Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
  • C23F11/187—Mixtures of inorganic inhibitors
  • C23F11/188—Mixtures of inorganic inhibitors containing phosphates
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
  • C23F11/12—Oxygen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
  • C23F11/182—Sulfur, boron or silicon containing compounds
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
  • C23F11/184—Phosphorous, arsenic, antimony or bismuth containing compounds

Definitions

• This present disclosure relates to a solid block or solid molded treatment composition comprising a sulfite-based oxygen scavenger that remains in a solid form at elevated temperatures, a method of manufacturing a solid block or solid molded treatment composition, and a method of using a solid block or solid molded treatment composition for treating water in boiler and heated water systems.
• Various water treatment compositions are used to reduce corrosion on metal components in water systems, such as open recirculating systems, closed loop cooling or heating systems, cooling towers and boilers. Effective treatment to reduce corrosion prolongs the life of the system equipment and can save significant amounts of money.
• Many prior art treatment compositions and methods involve the use of liquid chemicals, typically shipped in large drums, which may make shipping and handling of the chemical compositions more difficult and expensive.
• Liquid treatments may be concentrated to reduce the volume of treatment product that must be shipped; however, the ingredients that may be useful in such treatment products are often not compatible in a concentrated liquid form, which limits the ability to use concentrated liquids. Additionally, shipping and handling concentrated liquid treatment compositions can still be more costly and hazardous than if the treatment composition were in a solid form.
• sulfite based oxygen scavengers are commonly used to treat heated water and boiler systems to reduce or prevent corrosion caused by dissolved oxygen in these systems, but is often provided as a liquid solution in drums. These are often heavy and can have significant hazards associated with them.
• Solid treatment compositions can avoid these drawbacks of liquids.
• Solid treatment compositions for boilers comprising either a one part or a two part formula are disclosed in U.S. Patent Nos. 9,506,016 and 9,441 ,190.
• the one part treatment which may be used alone according to the ‘190 patent, comprises a complex amine salt comprising cyclohexylamine, morpholine, monosodium phosphate and/or sodium metabisulfite or sodium sulfite, and deionized water.
• the total amount of sulfite in the one-part composition taught in the ‘190 patent is 30-40% (when ingredients amounts are normalized to total 100%) and the composition must also include a neutralizing amine (cyclohexylamine or morpholine), phosphate, and water.
• the two-part treatment comprises the complex amine salt (from the one part treatment) and a polymer, sodium sulfite, and disodium phosphate.
• the total amount of sulfite in the two-part composition disclosed is 16-56%; however, because the two-part formula contains amines, in use the amount fed would be limited based on FDA regulations (or similar governmental regulations or rules) on maximum amount of amines allowable.
• Powdered sulfite treatments are also known. These typically include a sodium sulfite alone, or sodium sulfite with a decharacterization additive and/or a sulfite catalyst.
• Chem-Aqua 10210 and Chem-Aqua 10100 are examples of powdered products available from Chem-Aqua. While the powdered products have some improvements over liquid treatment compositions, they also have some drawbacks. The powdered products need to be dissolved on-site using warm water prior to use, which typically requires a large mixing tank. Handling the powder to load the mixing tank can also create hazards with dust particles.
• These commercial powdered products also have limitations in that a 15% maximum solution can be feed into the water system to be treated, which results in a low active sulfite (as SO3) concentration in the water system of less than 20% by weight.
• solid treatment compositions provide improved ease of transportation, lower costs of shipping, and reduced risk of handling hazardous liquids.
• solid treatment compositions have some of their own drawbacks. For example, they must be formulated to allow for effective feeding into the water system using either a solid feeder or a feeder that dissolves the treatment composition prior to adding the dissolved solution into the water.
• commercially available solid sulfite-based oxygen scavenger compositions are generally not stable at the elevated temperatures encountered near heating and boiler systems and begin to melt, separate, or otherwise degrade.
• the HandiPak 910 and HandiPak 920 available from Chem-Aqua contain 60% or more sodium sulfite by weight and are effective at reducing corrosion; however, they begin to degrade at around 33 °C - 35 °C.
• compositions such as HandiPak 900+, HandiPak 910, and HandiPak 920, most commonly comprise sodium anhydrous as a raw material/ingredient, which forms sodium sulfite heptahydrate (Na2SOs 7H2O) in situ as the sulfite source.
