingredients that enter the finished product (see, for example, WO 03/093171).
  • the compositions that are obtained using solid halogenating agents possess lower levels of water, as well as lower levels of dissolved salts or other extraneous materials, which would otherwise dilute the available halogen content of the product and adversely impact its chemical and physical stability.
  • Another remarkable benefit of this invention is that the methods of the second and third embodiments make possible the formation of highly concentrated liquid bromine- containing compositions employing methods that generate no solid wastes.
  • TCCA trichloroisocyanuric acid
  • NaDCC sodium dichlorisocyanurate
  • NaDCC.2H 2 0 sodium dichloro-s-triazinetrione dihydrate
  • potassium dichloroisocyanurate or dichloroisocyanuric acid
  • CA cyanuric acid
  • CA wetcake Upon filtration and washing, highly purified CA wetcake is recovered. This can be recycled to other methods to make additional quantities of TCCA, NaDCC, or NaDCC.2H 2 O that can be used in the methods of this invention.
  • a notable discovery of this invention is that the method of the fourth embodiment can be performed under conditions that exceed the solubility of the hydrated alkali metal or earth alkali metal salt of N-bromosulfamate, and further, that the resulting solid can be crystallized and recovered in good yield.
  • the First Embodiment is a method for preparing highly concentrated liquid bromine-containing solutions using Br 2 or BrCl.
  • Table III lists the basic components of solutions prepared using Br 2 or BrCl that contain an active ingredient of 18.1% as Br 2 (8.04%) as Cl 2 ) and which possess a hydroxide ion to hydrogen ion source (sulfamic acid plus Br 2 or BrCl) mole ratio of 2.3:1. Higher concentrations than this are prepared by employing more elemental Br 2 or BrCl at the expense of sulfamic acid, water, or 50%> sodium hydroxide solution provided the hydroxide ion to hydrogen ion source mole ratio does not drop below 1.9:1.
  • the golden colored solutions that are produced using this method contain 27-39% or 35-52%o more active bromine than solutions that are available commercially, respectively, depending on whether Br 2 or BrCl is used.
  • the method of this embodiment includes the following steps. Steps (a), (b), (c), and (d) may be performed sequentially or as otherwise set forth below. Steps (a) and (b) may be performed simultaneously, followed by the remaining steps. Steps (b) and (d) may be combined so that all of the alkaline source is added in step (b). If performed, step (d) may be conducted at the same time as step (c). a. Dispersing solid sulfamic acid in an aqueous phase.
  • Sulfamic acid displays moderate solubility in water (14.7 g/100 g at 0°C). When the amount of sulfamic acid added to water exceeds the solubility limit at any given temperature, some of the solid remains undissolved. Upon stirring the mixture, the sulfamic acid solids are dispersed in the aqueous phase. As indicated in Table III, the amount of water used to disperse the sulfamic acid depends on whether elemental bromine or bromine chloride is used. Preferably, a slurry of between about 25%> and about 75% solid sulfamic acid in water is employed, with about 30% to about 40% being the most preferred range. b.
  • an alkaline source in order to form a solution of the alkali metal or earth alkali metal salt of sulfamic acid.
  • Any alkaline source may be employed. Examples include, but are not limited to, alkali metal or earth alkali metal carbonates, bicarbonates, oxides, and hydroxides. When solutions are preferred, sodium hydroxide or potassium hydroxide solutions may be used, alone or in combination with each other.
  • a particularly preferred alkaline source is 50% NaOH solution.
  • the 50%> NaOH solution may be diluted with water and used.
  • the sodium hydroxide solution is introduced to the reaction medium slowly, with stirring and cooling, such that the temperature preferably does not exceed about 85° F.
  • the amount of 50% NaOH solution employed should preferably be at least sufficient to fully neutralize the sulfamic acid and form sodium sulfamate according to equation (1).
  • a molar excess of 50% NaOH is utilized relative to the amount of sulfamic acid.
  • the mole ratio of hydroxide ion to sulfamic acid is preferably between about 2:1 and about 4:1, most preferably between about 2:1 and about 3:1. If available, solid alkali metal salts of sulfamic acid may be used. In these circumstances, it is only necessary to dissolve the salts in water to make a solution. Preferably, an additional quantity of 50% NaOH is then utilized.
  • the mole ratio of hydroxide ion to alkali metal salt of sulfamic acid is preferably between about 1 : 1 and about 3:1, most preferably between about 1 : 1 and about 2:1.
  • Introducing bromine chloride or elemental bromine The amount of bromine chloride or elemental bromine added depends on the amount of sulfamic acid originally present.
  • a mole ratio of about 0.75 : 1 to about 1.5:1 sulfamic acid to bromine chloride or elemental bromine is advantageous to the stability of the final product, with about 0.95:1 to about 1.2:1 being the most preferred mole ratio range.
  • Table III shows the quantities of elemental bromine or bromine chloride needed to introduce to the reaction medium in order for the resulting solution to have an active ingredient concentration of 18.1% as Br 2 (8.04% as Cl 2 ).
  • the bromine chloride or elemental bromine is dropped into the reaction medium from above the surface, or it may be introduced subsurface via a dip tube.
  • the dip tube should be positioned so . that the BrCl or Br 2 is introduced to an area of high turbulence, e.g. near the tip of a rotating agitator blade so that it is well dispersed into the reaction medium.
  • the BrCl or Br 2 is added with sufficient mixing and at a rate to avoid significant phase separation and pooling of the materials at the bottom of the reactor. With adequate mixing and dispersion, the BrCl or Br 2 introduced to the reactor containing the solution of sodium hydroxide and sodium sulfamate hydrolyzes readily according to reaction (2).
  • alkali metal or earth alkali metal carbonates, bicarbonates, oxides, and hydroxides examples include, but are not limited to, alkali metal or earth alkali metal carbonates, bicarbonates, oxides, and hydroxides.
  • sodium hydroxide or potassium hydroxide solutions can be used, alone or in combination with each other.
  • a particularly preferred alkaline source is 50% NaOH solution. To prevent storage problems in cold climates, the 50%> NaOH solution may be diluted with water and used. The alkaline source is introduced to the reaction medium slowly, with stirring and cooling, such that the temperature preferably does not exceed about 85° F.
