# Patent

## Title
MG++ chemistry and method for fouling inhibition in heat processing of liquid foods and industrial processes

## Abstract

The present invention relates to methods for removing or preventing scale formation in a liquid food processing operation. The present invention also relates to methods and compositions for increasing the solubility of insoluble calcium salts in an acidic environment. Aqueous antiscalant solutions comprising soluble magnesium salts are used to prevent the precipitation of insoluble calcium salts and/or to increase the solubility of insoluble calcium salts.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 12/114,428 filed on May 2, 2008 and entitled “MG++ Chemistry and Method Fouling Inhibition In Heat Processing of Liquid Foods and Industrial Processes” which claims priority and is related to U.S. Provisional Application Ser. No. 60/927,575 filed on May 4, 2007 and entitled “Compositions Containing Magnesium Salts and Methods of Using.” The entire contents of these patent applications are hereby expressly incorporated herein by reference including, without limitation, the specification, claims, and abstract, as well as any figures, tables, or drawings thereof.
This application is also related to: U.S. patent application Ser. No. 12/114,486, entitled “Cleaning Compositions with Water Insoluble Conversion Agents and Methods of Making and Using Them”; U.S. patent application Ser. No. 12/114,355, entitled, “Composition For In Situ Manufacture Of Insoluble Hydroxide When Cleaning Hard Surfaces And For Use In Automatic Warewashing Machines, And Methods For Manufacturing And Using”; U.S. patent application Ser. No. 12/114,448, entitled “Water Treatment System and Downstream Cleaning Methods”; U.S. patent application Ser. No. 12/114,327, entitled “Water Soluble Magnesium Compounds as Cleaning Agents and Methods of Using Them”; U.S. patent application Ser. No. 12/114,513, entitled “Cleaning Compositions Containing Water Soluble Magnesium Compounds and Methods of Using Them”; U.S. patent application Ser. No. 12/114,329, entitled “Compositions Including Hardness Ion and Gluconate and Methods Employing Them to Reduce Corrosion and Etch”; U.S. patent application Ser. No. 12/114,342, entitled “Compositions Including Hardness Ion and Silicate and Methods Employing Them to Reduce Corrosion and Etch”; U.S. patent application Ser. No. 12/114,364, entitled “Compositions Including Hardness Ion and Threshold Agent and Methods Employing Them to Reduce Corrosion and Etch”; and U.S. patent application Ser. No. 12/114,385, entitled “Warewashing Compositions for Use in Automatic Dishwashing Machines and Method for Using”, all commonly assigned to Ecolab Inc., and are all incorporated herein by reference for all purposes.


FIELD OF THE INVENTION
The present invention relates generally to removing or preventing scale formation in a food processing operation. In particular, the present invention is related to a method of preventing the precipitation of calcium salts and/or increasing the solubility of calcium salts in a food processing operation.
BACKGROUND
The formation of calcium salt scales such as calcium phosphate, calcium oxalate, calcium carbonate, and calcium silicate, during liquid food processing is a significant problem for the food and beverage industry, particularly for breweries, vegetable juice processors, and evaporators in food processing plants. Exemplary liquid food streams that require processing include, but are not limited to: milk, whey, whey permeate, fruit and vegetable juices, calcium fortified beverages, sugar, corn wet milling steeping liquor, and fuel ethanol process streams from corn, sugar, or other biomass conversions. In particular, calcium phosphate may form during the processing of milk, and calcium oxalate may form during the processing of sugar, spinach, and other juices.
The formation of the calcium salt scales on processing equipment surfaces causes scaling or fouling, and decreases in the flow rate and the run-time. Various stages of food processing operations involve concentrating or heating liquid food process streams, such as during evaporation, filtration, or pasteurization. Typically, equipment scaling occurs during heat exchange stages, such as the evaporation stage and the ultra high temperature (UHT) stage of food processing operations. For example, during the UHT stage, the liquids are pasteurized at temperatures of around about 146 degrees Celsius as the liquid goes through the tube. The heat facilitates the formation and deposition of calcium salts on the surfaces of the equipment, decreasing the flow rate and run time of the equipment.