• the compositions are typically formed by creating a sodium sulfite slurry in deionized water and then pouring into molds or bottles. The slurry then cures overnight at room temperature to form a solid. The formation and structure of the solid is created by the formation of sodium sulfite heptahydrate.
• HandiPak 900+, HandiPak 910, and HandiPak 920 contain sodium erythorbate and sodium lignosulfonate in addition to sodium sulfite.
• the cause for the thermal instability of these products to be the melting point of sodium sulfite heptahydrate, which is 33 °C. Testing of these products in the lab showed the formation of a liquid layer and degradation of the physical form from a single hard solid to a soft slurry above the melting point of 33 °C (as shown in FIG. 1 ).
• the present disclosure relates to thermally stable, solid sulfite- based treatment compositions and methods for making such compositions.
• the compositions are particularly useful for treating water systems in which an oxygen scavenger is needed, such as heated water systems and steam boilers.
• the compositions are thermally stable and do not degrade or experience melting issues at temperatures commonly found in non-climate controlled environments around such water systems where the composition would be stored and used, including temperatures of 35 °C to 45 °C. This allows the compositions to be formed into solid blocks or other molded forms that retain their form/shape at these elevated temperatures, where prior art solid block sulfite treatment products would experience degradation, loss of form/shape integrity, or melting.
• the treatment compositions are capable of being stored at or above this temperature range for extended periods of time until dissolved on site at the point of use to feed a sulfite solution into the water system being treated.
• a sulfite-based treatment composition comprises the following ingredients by weight: around 50 to 90% of a sulfite salt, around 5 to 30% of a second inorganic salt, and around 10 to 30 % water (preferably deionized water).
• these amounts of the salts are of raw materials that may include impurities or additives, making the actual amount of the target ingredients somewhat lower, such as a 0.1 -1 .5% difference.
• 60% by weight raw material sodium metabisulfite may comprise only around 59.16% sodium metabisulfite.
• dipotassium phosphate may comprise only around 9.8% dipotassium phosphate. Accordingly, the ranges indicated may include some impurities. It is preferred to use deionized water as it does not interfere with hydrate formation.
• the sulfite salt is sodium metabisulfite.
• a sulfite-based treatment composition comprises at least 50% active sulfite by weight, more preferably at least 60% active sulfite, and most preferably no more than 75.8% active sulfite by weight.
• the second inorganic salt is a phosphate.
• the phosphate is dipotassium phosphate.
• a sulfite-based treatment composition comprises at least 2.7% active phosphate (as PO4) by weight (when the second inorganic salt is a phosphate), more preferably at least 7% active phosphate, and most preferably no more than 17% active phosphate by weight.
• a sulfite-based treatment composition comprises at least 2.7% active phosphate (as PO4) by weight (when the second inorganic salt is a phosphate) and no more than 16.2% active phosphate by weight and in still other embodiments no more than 16.4% active phosphate by weight.
• the salts do not include any divalent cations, which could interfere with solubility in the water being treated.
• a sulfite-based treatment composition further comprises one or more optional ingredients.
• Optional ingredients may include a catalyst or a decharacterization additive or a combination thereof.
• a catalyst comprises cobalt sulfate heptahydrate, preferably in an amount of 0-1 % by weight.
• a catalyst comprises sodium erythorbate, preferably in an amount of 0-3% by weight.
• a decharacterization additive comprises a lignosulfonate, preferably sodium lignosulfonate and preferably in an amount of 0- 5% by weight.
• a method of making a thermally stable, solid sulfite-based treatment composition comprises heating deionized water to a first temperature range, adding a sulfite salt and stirring or mixing to create a slurry and until the temperature of the mixture returns to the first temperature range, slowly adding a second inorganic salt and continuing to stir or mix and maintaining the temperature at around the first temperature range until the mixture is homogenous, pouring the mixture into a mold and allowing it to cure at room temperature to form the thermally stable, solid sulfite-based treatment composition.
• the method preferably forms a hydrate of the second inorganic salt.
• the first temperature range is 10-20 °C higher than the corresponding melting point for the second inorganic salt hydrate.
• the first temperature range is around 68 to 72 °C, most preferably around 70 °C.