  • the overall mole ratio of hydroxide ion to sodium sulfamate is preferably between about 2 : 1 and about 4:1, most preferably between about 3 : 1 and about 4:1.
  • Example 1 Deionized water (52.5 ml) was introduced to a four-necked round bottom flask and solid sulfamic acid (24.9 g) was added. The slurry was stirred and 50%> NaOH (44.6 g) was slowly added as the flask was chilled in an ice bath to keep the temperature of the flask contents below about 85°F.
  • Example 2 From the data in Table III, it is apparent that solutions prepared using BrCl will always contain more water than equivalent solutions prepared using elemental bromine. This is because BrCl has a molecular weight of 115.4 compared to 159.8 for elemental bromine. Therefore, because of their higher relative water content, solutions prepared using BrCl should be able to support the dissolution of even higher levels of active ingredient than their counterparts prepared using elemental bromine.
  • the Br 2 that was used in Example 1 is replaced with a molar equivalent amount of BrCl.
  • Deionized water (52.5 ml) is introduced to a four-necked round bottom flask and solid sulfamic acid (24.9 g) is added.
  • Example 3 For the purposes of comparative elevated temperature stability testing, the reaction of Example 1 was repeated, except that a hydroxide ion to hydrogen ion source (sulfamic acid plus Br 2 ) mole ratio of 1.69:1 was employed.
  • Deionized water 69.1 ml
  • solid sulfamic acid (24.6 g) was added.
  • the slurry was stirred and 50%> NaOH (44.6 g) was slowly added as the flask was chilled in an ice bath to keep the temperature of the flask contents below about 85°F.
  • the Second Embodiment is a method for preparing highly concentrated liquid bromine- containing solutions using elemental bromine in conjunction with a solid organic or inorganic halogenating agent.
  • the golden colored solutions produced as a result of this method contain 48-62% more available bromine than solutions that are available commercially.
  • the solutions are stabilized to physical and chemical degradation reactions by adjusting the hydroxide ion to hydrogen ion source (sulfamic acid plus Br 2 ) mole ratio to 2.3:1.
  • a typical reaction is described in Example 4.
  • the method resulted in a solution containing 22.9% as Br 2 (10.2% as Cl 2 ).
  • the method preferably includes the following steps. Steps (a)-(g) may be performed sequentially or as otherwise set forth below.
  • Steps (a) and (b) may be performed simultaneously, followed by the remaining steps. Steps (e) and (g) may be combined.
  • a. Dispersing solid sulfamic acid in an aqueous phase. Sulfamic acid displays moderate solubility in water (14.7 g/100 g at 0°C). When the amount of sulfamic acid added to water exceeds the solubility limit at any given temperature, some of the solid remains undissolved. Upon stirring the mixture, the sulfamic acid solids are dispersed in the aqueous phase. Preferably, a slurry of between about 25% to about 75%> solid sulfamic acid in water is employed, with about 30% to about 40%) being the most preferred range.
  • an alkaline source in order to form a solution of the alkali metal or earth alkali metal salt of sulfamic acid.
  • Any alkaline source may be employed. Examples include, but are not limited to, alkali metal or earth alkali metal carbonates, bicarbonates, oxides, and hydroxides. When solutions are preferred, sodium hydroxide or potassium hydroxide solutions are convenient to use, alone or in combination with each other.
  • a particularly preferred alkaline source is 50% NaOH solution.
  • the 50%) NaOH solution may be diluted with water and used.
  • the alkaline source is introduced to the reaction medium slowly, with stirring and cooling, such that the temperature preferably does not exceed 85° F.
  • the amount of 50% NaOH solution employed should preferably be at least sufficient to fully neutralize the sulfamic acid and form sodium sulfamate according to equation (5).
  • a molar excess of 50% NaOH is utilized relative to the amount of sulfamic acid.
  • steps (c) and (d) about 1.2 to about 1.8 moles of hydroxide ions are introduced for every mole of sulfamic acid present.
  • solid alkali metal salts of sulfamic acid may be used in the method of this embodiment. In these circumstances, it is only necessary to dissolve the salts in water to make a solution. Preferably, an additional quantity of 50% NaOH is then utilized.
  • about 0.2 to about 0.8 moles of hydroxide ions are introduced for every mole of alkali metal salt of sulfamic acid present. c. Introducing elemental bromine.
  • the amount of elemental bromine added depends on the amount of sulfamic acid originally present. A mole ratio of about 0.4: 1 to about 0.8:1 sulfamic acid to elemental bromine is advantageous to the stability of the final product, with about 0.45:1 to about 0.6:1 being the most preferred mole ratio range.
  • the elemental bromine is dropped into the reaction mixture from above the surface, or it may be introduced subsurface via a dip tube. When the latter is preferred, the dip tube should be positioned so that the Br 2 is introduced to an area of high turbulence, e.g. near the tip of a rotating agitator blade for efficient mixing in the reaction medium.
  • the Br 2 is added with sufficient mixing and at a rate to avoid significant phase separation and pooling at the bottom of the reactor. With adequate mixing, the Br 2 introduced to the reactor containing the solution of sodium hydroxide and sodium sulfamate hydrolyzes readily according to reaction (6).
  • the hypobromous acid formed reacts with sodium sulfamate to form sodium N- bromosulfamate according to reaction (7).
  • the pH should be between about 0.5 and about 9, preferably between about 1.0 and about 4.5. These pH conditions facilitate the chemical reaction of step (d).
  • Solid inorganic halogenating agents include, but are not limited to, alkali metal and earth alkali metal hypochlorite salts. Suitable examples include lithium hypochlorite, calcium hypochlorite, and magnesium hypochlorite. Due to its low cost and high available chlorine content, calcium hypochlorite is particularly preferred. The higher strength granular forms of the product (containing about 65-75% available chlorine) are most preferred.
  • Solid organic halogenating agents include any organic compound in which one or more halogen atoms such as Cl, Br, or I is present in oxidation state +1 and is covalently bound to a nitrogen or phosphorus atom within the same molecule.
  • Suitable examples include, but are not limited to, trichloroisocyanuric acid (TCCA), sodium dichlorisocyanurate (NaDCC), sodium dichlorisocyanurate dihydrate (NaDCC.2H 2 O), potassium dichloroisocyanurate, dichloroisocyanuric acid, trichloromelamine, N-chloro-p-toluenesulfonamide, N-chloromethanesulfonamide, N- chlorosuccinimide, N,N'-l,3-bromochloro-5,5-dimethylhydantoin, N,N'-1 ,3- bromochloro-5-ethyl-5-methylhydantoin, and l,