Current methods for removing calcium salts deposited on equipment surfaces typically involve using the alkaline salts of ethylene diamine triacetic acid (EDTA), biodegradable chelants, or strong solutions of nitric acid, phosphoric acid, or sulfuric acid. In the case of calcium oxalate deposits, hydrochloric acid and hydrofluoric acid may be used. These solutions dissolve the calcium salts and remove the scale, i.e., the calcium salt deposits, from the surface of the equipment. The equipment is cleaned daily with the calcium salts being removed during an acid rinse cycle.
SUMMARY
In some aspects, the present invention provides a method for preventing scale formation on industrial food processing equipment used to process a liquid food source. In some embodiments, the method comprises applying an antiscalant aqueous solution comprising a water soluble source of magnesium ion to the equipment, wherein the antiscalant solution is applied to the equipment by at least one of direct injection into the liquid food source prior to evaporation and direct injection in the process lines of the equipment prior to evaporation, such that the formation of scale on the equipment is substantially prevented.
In some embodiments, the water soluble source of magnesium ion is selected from the group consisting of magnesium chloride, magnesium sulfate, magnesium acetate, and mixtures thereof. In other embodiments, the antiscalant aqueous solution comprises about 1 ppm to about 1000 ppm of the water soluble source of magnesium ion. In other embodiments, the antiscalant aqueous solution comprises about 50 ppm to about 150 ppm of the water soluble source of magnesium ion.
In some embodiments, the food processing equipment is selected from the group consisting of an evaporator, equipment used in an ultra high temperature pasteurization process, and equipment used in a high temperature short time pasteurization process. In other embodiments, the liquid food source is selected from the group consisting of milk, whey, whey permeate, juice, calcium fortified beverages, sugar, corn wetmilling steeping liquour, and mixtures thereof. In other embodiments, the liquid food source is a fuel ethanol process stream selected from the group consisting of corn, sugar, and mixtures thereof. In still yet other embodiments, the juice is a juice subjected to an evaporation process. In yet another embodiment, the juice is selected from the group consisting of tomato juice, and carrot juice.
In some embodiments, the magnesium ion is a food grade version. In other embodiments, the scale is selected from the group consisting of a calcium salt, a mixed calcium/magnesium salt wherein the calcium is the major component, and mixtures thereof. In still yet other embodiments, the calcium salt is selected from the group consisting of calcium phosphate, calcium oxalate, calcium silicate and mixtures thereof.
In some aspects, the present invention provides a method for removing scale on industrial food processing equipment used to process a liquid food source. The method comprises applying an antiscalant aqueous solution comprising a water soluble source of magnesium ion and at least one of an acidic detergent and an alkaline detergent, to the equipment, wherein the aqueous solution is applied as a clean in place process, such that the scale on the equipment is substantially removed.
In some embodiments, the antiscalant solution comprises about 1 ppm to about 1000 ppm of the water soluble source of magnesium ion. In some embodiments, the water soluble source of magnesium ion is selected from the group consisting of magnesium chloride, magnesium sulfate, and mixtures thereof.
In other embodiments, the antiscalant aqueous solution comprises about 0.25 wt % to about 10 wt % of the acidic detergent. In some embodiments, the acidic detergent comprises at least one of phosphoric acid, nitric acid, sulfuric acid, lactic acid, acetic acid, hydroxyacetic acid, glutamic acid, glutaric acid, and citric acid.
In still yet other embodiments, the antiscalant aqueous solution comprises about 0.5 wt % to about 3 wt % of an alkaline detergent. In some embodiments, the alkaline detergent comprises at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, triethanol amine, diethanol amine, monoethanol amine, sodium metasilicate, potassium metasilicate, sodium orthosilicate, potassium orthosilicate and combinations thereof.
In some aspects, the present invention provides a method for removing scale from a surface during a cleaning process. The method includes applying a composition comprising an acidic detergent and an antiscalant solution comprising a water soluble source of magnesium ion to the surface. The composition may increase the solubility of the scale present on the surface by at least about 5%.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic of an exemplary method for processing whey illustrating the multiple dosing points available using the methods of the present invention.
FIG. 2 is a graphical depiction of the amount of inhibition of calcium salt precipitation using an antiscalant aqueous composition of the present invention compared to a known antiscalant composition.
FIG. 3 is a graphical depiction of the inhibition of calcium oxalate precipitation using antiscalant aqueous compositions of the present invention including varying amounts of magnesium.
FIG. 4 is a graphical depiction of the actual concentration of magnesium ions in solution compared to the predicted concentration of magnesium ions in solution using antiscalant aqueous solutions of the present invention at varying levels of pH.