• a method of making a thermally stable, solid sulfite-based treatment composition further comprises adding and stirring or mixing a catalyst or a decharacterization additive or both.
• a catalyst, a decharacterization additive, or both are added prior to adding the sulfite salt.
• a thermally stable, solid sulfite-based treatment composition may comprise a dipotassium phosphate heptahydrate, with preferably around 16.9 to 33.8 % by weight of the dipotassium phosphate heptahydrate.
• the composition comprises dipotassium heptahydrate and no sulfite heptahydrate (or other sulfite hydrates).
• the composition comprises dipotassium heptahydrate and some sulfite heptahydrate.
• a solid sulfite-based treatment composition is in a solid molded form, such as a block.
• a solid molded form such as a block.
• other solid forms may be used, including pellets or powdered forms.
• a powdered form is excluded.
• Solid sulfite-based treatment compositions according to embodiments herein provide effective treatment to reduce or prevent corrosion in heated water systems and boiler systems like prior art liquid treatments but have the advantage of reduced size and weight for ease of shipping, handling, and storage, and safety. They also have advantages over prior art solid treatments in that they are thermally stable at elevated temperatures above 33 °C, more preferably above 35 °C, that are typically encountered near these water systems where the treatment composition will be stored and used.
• the solid sulfite-based treatment compositions according to embodiments herein do not experience melting, separation, or other physical or chemical degradation or instability, or loss of molded form/shape at these elevated temperatures like prior art solid treatments compositions do.
• solid treatment compositions according to embodiments herein can be dissolved on site using commercially available feeders or dissolvers that are usable with prior art treatments without experiencing any issues with clogging, failure to properly dissolve, or incorrect active ingredient concentrations in the solution and do not require any specialized feeder or dissolver to deliver an effective treatment solution to the water system being treated.
• FIG. 1 contains a photograph showing a bottle of prior art HandiPak 900+ after exposure to a temperature of 40 °C for 6 days, where a liquid layer above a soft slurry;
• FIG. 2 contains a photograph showing the stable solid form of a treatment composition of Example 1 according to an embodiment herein after exposure to a temperature of 40 °C for five days.
• a sulfite-based treatment composition comprises the following ingredients by weight: around 60 to 65% of a sulfite, around 15 to 22 % of a second inorganic salt, and around 18 to 24 % water (preferably deionized water, which does not interfere with the hydrate formation).
• these ingredients When mixed together and allowed to cure, preferably according to a method as described herein, these ingredients will form a thermally stable, solid sulfite-based treatment composition comprising a sulfite salt hydrate and a salt hydrate of the second inorganic salt.
• a sodium erythorbate catalyst may be in an amount of 0 to around 3% by weight, more preferably around 1 % to 2% by weight, and most preferably around 1 .3% to 1 .8% by weight.
• Other forms of these catalysts such as ethorybic acid, may also be used.
• any sulfite catalyst suitable for use in a heated water system or boiler including those listed in 21 CFR 173.310, may also be used. In other embodiments, only sulfite catalysts listed in 21 CFR 173.310 may be used. If more than one catalyst is used, a total amount of catalyst may be in an amount of 0 to around 4% by weight, more preferably around 1.0% to around 2.5% by weight, and more preferably around 1 .3% to around 2.1 % by weight.
• Trisodium Phosphate Dodecahydrate 65 °C melting point
• Sodium Acetate trihydrate 58 °C melting point
• Sodium Thiosulfate Pentahydrate 48 °C melting point
• Disodium Phosphate Heptahydrate 48 °C melting point
• Sodium Pyrophosphate Decahydrate 76 °C melting point
• Trisodium Phosphate Dodecahydrate 65 °C Melting point
• Sodium Acetate trihydrate 58 °C melting point
• Sodium Thiosulfate Pentahydrate 48 °C melting point
• Disodium Phosphate Heptahydrate 48 °C melting point
• Sodium Pyrophosphate Decahydrate 76 °C melting point
• Trisodium Phosphate Dodecahydrate 65 °C Melting point
• Sodium Acetate trihydrate 58 °C melting point
• Sodium Thiosulfate Pentahydrate 48 °C melting point
• the treatment compositions are most preferably fed into the water system using a solid product feeder that dissolves the composition into a solution that is discharged into the water system.