  • a particularly preferred source of a solid, organic halogenating agent is trichloroisocyanuric acid (TCCA).
  • TCCA trichloroisocyanuric acid
  • the TCCA reacts rapidly with the NaBr generated in reactions (8) and (9) according to reaction (10).
  • dry powdered TCCA is favored because of its easy handling characteristics, TCCA powdered wetcake may also be employed. The advantage of using TCCA wetcake is that it may be taken directly from the TCCA-producing reactors and so costs associated with drying of the material are eliminated.
  • Filtration is a particularly preferred technique for effecting solid-liquid separation.
  • the solid organic halogenating agent is TCCA
  • cyanuric acid is a reaction by-product that is insoluble in the reaction medium (see reaction (10)).
  • Filtration of the cyanuric acid (CA) residue is carried out at about pH 1-9, but preferably at about pH 1- 6 to maximize its recovery from solution and minimize the amount of bromine vapors that fume from the reaction medium.
  • Upon washing the filtercake with water to remove the mother liquors, a highly pure CA wetcake is recovered. This can be recycled to other processes to make additional quantities of TCCA, NaDCC, or NaDCC.2H 2 O that can be used in the method of the current invention.
  • this step can be modified so that the sodium salt of cyanuric acid is recovered from the reaction medium instead of cyanuric acid.
  • This is accomplished by introducing, before performing the solid-liquid separation, sufficient 50%> NaOH to react with cyanuric acid according to the following reaction: CA + NaOH ⁇ NaCA + H 2 0 ...(11)
  • the amount of 50% sodium hydroxide solution employed depends on the amount of solid organic halogenating agent used in step (d).
  • TCCA is the solid organic halogenating agent
  • sufficient 50%> NaOH solution is introduced slowly with mixing and cooling to convert all or substantially all of the cyanuric acid liberated in reaction (10) into its monosodium salt via reaction (11).
  • Monosodium cyanurate is insoluble in the reaction medium at pH ⁇ 9.
  • cyanuric acid monosodium cyanurate can be separated and recycled to other processes in order to make additional quantities of TCCA, NaDCC, or NaDCC.2H 2 O that can be used in the method of the current invention. This is accomplished by performing a solid-liquid separation, as described above, which is done when the pH stabilizes at about 9. f. Adding an alkaline source to the reaction mother liquors, such that if the alkaline source is a hydroxide salt, the overall mole ratio of hydroxide ion to sulfamic acid is between about 3 : 1 and about 5:1, preferably between about 4:1 and about 5:1.
  • any hydroxide salt that may be used to convert cyanuric acid into its alkali metal or earth alkali metal salt as described in step (e).
  • Any alkaline source may be employed. Examples include, but are not limited to, alkali metal or earth alkali metal carbonates, bicarbonates, oxides, and hydroxides. When solutions are preferred, sodium hydroxide or potassium hydroxide solutions are convenient to use, alone or in combination with each other.
  • a particularly preferred alkaline source is 50%> NaOH solution. To prevent storage problems in cold climates, the 50%) NaOH solution may be diluted with water and used. The alkaline source is introduced to the reaction medium slowly, with stirring and cooling, such that the temperature preferably does not exceed 85°F.
  • the purpose is to deprotonate the bromo derivative of sulfamic acid to form the bromo derivative of sodium sulfamate according to reaction (12).
  • step (e) when TCCA is the halogenating agent, almost 90% of CA reaction by-product is recovered as a highly pure wetcake in the first solid-liquid separation step described in step (e). While not wishing to be bound by theory, it is believed that salts of cyanuric acid are precipitated from the reaction mother liquors upon the addition of alkaline sources.
  • the alkaline source is, for example, 50% sodium hydroxide solution
  • the mono-, di-, and trisodium salts of cyanuric acid are precipitated.
  • the di-and trisodium salts display exceptional solubility in ordinary water and are thus useful water treating agents in their own right.
  • step (e) the amount of solid that may subsequently develop is relatively low, and step (g) may require only a polishing solid- liquid separation, with, for example, a cartridge filter. Moreover, the two solid-liquid separation steps of (e) and (g) may be combined into a single operation performed at step (e).
  • Example 4 Deionized water (120 ml) was introduced to a 4-necked round bottom flask and solid sulfamic acid (85 g) was added. The slurry was stirred and 50%o NaOH (88.2g) was slowly added as the flask was chilled in an ice bath to keep the temperature of the flask contents at around 75 °F. Using a dropping funnel, elemental bromine (58.7 g) was dispensed at a rate of about one drop per second to the reaction medium, also with stirring and cooling to maintain a reaction temperature of 68 °F. When the bromine addition was complete, the pH of the reaction medium was measured to be 1.80.
  • the Third Embodiment is a method for preparing a highly concentrated mixed halogen solution that contains both bromine and chlorine.
  • the method utilizes elemental bromine in conjunction with a solid organic or inorganic chlorinating agent.
  • This light golden-colored composition contains 46-60%> more available halogen than the all- bromine solutions that are currently available commercially.
  • a typical reaction is described in Example 6.
  • the method resulted in a solution containing a total halogen content of 22.4%> when expressed as Br 2 (10.1%o when expressed as Cl 2 ).
  • a major benefit of a mixed halogen biocide is in the treatment of contaminated water that exerts a considerable halogen demand.
  • compositions based on mixtures of stabilized bromine and chlorine are particularly significant aspects that in water systems employing long contact times, there may be sufficient time for the N-chloro sulfamate to react with "spent" bromide ion and regenerate N-bromosulfamate according to the following reaction.
  • [Br -NH- SO 3 " ] + H 2 O HOBr + NH 2 SO 3 "
  • HOBr Upon performing biocidal and oxidative reactions, HOBr reverts to soluble bromide ion. This can enter into reaction with N-chlorosulfamate to generate additional N-bromosulfamate.
  • This highly water-soluble composition exhibits improved physical stability as it becomes less prone to solid precipitation on storage.
  • the method preferably includes the following steps. Steps (a)-(g) may be performed sequentially or as otherwise set forth below. Steps (a) and (b) may be performed simultaneously, followed by the remaining steps. Steps (e) and (g) may be combined.