FIG. 5 is a graphical depiction of the concentration of calcium ions in solution versus the concentration of magnesium ions included in the antiscalant solution as described in Example 6.



DETAILED DESCRIPTION
In some aspects, the present invention relates to a method for preventing scale formation on industrial equipment. The method includes preventing the precipitation of and/or increasing the solubility of calcium salts during a high temperature liquid food processing operation or a cleaning process by applying an antiscalant aqueous solution including a water soluble source of magnesium ions to the industrial equipment. The addition of an effective amount of an antiscalant solution to a liquid food processing stream aids in the prevention of scale, e.g., insoluble calcium salt formation. An effective amount of an antiscalant solution may also be added to an acidic detergent to increase the solubility of calcium salts during a cleaning process. The antiscalant can be applied to the processing equipment in a variety of ways, including, but not limited to by direct injection into the liquid food source being processed, and/or by direct injection into the equipment processing lines.
In other aspects, the present invention relates to the removal of already developed scale, e.g., insoluble calcium salts, from industrial equipment by applying an aqueous antiscalant solution including a water soluble source of magnesium ions to the industrial equipment, for example, as part of a clean in place cleaning regimen. The antiscalant solution may be introduced by direct injection in the food processing lines.
By reducing or preventing the amount of scale formation, the flow rate of the liquid food processing stream can be increased, increasing the run-time of the equipment and the overall efficiency of the process.
So that the invention may be more readily understood certain terms are first defined.
The term “water soluble” as used herein refers to a compound that can be dissolved in water at a concentration of more than 1 wt %.
The term “water insoluble” as used herein refers to a compound that can be dissolved in water only to a concentration of less than 0.1 wt %.
As used herein, the terms “sparingly soluble” or “slightly water soluble” refer to a compound that can be dissolved in water only to a concentration of 0.1 to 1.0 wt %.
As used herein, the term “liquid food processing” refers to any process used to formulate, e.g., concentrate and/or evaporate, substantially liquid food product streams where it is desirable to reduce or prevent the formation of scale, e.g. insoluble calcium salts. Liquid food products that can be processed using the methods of the present invention include, but are not limited to, milk, whey, whey permeate, fruit and vegetable juices, calcium fortified beverages, sugar, com wetmilling steeping liquor, and fuel ethanol process streams from corn, sugar, or other biomass conversions. Exemplary processes involved in formulating these liquid food products include, but are not limited to, evaporation, filtration (e.g., reverse osmosis (RO) membranes and ultrafiltration (UF) membranes), and pasteurization (e.g., via high temperature short time (HTST) pasteurization processes, and ultra high temperature (UHT) pasteurization processes). The methods of the present invention are particularly beneficial in the high temperatures stages of the food processing operation.
As used herein, the term “scale” refers to an insoluble or sparingly soluble salt deposit, for example: an insoluble or sparingly soluble calcium salt deposit; an insoluble or sparingly soluble magnesium salt deposit; or a combination thereof.
As used herein, “weight percent,” “wt-%,” “percent by weight,” “% by weight,” and variations thereof refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, “percent,” “%,” and the like are intended to be synonymous with “weight percent,” “wt-%,” etc.
As used herein, the term “about” refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods; and the like. The term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term “about,” the claims include equivalents to the recited quantities.
It should be noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and, and “the” include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a composition containing “a compound” includes having two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
The methods of the present invention can be used generally in any application where scale, e.g., insoluble calcium salts, needs to be removed or in any application where the prevention of scale formation is beneficial. The system to which the antiscalant is added may contain metal ions, such as ions of calcium, barium, magnesium, aluminum, strontium, iron, etc. and anions such as bicarbonate, carbonate, oxalate, sulfate, phosphate, silicate, etc. The methods of the present invention are especially effective at preventing or removing scale including calcium salts, e.g., calcium phosphate, calcium oxalate, calcium carbonate, or calcium silicate, or a calcium/magnesium salt wherein calcium is the major component. The scale which is intended to be prevented or removed by the present invention may be formed by any combination of the above-noted ions. For example, the scale may involve a combination of calcium carbonate and calcium oxalate.
Exemplary industries in which the methods of the present invention can be applied include, but are not limited to: the food and beverage industry, e.g., the dairy, cheese, sugar, and brewery industries; oil processing industry; industrial agriculture and ethanol processing; and the pharmaceutical manufacturing industry.