• a solid product feeder that dissolves the composition into a solution that is discharged into the water system.
• dissolvers are as described in U.S. Patent Application Publication No. 20110293481 or the commercially available Ultra-B and Ultra-M dissolvers from Chem-Aqua.
• the use of a product feeder that pre-dissolves the treatment composition is preferred, since it gives the ease of mixing with the water in the water system found in a liquid formula with the shipping and handling advantages of a solid formula.
• Solid sulfite-based compositions according to embodiments herein are thermally stable at temperatures of at least 33 °C, more preferably of at least 35 °C, and most preferably of at least 40 °C.
• the treatment composition would most likely be stored and used near a heating or boiler water system in a nonclimate controlled environment, which is unlikely to experience ambient temperatures above 50 °C or even 45 °C.
• treatment compositions according to embodiments herein may be thermally stable at temperatures above 45 °C, they do not need to be stable above this temperature.
• thermally stable means the compositions remain in a solid form and without physical and/or chemical deterioration, degradation, or instability when held at temperatures above the specified temperature for at least 1 day, more preferably at least 3 days, and most preferably at least 5 days.
• Physical and/or chemical deterioration or degradation may be shown by one or more of the following characteristics: (i) formation of a soft slurry; (ii) separation into visible layers; (iii) presence of liquid water; and/or (iv) failure of the composition to properly dissolve in a dissolution device/feeder (such as clogging or jamming the feeder and/or breaking off in chunks that do not fully dissolve prior to discharge from the feeder, and/or otherwise resulting in incorrect feed amounts or incorrect active concentrations in the dissolved solution for the desired sulfite treatment product that are above or below a target range.
• a dissolution device/feeder such as clogging or jamming the feeder and/or breaking off in chunks that do not fully dissolve prior to discharge from the feeder, and/or otherwise resulting in incorrect feed amounts or incorrect active concentrations in the dissolved solution for the desired sulfite treatment product that are above or below a target range.
• a method of making or manufacturing a thermally stable, solid sulfite-based treatment composition comprises the following steps: (1) adding deionized water to a mixing tank; (2) heating the water to a first temperature range; (3) adding a sulfite salt to the mixing tank; (4) stirring or mixing the sulfite salt with the water to create a slurry and continuing until the temperature of the mixture returns to the first temperature range; (5) slowly adding the second inorganic salt in manner in which the temperature of the mixture stays within the first temperature range or near the first temperature range (preferably within 5 °C of the first temperature range); (6) stirring or mixing during step 5 until all of the second inorganic salt has been added and the mixture is homogenous; (7) pouring the mixture into a mold; and (8) allowing the mixture to cool and cure at room temperature (preferably around 15 °C to 25 °C) for around 16 to 24 hours to form the thermally stable, solid sulfite-
• a method of making or manufacturing a thermally stable, solid sulfite-based treatment composition comprises the above steps except that the second inorganic salt is added in step (3) and the sulfite salt is added in step (5).
• the second inorganic salt is a phosphate
• the mixture when added in this order can be thicker.
• the phosphate is preferably added in step (5) after the sulfite is added in step (3).
• one or more optional ingredients are added as part of a method of making or manufacturing a thermally stable, solid sulfite-based treatment composition (preferably a composition according to an embodiment herein).
• a method comprises the steps in the preceding paragraphs and further comprises adding and stirring or mixing the one or more optional ingredients between steps (1 ) and (2).
• one or more optional ingredients may be (i) added prior to step (1 ) or (ii) during step (1 ) or (iii) after step (3) or (iv) during step (3).
• one or more optional ingredients comprises a catalyst and/or a decharacterization additive, the optional ingredients are added prior to adding the sulfite (in either step (3) or step (5)).
• the first temperature range may be around 10 to 20°C higher than the melting point of the second inorganic salt hydrate that will be formed.
• the first temperature range may be 68 to 78 °C.
• the first temperature range is around 65 to 75°C, more preferably around 68 to 72°C, and most preferably around 70°C.
• the curing time in step 8 will vary depending on the size of the mold and the temperature, but usually at least 16 hours is needed to complete the cure. In some embodiments, curing at cooler temperatures or in refrigeration may also be used; but most preferably, room temperature cooling is used to save on costs and to avoid potential issues with formation of the crystal structures during the curing, which may be negatively impacted by refrigeration temperatures.