  • the sulfamic acid solids are dispersed in the aqueous phase.
  • a slurry of between about 25% to about 75% solid sulfamic acid in water is employed, with about 30% to about 40% being the most preferred range.
  • b. Forming a solution of the alkali metal or earth alkali metal salt of sulfamic acid in the aqueous phase.
  • an alkaline source in order to form a solution of the alkali metal or earth alkali metal salt of sulfamic acid. Any alkaline source may be employed.
  • alkali metal or earth alkali metal carbonates, bicarbonates, oxides, and hydroxides examples include, but are not limited to, alkali metal or earth alkali metal carbonates, bicarbonates, oxides, and hydroxides.
  • sodium hydroxide or potassium hydroxide solutions are convenient to use, alone or in combination with each other.
  • a particularly preferred alkaline source is 50%o NaOH solution. To prevent storage problems in cold climates, the 50% NaOH solution may be diluted with water and used. The alkaline source is introduced to the reaction medium slowly, with stirring and cooling, such that the temperature preferably does not exceed 85° F. The amount of 50% NaOH solution employed should preferably be at least sufficient to fully neutralize the sulfamic acid and form sodium sulfamate according to equation (13).
  • a molar excess of 50% NaOH is utilized relative to the amount of sulfamic acid.
  • a molar excess of 50% NaOH is utilized relative to the amount of sulfamic acid.
  • about 1.2 to about 1.8 moles of hydroxide ions are introduced for every mole of sulfamic acid present.
  • solid alkali metal salts of sulfamic acid may be used in the method of this embodiment. In these circumstances it is only necessary to dissolve the salts in water to make a solution.
  • an additional quantity of 50%) NaOH is then utilized.
  • step (c) and (d) about 0.2 to about 0.8 moles of hydroxide ions are introduced for every mole of alkali metal salt of sulfamic acid present.
  • elemental bromine The amount of elemental bromine added depends on the mole ratio of bromine to chlorine that is desired in the final product, and the amount of sulfamic acid used in step (a). For example, a mixed halogen composition containing 80 mole % bromine and 20 mole % chlorine is prepared using 0.66 moles of bromine per mole of available chlorine provided by the solid chlorinating agent used in step (d).
  • a mole ratio of about 0.75:1 to about 1.5:1 sulfamic acid to available halogen provided by the sum of the bromine and the solid chlorinating agent is advantageous to the stability of the final product, with about 0.95:1 to about 1.2:1 being the most preferred mole ratio range.
  • the elemental bromine is dropped into the reaction mixture from above the surface, or it may be introduced subsurface via a dip tube. When the latter is preferred, the dip tube should be positioned so that the Br 2 is introduced to an area of high turbulence, e.g. near the tip of a rotating agitator blade for efficient mixing in the reaction medium.
  • the Br 2 is added with sufficient mixing and at a rate to avoid significant phase separation and pooling at the bottom of the reactor. With adequate mixing, the Br 2 introduced to the reactor containing the solution of sodium hydroxide and sodium sulfamate hydrolyzes readily according to reaction (14). Br 2 + H 2 O ⁇ HOBr + HBr ...(14) The hypobromous acid formed reacts with sodium sulfamate to form sodium N- bromosulfamate according to reaction (15).
  • the pH is between about 0.5 and about 9, preferably between about 1.0 and about 4.5. These pH conditions facilitate the chemical reaction of step (d).
  • Solid inorganic chlorinating agents include, but are not limited to, alkali metal and earth alkali metal hypochlorite salts. Suitable examples include lithium hypochlorite, calcium hypochlorite, and magnesium hypochlorite. Due to its low cost and high available chlorine content, calcium hypochlorite is particularly preferred.
  • Solid organic chlorinating agents include any organic compound in which one or more chlorine atoms is present in oxidation state +1 and is covalently bound to a nitrogen or phosphorus atom within the same molecule.
  • Suitable examples include, but are not limited to, trichloroisocyanuric acid (TCCA), sodium dichlorisocyanurate (NaDCC), sodium dichlorisocyanurate dihydrate (NaDCC.2H 2 O), potassium dichloroisocyanurate, dichloroisocyanuric acid, trichloromelamine, N-chloro-p-toluenesulfonamide, N- chloromefhanesulfonamide, N-chlorosuccinimide, N,N'- 1 ,3-bromochloro-5,5- dimethylhydantoin, N,N'-l,3-bromochloro-5-ethyl-5-methylhydantoin, and 1,3-dichloro- 5,5-dimethylhydantoin.
  • TCCA trichloroisocyanuric acid
  • NaDCC sodium dichlorisocyanurate
  • NaDCC.2H 2 O sodium dichlorisocyan
  • a particularly preferred source of a solid, organic chlorinating agent is trichloroisocyanuric acid (TCCA).
  • TCCA trichloroisocyanuric acid
  • the solid chlorinating agent has two functions. First, it oxidizes all of the bromide ions released in reactions (16) and (17) into bromine which reacts with the sulfamic acid to form N-bromosulfamic acid. When the solid chlorinating agent is TCCA, it reacts as indicated in reaction (18).
  • Suitable examples include, but are not limited to, centrifugation, clarification, gravity sedimentation, and vacuum filtration. Filtration is a particularly preferred technique for effecting solid-liquid separation.
  • the solid organic chlorinating agent is TCCA
  • cyanuric acid is a reaction by-product that is insoluble in the reaction medium (see reactions (18) and (19)).
  • Filtration of the cyanuric acid (CA) residue is carried out at about pH 1-9, but preferably at about pH 1- 6 to maximize its recovery from solution and minimize the amount of bromine vapors that fume from the reaction medium. Upon washing the filtercake with water to remove the mother liquors, a highly pure CA wetcake is recovered.
  • this step can be modified so that the sodium salt of cyanuric acid is recovered from the reaction medium instead of cyanuric acid. This is accomplished by introducing, before performing the solid-liquid separation, sufficient 50% NaOH to react with cyanuric acid according to the following reaction: CA + NaOH ⁇ NaCA + H 2 0 ...(20) The amount of 50%> sodium hydroxide solution employed depends on the amount of solid organic chlorinating agent used in step (d).
  • an alkaline source to the reaction mother liquors, such that if the alkaline source is a hydroxide salt, the overall mole ratio of hydroxide ion to sulfamic acid is between about 3:1 and about 5: 1, preferably between about 4: 1 and about 5:1.