In some aspects, the methods of the present invention apply to equipment, e.g., industrial equipment, generally cleaned using clean-in-place (i.e., CIP) cleaning procedures. Examples of such equipment include evaporators, heat exchangers (including tube-in-tube exchangers, direct steam injection, and plate-in-frame exchangers), heating coils (including steam, flame or heat transfer fluid heated) re-crystallizers, pan crystallizers, spray dryers, drum dryers, membranes and tanks. In some embodiments, the equipment treated does not include spray dryers.
Conventional CIP processing is generally well-known. The process includes applying a dilute solution (typically about 0.5-3%) onto the surface to be cleaned. The solution flows across the surface (e.g., 3 to 6 feet/second), slowly removing the soil. Either new solution is re-applied to the surface, or the same solution is recirculated and re-applied to the surface.
A typical CIP process to remove a soil (including organic, inorganic or a mixture of the two components) includes at least three steps: an alkaline solution wash, an acid solution wash, and then a fresh water rinse. The alkaline solution softens the soils and removes the organic alkaline soluble soils. The subsequent acid solution removes mineral soils left behind by the alkaline cleaning step. The strength of the alkaline and acid solutions and the duration of the cleaning steps are typically dependent on the durability of the soil. The water rinse removes any residual solution and soils, and cleans the surface prior to the equipment being returned on-line.
Antiscalant Solutions
In some aspects, the present invention relates to methods for reducing and/or preventing scale formation on industrial equipment including applying an aqueous antiscalant solution to the equipment. In some embodiments, the antiscalant solution includes a water soluble source of magnesium ions. The magnesium ion source can be an organic or inorganic magnesium ion source. Suitable water soluble magnesium ion sources include, but are not limited to, magnesium perborate, magnesium percarbonate, magnesium acetate, magnesium acetate tetrahydrate, magnesium acetylsalicylate, magnesium di-aluminate, magnesium benzoate, magnesium benzoate trihydrate, magnesium bromate, magnesium bromide hexahydrate, magnesium chloride, magnesium chloride hexahydrate, magnesium citrate, magnesium citrate pentahydrate, magnesium diphosphate, magnesium hydrogen phosphate, magnesium iodate, magnesium iodate tetrahydrate, magnesium iodide, magnesium iodide octahydrate, magnesium lactate, magnesium lactate trihydrate, magnesium molybdate, magnesium nitrate, magnesium nitrate hexahydrate, magnesium nitride, magnesium nitrite, magnesium peroxoborate, magnesium phosphate, magnesium phosphinate, magnesium salicylate, magnesium salicylate tetrahydrate, magnesium sulfate, magnesium sulfate heptahydrate, magnesium sulfite hexahydrate, magnesium tartrate pentahydrate, magnesium thiosulfate, magnesium thiosulfate hexahydrate, magnesium sulfite, and magnesium tartrate. In some embodiments, the magnesium ion source is selected from the group consisting of magnesium chloride, magnesium sulfate, magnesium acetate, and combinations and mixtures thereof.
The magnesium ion source is typically provided in solution. In some embodiments, the water soluble magnesium ion source is formulated on site. That is, in some embodiments, the water soluble magnesium ion source can be made at the point of use. For example, a solution of magnesium hydroxide can be combined on site with a solution of sulfuric acid. The resulting solution of magnesium sulfate can then be used as part of an antiscalant solution according to the methods of the present invention to prevent or remove scale formation. In other embodiments, the magnesium ion source is pre-formed, e.g., an antiscalant aqueous solution including the water soluble magnesium ion source, e.g., magnesium sulfate, is provided for on site use.
In some aspects, the present invention provides methods for removing and/or preventing scale formation on industrial food processing equipment used to process a liquid food source. The method includes applying an antiscalant aqueous solution having a water soluble magnesium ion source to the equipment. The antiscalant solution can be applied to the equipment in a variety of ways including, but not limited to, by direct injection into the liquid food source being processed prior to evaporation and/or by direct injection in the process lines of the equipment.
When application of the antiscalant solution occurs via direct injection into the liquid food source, the magnesium ion sources chosen should either be characterized by the United States Food and Drug Administration as direct or indirect food additives or as stable water solutions. Water soluble magnesium salts approved as generally recognized as safe (GRAS) for direct food contact include magnesium chloride, magnesium carbonate, magnesium sulfate, and magnesium phosphate.