• Example 1 An example product according to an embodiment of a treatment composition herein, Example 1 , was made according to a method of manufacture herein using the above method steps and the following ingredient amounts: 20% deionized water, 60 % sodium metabisulfite, and 20% dipotassium phosphate by weight. This Example 1 product did not include any catalysts or decharacterization additives. After curing, the example product was stored in a 40 °C oven for 5 days to test its thermal stability. The example product at the end of the 5 day is shown in FIG. 2. Unlike the prior art product in FIG. 1 , which separated and layered at a temperature of around 33 °C, the example product in FIG. 2 remained in a solid form and did not show any physical degradation.
• the example product was then tested in an Ultra-B dissolver (a commercially available device to dissolve solid treatments into a solution to be added to a water system being treated). This test was to confirm the example product dissolved correctly and would provide a treatment solution with the required sulfite activity, both of which were confirmed. This testing showed that no chemical instabilities occurred while in the 5 day 40 °C environment.
• Ultra-B dissolver a commercially available device to dissolve solid treatments into a solution to be added to a water system being treated.
• each of Examples 2-4 were stored in a 40 °C oven for 5 days to test thermal stability.
• Each of Examples 2-4 at the end of the 5 day heated test was similar in appearance to Example 1 as shown in FIG. 2, with each remaining in a solid form and without showing any physical degradation.
• Each of Examples 2-4 were then tested in an Ultra-B dissolver (a commercially available device to dissolve solid treatments into a solution to be added to a water system being treated). These tests were to confirm each example product dissolved correctly and would provide a treatment solution with the required sulfite activity, both of which were confirmed for Examples 2-4. This testing showed that no chemical instabilities occurred while in the 5 day 40 °C environment when a catalyst or decharacterization additive were included.
• treatment compositions and/or methods disclosed herein may include one or more of the following embodiments:
• Embodiment 1 A solid sulfite-based composition comprising: a first inorganic salt; and a hydrate of a second inorganic salt; wherein the first inorganic salt is a sulfite; and wherein the solid sulfite-based composition is thermally stable at temperatures between 35 °C - 40 °C.
• Embodiment 2 The solid sulfite-based composition according to Embodiment 1 wherein the solid sulfite-based composition comprises at least 50% active sulfite as SO3 by weight.
• Embodiment 3 The solid sulfite-based composition according to any one of Embodiments 1-2 wherein the second inorganic salt is a phosphate.
• Embodiment 4 The solid sulfite-based composition according to Embodiment 3 wherein the phosphate is dipotassium phosphate.
• Embodiment 5 The solid sulfite-based composition according to any one of Embodiments 1 -4 wherein the hydrate of the second inorganic salt is dipotassium heptahydrate.
• Embodiment 6 The solid sulfite-based composition according to any one of Embodiments 1-5 wherein the sulfite is sodium metabisulfite.
• Embodiment 7 The solid sulfite-based composition according to any one of Embodiments 1 -6 wherein the hydrate has a melting point of at least 40 °C.
• Embodiment 8 The solid sulfite-based composition according to any one of Embodiments 1 -6 wherein the hydrate has a melting point of at least 48 °C.
• Embodiment 9 The solid sulfite-based composition according to any one of Embodiments 1-8 further comprising a catalyst or a decharacterization additive or both.
• Embodiment 10 The solid sulfite-based composition according to Embodiment 9 wherein the catalyst comprises sodium erythorbate or cobalt sulfate heptahydrate or both; and wherein the decharacterization additive comprises a lignosulfonate.
• Embodiment 11 The solid sulfite-based composition according to Embodiment 10 wherein the lignosulfonate comprises sodium lignosulfonate.
• Embodiment 12 The solid sulfite-based composition according to any one of Embodiments 1 -11 wherein the solid sulfite-based composition is in a molded form that is thermally stable and maintains the molded form at temperatures between 35 °C - 40 °C for at least 5 days.
• Embodiment 13 A sulfite-based composition for treating heated water systems to reduce corrosion, the sulfite-based composition comprising the following ingredients: 60 to 80 % by weight of a first inorganic salt; 5 to 30 % by weight of a second inorganic salt; and 10 to 30 % by weight of deionized water; wherein the first inorganic salt is a sulfite; and wherein the second inorganic salt is capable of forming a hydrate having a melting point of at least 40 °C.