  • Any alkaline source may be employed. Examples include, but are not limited to, alkali metal or earth alkali metal carbonates, bicarbonates, oxides, and hydroxides. When solutions are preferred, sodium hydroxide or potassium hydroxide solutions are convenient to use, alone or in combination with each other.
  • a particularly preferred alkaline source is 50% NaOH solution.
  • the 50% NaOH solution may be diluted with water and used.
  • the alkaline source is introduced to the reaction medium slowly, with stirring and cooling, such that the temperature preferably does not exceed 85°F.
  • the purpose is to deprotonate the bromo derivative of sulfamic acid to form the bromo derivative of sodium sulfamate according to reaction (21).
  • step (e) In comparison to the amount of solids recovered in step (e), the amount of solid that may subsequently develop is relatively low, and step (g) may require only a polishing solid- liquid separation, with, for example, a cartridge filter. Moreover, the two solid-liquid separation steps of (e) and (g) may be combined into a single operation performed at step (e).
  • Example 5 This example describes the preparation of a mixed halogen solution that was formulated to contain a theoretical 80 mole % bromine and 20 mole % chlorine. Deionized water (138.2 ml) was introduced to a four-necked round bottom flask and solid sulfamic acid (85.0 g) was added.
  • the fourth embodiment is a method of preparing highly water soluble, bromine- containing solid compounds, namely, the alkali metal or earth alkali metal salt of hydrated N-bromosulfamate and the alkali metal or earth alkali metal salt of anhydrous N-bromosulfamate.
  • the method uses elemental Br 2 in conjunction with a solid organic or inorganic halogenating agent under reaction conditions designed to promote the formation of the solid, e.g. above the solubility limit.
  • the solubility of the sodium salt of hydrated N-bromosulfamate in the reaction medium of this embodiment is about 23.6%> as Br 2 (10.6% as Cl 2 ).
  • the combination product, a slurry may be advantageously packaged and transported to a separate location for subsequent reconstitution by simple addition of water to yield an aqueous stabilized, liquid bromine composition whose concentration can be tailored to the amount of reconstitution water used.
  • the second and third products are the solid alkali metal or earth alkali metal salt of hydrated N-bromosulfamate and the solid alkali metal or earth alkali metal salt of anhydrous N-bromosulfamate, respectively. These high-activity solids are stable and dissolve rapidly and completely to yield a highly concentrated bromine containing solution.
  • the method preferably includes the following steps. Steps (a)-(h) or (a)-(i) may be performed sequentially or as otherwise set forth below.
  • Steps (a) and (b) may be performed simultaneously, followed by the remaining steps. Steps (e) and (g) may be combined.
  • a. Dispersing solid sulfamic acid in an aqueous phase. Sulfamic acid displays only moderate solubility in water (14.7 g/100 g at 0°C). When the amount of sulfamic acid added to water exceed the solubility limit at any given temperature some of the solid remains undissolved. Upon stirring the mixture, the sulfamic acid solids are dispersed in the aqueous phase. Preferably, solid sulfamic acid is slurried into % to 3 / 4 its weight of water, with about l ⁇ its weight of water being especially preferred. b.
  • an alkaline source in order to form a solution of the alkali metal or earth alkali metal salt of sulfamic acid.
  • Any alkaline source may be employed. Examples include, but are not limited to, alkali metal or earth alkali metal carbonates, bicarbonates, oxides, and hydroxides. When solutions are preferred, sodium hydroxide or potassium hydroxide solutions are convenient to use, alone or in combination with each other.
  • a particularly preferred alkaline source is 50%> NaOH solution.
  • the 50%) NaOH solution may be diluted with water and used.
  • the alkaline source is introduced to the reaction medium slowly, with stirring and cooling, such that the temperature preferably does not exceed 85° F.
  • the amount of 50%> NaOH solution employed should preferably be at least sufficient to fully neutralize the sulfamic acid and form sodium sulfamate according to equation (22).
  • a molar excess of 50% NaOH is utilized relative to the amount of sulfamic acid.
  • steps (c) and (d) about 1.2 to about 1.8 moles of hydroxide ions are introduced for every mole of sulfamic acid present.
  • solid alkali metal salts of sulfamic acid may be used in the method of this embodiment. In these circumstances, it is only necessary to dissolve the salts in water to make a solution. Preferably, an additional quantity of 50%> NaOH is then utilized.
  • about 0.2 to about 0.8 moles of hydroxide ions are introduced for every mole of alkali metal salt of sulfamic acid present. c. Introducing elemental bromine.
  • the amount of elemental bromine added depends on the amount of sulfamic acid originally present. A mole ratio of about 0.4:1 to about 0.8:1 sulfamic acid to elemental bromine is advantageous to the stability of the final product, with about 0.45:1 to about 0.6: 1 being the most preferred mole ratio range.
  • the elemental bromine is dropped into the reaction mixture from above the surface, or it may be introduced sub-surface via a dip tube. When the latter is preferred, the dip tube should be positioned so that the Br 2 is introduced to an area of high turbulence, e.g. near the tip of a rotating agitator blade for efficient mixing in the reaction medium.
  • the Br 2 is added with sufficient mixing and at a rate to avoid significant phase separation and pooling at the bottom of the reactor.
  • the Br 2 introduced to the reactor containing the solution of sodium hydroxide and sodium sulfamate hydrolyzes readily according to reaction (23).
  • the hypobromous acid formed reacts with sodium sulfamate to form sodium N- bromosulfamate according to reaction (24).
  • the pH is between about 0.5 and about 9, preferably between about 1.0 and about 4.5. These pH conditions facilitate the chemical reaction of step (d).
  • Solid inorganic halogenating agents include, but are not limited to, alkali metal and earth alkali metal hypochlorite salts. Suitable examples include lithium hypochlorite, calcium hypochlorite, and magnesium hypochlorite. Due to its low cost and high available chlorine content, calcium hypochlorite is particularly preferred. The higher strength granular forms of the product (containing about 65-75%> available chlorine) are most preferred.
  • Solid organic halogenating agents include any organic compound in which one or more halogen atoms such as Cl, Br, or I is present in oxidation state +1 and is covalently bound to a nitrogen or phosphorus atom within the same molecule.