In some embodiments, the antiscalant aqueous solution includes about 1 ppm to about 1000 ppm, about 25 ppm to about 400 ppm, about 50 ppm to about 150 ppm, or about 100 ppm of the water soluble magnesium ion source. It is to be understood that all values and ranges between these values and ranges are encompassed by the present invention.
The antiscalant solutions of the present invention can be used under various pH conditions. For example, the antiscalants of the present invention can be used at a pH from about 1 to 14, more preferably about 3 to 14, and most preferably about 4 to 14. The aqueous antiscalants of the present invention can also be used under acidic conditions against some forms of scale, e.g., oxalate scales. For example, in liquid food processing systems or equipment that develop oxalate scaling, the liquid food processing stream often has a pH less than about 8, such as about 2 to 8, even more usually about 3 to 7. In other embodiments, for example, the pH of a liquid food stream being processed can be about 2 to about 12, about 2 to about 7, or about 2.5 to about 5. The pH of the antiscalant solution may be, for example, about 2 to about 12, about 2 to about 7, or about 2.5 to about 5.
For carbonate scaling, the liquid food processing stream to which the antiscalant is added has a basic pH. In some embodiments, the pH is at least about 9, with ranges of between about 9 to about 14, about 10 to about 13, and about 10.2 to about 12. Thus, the pH of the antiscalant aqueous solution may be, e.g., about 9 to about 14, about 10 to about 13, and about 10.2 to about 12.
The antiscalant solution can be used with an acid or alkaline detergent, for example to remove scale that has already formed on industrial food processing equipment. When used with an alkaline detergent, e.g., a conventional CIP alkaline detergent, the antiscalant solution can be applied as a separate additive to the detergent, e.g., a CIP solution formulated on site, or it can be added to a detergent which has been previously formulated.
Exemplary acidic detergents include, but are not limited to, phosphoric acid, nitric acid, sulfuric acid, lactic acid, acetic acid, hydroxyacetic acid, glutamic acid, glutaric acid, citric acid, and mixtures thereof. Exemplary alkaline detergents suitable for use with the methods of the present invention include, but are not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide, triethanol amine, diethanol amine, monoethanol amine, sodium metasilicate, potassium metasilicate, sodium orthosilicate, potassium orthosilicate, and combinations thereof.
The antiscalant composition can include about 0.25 wt % to about 10 wt %, about 2 to about 5 wt %, or about 0.5 to about 1.5 wt % of a detergent. It is to be understood that all values and ranges between these values and ranges are encompassed by the present invention.
In some embodiments, an effective amount of antiscalant solution is applied to industrial food processing equipment such that the scale on the equipment is substantially removed. In some embodiments, at least about 10%, at least about 25%, or at least about 50% of scale deposition is removed. In some embodiments, about 90% of scale deposition is removed.
In some embodiments, an effective amount of antiscalant solution is applied to industrial food processing equipment such that formation of scale on the equipment is substantially prevented. In some embodiments, at least about 10%, at least about 25%, or at least about 50% of scale deposition is prevented. In some embodiments, about 90% of scale deposition is prevented.
The antiscalant solutions can be used to increase the solubility of scale, e.g., calcium salt scale, during a cleaning process, e.g., a CIP cleaning process. In some embodiments, the antiscalant solutions increase the solubility of scale by about 2%, about 5%, about 10%, about 15% or about 20%.
Additional Functional Ingredients
In some embodiments, the antiscalant solution further includes additional functional ingredients. The term “functional ingredients” refers to an active compound or material that affords desirable properties to the antiscalant solution. Examples of functional ingredients suitable for use with the present invention include, but are not limited to, chelating/sequestering agents, alkalinity sources, penetrants/surfactants, cleaning agents, softening agents, buffers, anti-corrosion agents, bleach activators secondary hardening agents or solubility modifiers, detergent fillers, defoamers, anti-redeposition agents, antimicrobials, rinse aid compositions, a threshold agent or system, aesthetic enhancing agents (i.e., dyes, perfumes), lubricant compositions, additional bleaching agents, functional salts, hardening agents, enzymes, or other such functional ingredients, and mixtures thereof.