• Embodiment 14 The sulfite-based composition according to Embodiment 13 wherein the sulfite-based composition comprises at least 50% active sulfite (as SO3) by weight.
• Embodiment 15 The sulfite-based composition according to any one of Embodiments 13-14 wherein the second inorganic salt is dipotassium phosphate and wherein the hydrate has a melting point of at least 48 °C.
• Embodiment 16 The sulfite-based composition according to any one of Embodiments 13-15 wherein the sulfite is sodium metabisulfite.
• Embodiment 17 The sulfite-based composition according to any one of Embodiments 13-16 further comprising a catalyst or a decharacterization additive or both.
• Embodiment 18 The sulfite-based composition according to Embodiment 17 wherein the catalyst comprises 0 to 3% sodium erythorbate or 0 to 1 % cobalt sulfate heptahydrate or both; and wherein the decharacterization additive comprises 0 to 5% sodium lignosulfonate.
• Embodiment 19 The sulfite-based composition according to Embodiment 17 wherein the catalyst comprises 0 to 3% sodium erythorbate or 0 to 1 % cobalt sulfate heptahydrate or both; and wherein the decharacterization additive comprises 0 to 5% sodium lignosulfonate.
• a method of making a solid sulfite-based composition comprising: heating water to a first temperature range; adding and mixing a first inorganic salt to the water after heating the water to form a first mixture; adding and mixing a second inorganic salt to the first mixture to form a second mixture; pouring the second mixture into a mold; curing the second mixture in the mold until it is solid; wherein the first inorganic salt is a sulfite salt; and wherein the solid sulfite-based composition is thermally stable at temperatures between 35 °C - 40 °C.
• Embodiment 21 The method according to any one of Embodiments 19-20 further comprising adding a catalyst or a decharacterization additive or both prior to adding and mixing the sulfite salt.
• Embodiment 22 The method according to Embodiment 21 wherein the catalyst comprises sodium erythorbate or cobalt sulfate heptahydrate or both; and wherein the decharacterization additive comprises sodium lignosulfonate.
• Embodiment 23 The method according to any one of Embodiments 19-22 further comprising heating during adding and mixing the first inorganic salt until the first mixture is within the first temperature range.
• Embodiment 24 The method according to any one of Embodiments 19-23 wherein adding and mixing the second inorganic salt comprises slowly adding the second inorganic salt in a manner in which the second mixture stays within 5 °C of the first temperature range.
• Embodiment 25 The method according to any one of Embodiments 19-24 wherein adding and mixing the second inorganic salt comprises, or further comprises, adding 5 to 30% of the second inorganic salt by weight of the solid sulfite-based composition and mixing until the second mixture is homogenous.
• Embodiment 26 The method according to any one of Embodiments 19-25 wherein curing the second mixture comprises allowing the second mixture to sit in the mold at a second temperature range for at least 16 hours.
• Embodiment 27 The method according to Embodiment 26 wherein the second temperature range is around 15 to 30 °C.
• Embodiment 28 The method according to any one of Embodiments 19-27 wherein the solid sulfite-based composition comprises around 60 to 80% of the first inorganic salt and around 5 to 30% of the second inorganic salt by weight.
• Embodiment 29 The method according to any one of Embodiments 19-28 further comprising heating during adding and mixing the first inorganic salt until the first mixture is within the first temperature range; wherein the first temperature range is around 65 to 70 °C; wherein adding and mixing the second inorganic salt comprises slowly adding the second inorganic salt in a manner in which the second mixture stays within 5 °C of the first temperature range; wherein curing the second mixture comprises allowing the second mixture to sit in the mold at a second temperature range for at least 16 hours; wherein the second temperature range is around 15 to 30 °C; wherein the solid sulfite-based composition comprises around 60 to 80% of the first inorganic salt and around 5 to 30% of the second inorganic salt by weight; wherein the first inorganic salt is sodium metabisulfite; and wherein the second inorganic salt is dipotassium phosphate.
• Embodiment 30 The method according to any one of Embodiments 19-29 wherein the solid sulfite-based composition is according to any one of Embodiments 1-12.