  • Suitable examples include, but are not limited to, trichloroisocyanuric acid (TCCA), sodium dichlorisocyanurate (NaDCC), sodium dichlorisocyanurate dihydrate (NaDCC.2H 2 O), potassium dichloroisocyanurate, dichloroisocyanuric acid, trichloromelamine, N-chloro-?-toluenesulfonamide, N-chloromethanesulfonamide, N-chlorosuccinimide, N,N'-1,3- bromochloro-5,5-dimethylhydantoin, N,N'-1 ,3-bromochloro-5-ethyl-5-methylhydantoin, and l,
  • a particularly preferred source of a solid, organic halogenating agent is trichloroisocyanuric acid (TCCA).
  • TCCA trichloroisocyanuric acid
  • TCCA trichloroisocyanuric acid
  • the TCCA reacts rapidly with the NaBr generated in reactions (25) and (26) according to reaction (27).
  • dry powdered TCCA is favored because of its easy handling characteristics, TCCA powdered wetcake may also be employed.
  • the advantage of using TCCA wetcake is that it may be taken directly from the TCCA-producing reactors and so costs associated with drying of the material are eliminated.
  • Filtration is a particularly preferred technique for effecting solid-liquid separation.
  • the solid organic halogenating agent is TCCA
  • cyanuric acid is a reaction by-product that is insoluble in the reaction medium (see reaction (27)).
  • Filtration of the cyanuric acid (CA) residue is carried out at about pH 1 -9, but preferably at about pH 1 - 6 to maximize its recovery from solution and minimize the amount of bromine vapors that fume from the reaction medium.
  • this step can be modified so that the sodium salt of cyanuric acid is recovered from the reaction medium instead of cyanuric acid.
  • This is accomplished by introducing, before performing the solid-liquid separation, sufficient 50%> NaOH to react with cyanuric acid according to the following reaction: CA + NaOH ⁇ NaCA + H 2 0 ...(28)
  • the amount of 50%> sodium hydroxide solution employed depends on the amount of solid organic halogenating agent used in step (d).
  • TCCA is the solid organic halogenating agent
  • sufficient 50%> NaOH solution is introduced slowly with mixing and cooling to convert all or substantially all of the cyanuric acid liberated in reaction (27) into its monosodium salt via reaction (28).
  • Monosodium cyanurate is insoluble in the reaction medium at pH ⁇ 9.
  • cyanuric acid monosodium cyanurate can be separated and recycled to other processes in order to make additional quantities of TCCA, NaDCC, or NaDCC.2H 2 O that can be used in the method of the current invention. This is accomplished by performing a solid-liquid separation, as described above, which is done when the pH stabilizes at about 9. f. Adding an alkaline source to the reaction mother liquors, such that if the alkaline source is a hydroxide salt, the overall mole ratio of hydroxide ion to sulfamic acid is between about 3:1 and about 5:1, preferably between about 4: 1 and about 5:1.
  • any hydroxide salt that may be used to convert cyanuric acid into its alkali metal or earth alkali metal salt as described in step (e).
  • Any alkaline source may be employed. Examples include, but are not limited to, alkali metal or earth alkali metal carbonates, bicarbonates, oxides, and hydroxides. When solutions are preferred, sodium hydroxide or potassium hydroxide solutions are convenient to use, alone or in combination with each other.
  • a particularly preferred alkaline source is 50%> NaOH solution. To prevent storage problems in cold climates, the 50%> NaOH solution may be diluted with water and used. The alkaline source is introduced to the reaction medium slowly, with stirring and cooling, such that the temperature preferably does not exceed 85° F.
  • the purpose is to deprotonate the bromo derivative of sulfamic acid to form the bromo derivative of sodium sulfamate according to reaction (29).
  • any suitable solid-liquid separation technique may be employed.
  • TCCA is the halogenating agent, almost 90% of CA reaction by-product is recovered as a highly pure wetcake in the first solid-liquid separation step described in step (e).
  • step (e) While not wishing to be bound by theory, it is believed that salts of cyanuric acid are precipitated from the reaction mother liquors upon the addition of alkaline sources.
  • the alkaline source is, for example, 50%> sodium hydroxide solution
  • the mono-, di-, and trisodium salts of cyanuric acid are precipitated.
  • the di-and trisodium salts display exceptional solubility in ordinary water and are thus useful water treating agents in their own right.
  • step (g) may require only a polishing solid- liquid separation, with, for example, a cartridge filter.
  • the two solid-liquid separation steps of (e) and (g) may be combined into a single operation performed at step (e).
  • Crystallization of the bromine-containing solid from its supersaturated solution may be achieved by any conventional means. These methods include, but are not limited to, chilling the reaction medium to reduce the solubility of the bromine-containing salt even further to trigger the precipitation process, seeding the reaction medium with bromine-containing salts obtained in an earlier crop so as to provide a surface on which additional crystals are encouraged to nucleate and grow, and evaporating the reaction medium under vacuum to drive off solvent water and promote the crystallization process.
  • Suitable examples include, but are not limited to, centrifugation, clarification, gravity sedimentation, and vacuum filtration. Filtration is a particularly preferred technique for effecting solid-liquid separation.
  • the solid recovered is the alkali metal or earth alkali metal salt of hydrated N-bromosulfamate as a crystalline material.
  • the hydrated solid In order to obtain the alkali metal or earth alkali metal salt of anhydrous N- bromosulfamate, the hydrated solid must be dried. Any suitable drying technique may be employed to dry the solid. Suitable examples include, but are not limited to, fluidized bed drying, vacuum oven drying, flash drying, and drying over dessicant, such as molecular sieves.
  • Example 6 Deionized water (50.5 ml) was introduced to a four-necked round bottom flask and solid sulfamic acid (98.3 g) was added. The slurry was stirred and 50% NaOH
  • the crystalline mass was observed to comprise mainly regular rhombohedral crystals of hydrated sodium N-bromosulfamate that possessed a yellow glass-like appearance. A portion of the crystalline mass was lightly dabbed with a paper towel to remove the mother liquors and a weighed amount of this was dissolved in water. It dissolved rapidly and completely. Iodometric titration of the solution was used to calculate that the crystalline solid contained 42.7% as Br 2 (18.9%o as Cl 2 ).
  • the invention has been described above with reference to the preferred embodiments. Those skilled in the art may envision other embodiments and variations of the invention that fall within the scope of the claims.