The additional function ingredients may vary according to the type of composition being manufactured, and the intended end use. For example, if the antiscalant solution is added directly to the food stream being processed, the additional functional ingredient may be one that is generally recognized as safe for use as a food additive. If the antiscalant solution is used to remove already formed scale, then the additional functional ingredients may include, for example, organic surfactants or cleaning agents.
In some embodiments, the disclosed antiscalant solutions can be used with one or more known antiscalants, for example, phosphates, acrylates, aminocarboxylates, hydroxycarboxylates, phosphonates, sulfonates, and maleates. The amount of other antiscalant to be combined with the antiscalant solution of the present invention can depend upon the type and/or condition of the equipment to be treated as well as the chosen antiscalant. The weight ratio of the known antiscalant to the antiscalant of the present invention is preferably from about 1:100 to 100:1, more preferably about 1:30 to 30:1, and most preferably about 1:10 to 10:1. The additional known antiscalant may be applied to the equipment before, after, or at substantially the same time as the disclosed antiscalant solution.
Organic Surfactants or Cleaning Agents
In some embodiments, the antiscalant solution can further include at least one cleaning agent which can be a surfactant or surfactant system. A variety of surfactants can be used, including anionic, nonionic, cationic, and zwitterionic surfactants, which are commercially available from a number of sources. Suitable surfactants include nonionic surfactants, for example, low foaming non-ionic surfactants. For a discussion of surfactants, see Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume 8, pages 900-912.
Nonionic surfactants suitable for use in the antiscalant solutions of the present invention include, but are not limited to, those having a polyalkylene oxide polymer as a portion of the surfactant molecule. Exemplary nonionic surfactants include chlorine-, benzyl-, methyl-, ethyl-, propyl-, butyl- and other like alkyl-capped polyethylene and/or polypropylene glycol ethers of fatty alcohols; polyalkylene oxide free nonionics such as alkyl polyglycosides; sorbitan and sucrose esters and their ethoxylates; alkoxylated ethylene diamine; carboxylic acid esters such as glycerol esters, polyoxyethylene esters, ethoxylated and glycol esters of fatty acids, and the like; carboxylic amides such as diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amides, and the like; and ethoxylated amines and ether amines commercially available from Tomah Corporation and other like nonionic compounds. Silicone surfactants such as the ABIL B8852 (Goldschmidt) can also be used.
Additional exemplary nonionic surfactants having a polyalkylene oxide polymer portion include nonionic surfactants of C6-C24 alcohol ethoxylates (e.g., C6-C14 alcohol ethoxylates) having 1 to about 20 ethylene oxide groups (e.g., about 9 to about 20 ethylene oxide groups); C6-C24 alkylphenol ethoxylates (e.g., C8-C10 alkylphenol ethoxylates) having 1 to about 100 ethylene oxide groups (e.g., about 12 to about 20 ethylene oxide groups); C6-C24 alkylpolyglycosides (e.g., C6-C20 alkylpolyglycosides) having 1 to about 20 glycoside groups (e.g., about 9 to about 20 glycoside groups); C6-C24 fatty acid ester ethoxylates, propoxylates or glycerides; and C4-C24 mono or dialkanolamides.
Exemplary alcohol alkoxylates include, but are not limited to, alcohol ethoxylate propoxylates, alcohol propoxylates, alcohol propoxylate ethoxylate propoxylates, alcohol ethoxylate butoxylates, and the like; nonylphenol ethoxylate, polyoxyethylene glycol ethers and the like; and polyalkylene oxide block copolymers including an ethylene oxide/propylene oxide block copolymer such as those commercially available under the trademark PLURONIC (BASF-Wyandotte), and the like.
Examples of suitable low foaming nonionic surfactants also include secondary ethoxylates, such as those sold under the trade name TERGITOLTM, such as TERGITOLTM 15-S-7 (Union Carbide), Tergitol 15-S-3, Tergitol 15-S-9 and the like. Other suitable classes of low foaming nonionic surfactant include alkyl or benzyl-capped polyoxyalkylene derivatives and polyoxyethylene/polyoxypropylene copolymers.
An additional useful nonionic surfactant is nonylphenol having an average of 12 moles of ethylene oxide condensed thereon, it being end capped with a hydrophobic portion including an average of 30 moles of propylene oxide. Silicon-containing defoamers are also well-known and can be employed in the compositions and methods of the present invention.
Suitable amphoteric surfactants include amine oxide compounds having the formula:




where R, R′, R′′, and R′′′ are each a C1-C24 alkyl, aryl or aralkyl group that can optionally contain one or more P, O, S or N heteroatoms.