• Embodiment 31 The method according to any one of Embodiments 19-29 wherein the solid sulfite-based composition is the sulfite-based composition according to any one of Embodiments 13-18. [0071] Embodiment 32.
• a method of treating a water system comprising: adding a sulfite-based composition to the water system, the sulfite-based composition comprising (1 ) first inorganic salt, and (2) a hydrate of a second inorganic salt; wherein the first inorganic salt is a sulfite; wherein the sulfite-based composition is in a solid form prior to adding the sulfite-based composition to the water system, wherein the solid form is thermally stable at temperatures between 35 °C - 40 °C; and wherein the water system is a heated water system or boiler system.
• Embodiment 33 The method of Embodiment 32 further comprising dissolving the solid form prior to adding the sulfite-based composition to the water system.
• Embodiment 34 The method of any one of Embodiments 32-33 wherein the sulfite-based composition provides an active sulfite concentration as SO3 in the water system of at least 10,000 ppm.
• Embodiment 35 The method of any one of Embodiments 32-34 wherein the sulfite-based composition comprises at least 50% active sulfite as SO3 by weight.
• Embodiment 36 The method of any one of Embodiments 32-35 wherein the second inorganic salt is a phosphate.
• Embodiment 37 The method of Embodiment 36 wherein the phosphate is dipotassium phosphate.
• Embodiment 38 The method of Embodiment 37 wherein the hydrate of the dipotassium phosphate is dipotassium heptahydrate.
• Embodiment 39 The method according to any one of Embodiments 32-38 wherein the sulfite-based composition is made according to any one of Embodiments 19-31.
• Embodiment 40 The method according to any one of Embodiments 32-34 wherein the sulfite-based composition is the solid sulfite-based composition according to any one of Embodiments 1-12.
• Embodiment 41 The method according to any one of Embodiments 32-34 wherein the sulfite-based composition is according to any one of Embodiments 13-18.
• references to “about” or “around” with respect to numerical values generally mean(1 ) +/- 1 for values expressed as whole numbers (without a decimal, e.g., around 15% means 14-16%); (2) +/- 0.1 for values expressed with a single decimal place (for example, around 9.5% means 9.4-9.6%; and (3) +/- 0.01 for values expressed with two or more decimal places (for example, around 0.02 means 0.01-0.03, each of the foregoing excluding values that would result in a negative number.
• References to ranges expressed as “at least” means greater than or equal to the value, including each individual value, up to 100% when the value is expressed as a percentage. For example, at least 50% means 50-100%, including all individual amounts and subranges therein.
• references to ranges expressed as “more than” a value means greater than the value, up to 100% when the value is expressed as a percentage. For example, more than 50% means 50.0001-100%, including all individual amounts and subranges therein. References to ranges expressed as “no more than” means less than or equal to the value, down to 0 when the value is expressed as a weight, volume, concentration. For example, no more than 16% means 0-16%, including all individual amounts and subranges therein. References to ranges expressed as “less than” or “below” means all values that are less than the value, down to 0 when the value is expressed as a weight, volume, concentration. For example, less than 16% means 0-15.9999%, including all individual amounts and subranges therein.
• references herein to water (without any modifier) as an ingredient in a treatment composition include potable water, distilled water, deionized water, or other forms of purified, filtered, or cleaned water. These forms of water may be substituted for references herein to deionized water, other than in the claims.
• thermoally stable, solid sulfite-based treatment compositions With respect to the discussion of various embodiments according to the disclosure, references herein to “thermally stable, solid sulfite-based treatment compositions,” “solid sulfite-based compositions,” “treatment compositions,” and similar phrases are used to refer to any of the composition embodiments herein.
• Any ingredient or method steps of an embodiment herein may be used with any other ingredients, features, components, or steps of other embodiments even if not specifically described with respect to that embodiment, unless such combination is explicitly excluded herein. Any ingredient or amount of an ingredient, or method steps described as excluded with any particular embodiment herein may similarly be excluded with any other embodiment herein even if not specifically described with such embodiment.
• Any treatment composition embodiment herein may comprise, consist essentially of, or consist of any combination of ingredients described herein. Any specific treatment composition ingredient described herein as one that may be included or may be optionally included in any embodiment herein, such as sodium phosphate as the specific second inorganic salt, may also be excluded from any embodiment herein.

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• 2024
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