Abstract

Cette invention propose des méthodes simples et pratiques afin de préparer : (1) des solutions biocides à forte concentration en brome liquide, (2) des solutions biocides à forte concentration en mélange de brome liquide et de chlore, et (3) des solides biocides contenant du brome à forte activité, solutions qui offrent toutes une excellente stabilité physique et chimique. L’une de ces méthodes permet de produire des solutions qui présentent des concentrations en brome du type Br2 supérieures à 18% (8% de C12) dans lesquelles le rapport moléculaire de l’ion d’oxyde hydraté à l’ion d’hydrogène de départ est d’au moins 1,9 :1. Une autre méthode utilise du brome élémentaire en association avec un agent solide organique ou inorganique favorisant l’halogénation, dans le but de produire des solutions halogénées à concentration en Br2 supérieures à 22,9% (10,2% de C12). Cette seconde méthode peut être utilisée sous des conditions chimiques qui excèdent la solubilité de la matière active, de telle façon qu’elle cristallise pour être ensuite récupérée sous la forme soit d’un sel hydraté soit d’un sel anhydre, de bon rendement.
EP04822042A 2004-05-10 2004-05-10 Préparation de solutions de brome concentré et de solides de brome à forte activité Ceased EP1744631A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP10158856.4A EP2236034B1 (fr) 2004-05-10 2004-05-10 Procédé de préparation de liquide contenant du bromure et de chlorure
EP11157553.6A EP2359694B1 (fr) 2004-05-10 2004-05-10 Préparation de solutions concentrées de brome et solides au brome à grande activité
EP10158859A EP2236035A2 (fr) 2004-05-10 2004-05-10 Procédé de préparation d'un solide contenant du brome en équilibre avec sa solution saturée
EP10158861A EP2236036A2 (fr) 2004-05-10 2004-05-10 Solide contenant du brome

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2004/014778 WO2005112649A1 (fr) 2004-05-10 2004-05-10 Préparation de solutions de brome concentré et de solides de brome à forte activité

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP11157553.6A Division EP2359694B1 (fr) 2004-05-10 2004-05-10 Préparation de solutions concentrées de brome et solides au brome à grande activité
EP10158856.4A Division EP2236034B1 (fr) 2004-05-10 2004-05-10 Procédé de préparation de liquide contenant du bromure et de chlorure

Publications (1)

Publication Number Publication Date
EP1744631A1 true EP1744631A1 (fr) 2007-01-24

Family

ID=35428197

Family Applications (5)

Application Number Title Priority Date Filing Date
EP10158856.4A Expired - Fee Related EP2236034B1 (fr) 2004-05-10 2004-05-10 Procédé de préparation de liquide contenant du bromure et de chlorure
EP11157553.6A Expired - Fee Related EP2359694B1 (fr) 2004-05-10 2004-05-10 Préparation de solutions concentrées de brome et solides au brome à grande activité
EP04822042A Ceased EP1744631A1 (fr) 2004-05-10 2004-05-10 Préparation de solutions de brome concentré et de solides de brome à forte activité
EP10158861A Withdrawn EP2236036A2 (fr) 2004-05-10 2004-05-10 Solide contenant du brome
EP10158859A Withdrawn EP2236035A2 (fr) 2004-05-10 2004-05-10 Procédé de préparation d'un solide contenant du brome en équilibre avec sa solution saturée

Family Applications Before (2)