Another class of suitable amphoteric surfactants includes betaine compounds having the formula:




where R, R′, R′′ and R′′′ are each a C1-C24 alkyl, aryl or aralkyl group that can optionally contain one or more P, O, S or N heteroatoms, and n is about 1 to about 10.

Suitable surfactants may also include food grade surfactants, linear alkylbenzene sulfonic acids and their salts, and ethylene oxide/propylene oxide derivatives sold under the PluronicTM trade name. Suitable surfactants include those that are compatible as an indirect or direct food additive or substance; especially those described in the Code of Federal Regulations (CFR), Title 21-Food and Drugs, parts 170 to 186.
Anionic surfactants suitable for use with the disclosed antiscalant solutions may also include, for example, carboxylates such as alkylcarboxylates (carboxylic acid salts) and polyalkoxycarboxylates, alcohol ethoxylate carboxylates, nonylphenol ethoxylate carboxylates, and the like; sulfonates such as alkylsulfonates, alkylbenzenesulfonates, alkylarylsulfonates, sulfonated fatty acid esters, and the like; sulfates such as sulfated alcohols, sulfated alcohol ethoxylates, sulfated alkylphenols, alkylsulfates, sulfosuccinates, alkylether sulfates, and the like; and phosphate esters such as alkylphosphate esters, and the like. Exemplary anionics include, but are not limited to, sodium alkylarylsulfonate, alpha-olefin sulfonate, and fatty alcohol sulfates. Examples of suitable anionic surfactants include sodium dodecylbenzene sulfonic acid, potassium laureth-7 sulfate, and sodium tetradecenyl sulfonate.
The surfactant can be present at amounts of about 0.01 to about 20 wt-%, about 0.1 to about 10 wt-%, or about 0.2 to about 5 wt-%. It is to be understood that all ranges and values within these ranges and values are to be encompassed by the present invention.
Oxidizing Agent
The antiscalant solutions can further include an oxidizing agent or an oxidizer, such as a peroxide or peroxyacid. Exemplary oxidizing agents are oxidants such as: peroxygen compounds, e.g., peroxides; peracids, e.g., percarboxylic acids; and perborates. Additional exemplary oxidizing agents include, but are not limited to, chlorites, bromine, bromates, bromine monochloride, iodine, iodine monochloride, iodates, permanganates, nitrates, nitric acid, borates, perborates, and gaseous oxidants such as ozone, oxygen, chlorine dioxide, chlorine, sulfur dioxide and derivatives thereof. Peroxygen compounds, which include peroxides and various percarboxylic acids, including percarbonates, are suitable.
Peroxycarboxylic (or percarboxylic) acids generally have the formula R(CO3H)n, where, for example, R is an alkyl, arylalkyl, cycloalkyl, aromatic, or heterocyclic group, and n is one, two, or three, and named by prefixing the parent acid with peroxy. The R group can be saturated or unsaturated as well as substituted or unsubstituted. Medium chain peroxycarboxylic (or percarboxylic) acids can have the formula R(CO3H)n, where R is a C5-C11 alkyl group, a C5-C11 cycloalkyl, a C5-C11 arylalkyl group, C5-C11 aryl group, or a C5-C11 heterocyclic group; and n is one, two, or three. Short chain fatty acids can have the formula R(CO3H)n where R is C1-C4 and n is one, two, or three.
Exemplary peroxycarboxylic acids include peroxypentanoic, peroxyhexanoic, peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxyisononanoic, peroxydecanoic, peroxyundecanoic, peroxydodecanoic, peroxyascorbic, peroxyadipic, peroxycitric, peroxypimelic, or peroxysuberic acid, mixtures thereof, or the like.
Branched chain peroxycarboxylic acids include, for example, peroxyisopentanoic, peroxyisononanoic, peroxyisohexanoic, peroxyisoheptanoic, peroxyisooctanoic, peroxyisonananoic, peroxyisodecanoic, peroxyisoundecanoic, peroxyisododecanoic, peroxyneopentanoic, peroxyneohexanoic, peroxyneoheptanoic, peroxyneooctanoic, peroxyneononanoic, peroxyneodecanoic, peroxyneoundecanoic, peroxyneododecanoic, mixtures thereof, or the like.