Application Number Title Priority Date Filing Date
EP10158856.4A Expired - Fee Related EP2236034B1 (fr) 2004-05-10 2004-05-10 Procédé de préparation de liquide contenant du bromure et de chlorure
EP11157553.6A Expired - Fee Related EP2359694B1 (fr) 2004-05-10 2004-05-10 Préparation de solutions concentrées de brome et solides au brome à grande activité

Family Applications After (2)

Application Number Title Priority Date Filing Date
EP10158861A Withdrawn EP2236036A2 (fr) 2004-05-10 2004-05-10 Solide contenant du brome
EP10158859A Withdrawn EP2236035A2 (fr) 2004-05-10 2004-05-10 Procédé de préparation d'un solide contenant du brome en équilibre avec sa solution saturée

Country Status (3)

Country Link
EP (5) EP2236034B1 (fr)
IL (1) IL179239A (fr)
WO (1) WO2005112649A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113614206A (zh) * 2019-03-28 2021-11-05 杰富意钢铁株式会社 煤混合物的制造方法和焦炭的制造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2821528T3 (es) 2012-11-14 2021-04-26 Grace W R & Co Composiciones que contienen un material biológicamente activo y un óxido inorgánico no ordenado

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5795487A (en) 1997-01-03 1998-08-18 Nalco Chemical Company Process to manufacture stabilized alkali or alkaline earth metal hypobromite and uses thereof in water treatment to control microbial fouling
US5683654A (en) 1996-03-22 1997-11-04 Nalco Chemical Co Process to manufacture stabilized alkali or alkaline earth metal hypobromite and uses thereof in water treatment to control microbial fouling
US5942126A (en) 1997-01-03 1999-08-24 Nalco Chemical Company Process to manufacture stabilized alkali or alkaline earth metal hypobromite and uses thereof in water treatment to control microbial fouling
US7087251B2 (en) * 1998-06-01 2006-08-08 Albemarle Corporation Control of biofilm
US6068861A (en) 1998-06-01 2000-05-30 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US8414932B2 (en) * 1998-06-01 2013-04-09 Albemarie Corporation Active bromine containing biocidal compositions and their preparation
US6652889B2 (en) 1998-06-01 2003-11-25 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation and use
US6348219B1 (en) 1998-06-01 2002-02-19 Albemarle Corporation Processes for preparing concentrated aqueous liquid biocidal compositions
US6511682B1 (en) 1998-06-01 2003-01-28 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US6352725B1 (en) 1998-06-01 2002-03-05 Albemarle Corporation Continuous processes for preparing concentrated aqueous liquid biocidal composition
US6123870A (en) * 1998-06-29 2000-09-26 Nalco Chemical Company Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control
US6270722B1 (en) 1999-03-31 2001-08-07 Nalco Chemical Company Stabilized bromine solutions, method of manufacture and uses thereof for biofouling control
US6669904B1 (en) * 1999-03-31 2003-12-30 Ondeo Nalco Company Stabilized bromine solutions, method of making and uses thereof for biofouling control
US6110387A (en) * 1999-04-22 2000-08-29 Albemarle Corporation Sulfamate stabilization of a bromine biocide in water
US6506418B1 (en) 1999-09-24 2003-01-14 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US6375991B1 (en) 2000-09-08 2002-04-23 Albemarle Corporation Production of concentrated biocidal solutions
IL149499A (en) 2002-05-06 2006-10-31 Bromine Compounds Ltd Process for the preparation of concentrated solutions of stabilized hypobromites
WO2004026770A1 (fr) * 2002-09-19 2004-04-01 Nalco Company Melange stabilise de brome et de chlore, son procede de fabrication et ses utilisations pour le controle d'encrassement biologique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005112649A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113614206A (zh) * 2019-03-28 2021-11-05 杰富意钢铁株式会社 煤混合物的制造方法和焦炭的制造方法

Also Published As

Publication number Publication date
WO2005112649A1 (fr) 2005-12-01
EP2236034A3 (fr) 2011-12-21
EP2359694B1 (fr) 2016-01-06
EP2236034B1 (fr) 2015-05-27
EP2359694A2 (fr) 2011-08-24
EP2359694A3 (fr) 2011-12-21
EP2236036A2 (fr) 2010-10-06
EP2236034A2 (fr) 2010-10-06
IL179239A (en) 2011-08-31
EP2236035A2 (fr) 2010-10-06

Similar Documents

Publication Publication Date Title
US8574605B2 (en) Methods for the preparation of concentrated aqueous bromine solutions and high activity bromine-containing solids
US8048435B2 (en) Preparation of concentrated aqueous bromine solutions and biocidal applications thereof
CN101253859B (zh) 含活性溴的杀生物剂组合物的制造方法
US7045153B2 (en) Highly concentrated bromine compositions and methods of preparation
JP3832399B2 (ja) 殺菌殺藻剤組成物及び水系の殺菌殺藻方法
WO2007142618A2 (fr) Compositions et mélanges aqueux à activité biocide et à concentration élevée
US7455859B2 (en) Highly concentrated bromine compositions and methods of preparation
EP1786266B1 (fr) Solutions aqueuses concentrees de brome et leur preparation
CA2322111C (fr) Compositions 1,3,5-triazine-2,4,6-trione stables a niveaux d'halogene eleves ayant des taux de dissolution rapides
IL179239A (en) Methods for the preparation of concentrated aqueous bromine solutions and high activity bromine-containing solids
US20060029680A1 (en) Methods of preparing highly concentrated aqueous bromine solutions
MXPA06000095A (en) Highly concentrated bromine compositions and methods of preparation
US8293795B1 (en) Preparation of concentrated aqueous bromine solutions and biocidal applications thereof
WO2006022694A2 (fr) Procedes de preparation de solutions de brome aqueux hautement concentrees

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20061123

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

DAX Request for extension of the european patent (deleted)
RBV Designated contracting states (corrected)

Designated state(s): DE FR GB

18R Application refused

Effective date: 20101125

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

R18R Application refused (corrected)

Effective date: 20100924