Exemplary peroxygen compounds include hydrogen peroxide (H2O2), peracetic acid, peroctanoic acid, persulphates, perborates, or percarbonates.
The amount of oxidant in the antiscalant solution, if present, may be, for example, at least 0.01 wt-% and no greater than about 1 wt-%. Acceptable levels of oxidant are about 0.01 to about 0.50 wt-%; about 0.3 wt-% is a particularly suitable level.
Builders
The antiscalant solution may further include a builder. Builders include chelating agents (chelators), sequestering agents (sequestrants), detergent builders, and the like. The builder may stabilize the antiscalant solution. Examples of builders include, but are not limited to, phosphonates, phosphates, aminocarboxylates and their derivatives, pyrophosphates, polyphosphates, ethylenediamene and ethylenetriamene derivatives, hydroxyacids, and mono-, di-, and tri-carboxylates and their corresponding acids. Other exemplary builders include aluminosilicates, nitroloacetates and their derivatives, and mixtures thereof. Still other exemplary builders include aminocarboxylates, including salts of ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetetraacetic acid (HEDTA), and diethylenetriaminepentaacetic acid. Preferred builders are water soluble.
Particularly preferred builders include EDTA (including tetra sodium EDTA), TKPP (tetrapotassium pyrophosphate), PAA (polyacrylic acid) and its salts, phosphonobutane carboxylic acid, and sodium gluconate.
The amount of builder in the antiscalant solution, if present, may for example be at least about 0.25 wt-% and no greater than about 5 wt-%. Acceptable levels of builder include about 0.5 to about 1.0 wt-% and about 1 wt-% to about 2.5 wt-%.
Methods of Use
In some aspects, the methods of the present invention are used to remove scale, e.g., calcium salt scale, or prevent scale formation on equipment used to process liquid food products. Exemplary liquid food products that can be treated using the methods of the present invention include, but are not limited to, milk, whey, whey permeate, juice, calcium fortified beverages, sugar, corn wetmilling steeping liquor, and mixtures thereof. In some embodiments, the methods of the present invention are used to remove scale or prevent scale formation on or in equipment used to process a liquid food source that is a fuel ethanol process stream selected from the group consisting of corn, sugar, and mixtures thereof. In other embodiments, the methods of the present invention remove or prevent scale formation on equipment used to evaporate or concentrate juice, e.g., tomato, carrot and sugar juice.
The antiscalant solution may be used to increase the solubility of scale, e.g., insoluble or sparingly soluble calcium salts, in an acidic or alkaline environment. For example, the antiscalant solutions may be added to an acid or alkaline detergent used to clean an article. Exemplary articles that can be cleaned, with the disclosed antiscalant solution and a detergent include, but are not limited to motor vehicle exteriors, textiles, food contacting articles, clean-in-place (CIP) equipment, health care surfaces and hard surfaces.
Exemplary motor vehicle exteriors include cars, trucks, trailers, buses, etc. that are commonly washed in commercial vehicle washing facilities. Exemplary textiles include, but are not limited to, those textiles that generally are considered within the term “laundry” and include clothes, towels, sheets, etc. In addition, textiles include curtains. Exemplary food contacting articles include, but are not limited to, dishes, glasses, eating utensils, bowls, cooking articles, food storage articles, etc. Exemplary CIP equipment includes, but is not limited to, pipes, tanks, heat exchangers, valves, distribution circuits, pumps, etc. Exemplary health care surfaces include, but are not limited to, surfaces of medical or dental devices or instruments. Exemplary hard surfaces include, but are not limited to, floors, counters, glass, walls, etc. Hard surfaces can also include the inside of dish machines, and laundry machines. In general, hard surfaces can include those surfaces commonly referred to in the cleaning industry as environmental surfaces. Such hard surfaces can be made from a variety of materials including, for example, ceramic, metal, glass, wood or hard plastic.
The antiscalant solution of the present invention can be applied to the equipment in a variety of ways. For example, when used to prevent scale formation, the antiscalant can be applied to the equipment by direct injection into the liquid food stream being processed, by application onto and/or into the equipment process lines, or process water, before or after a food stream has been processed, and/or by supplying the antiscalant solution to the balance tank. When used to remove scale already formed on equipment the antiscalant solution can be applied to the surface of the equipment by a variety of methods. For example, the antiscalant solution can be applied by direct injection onto and/or into the process lines of the equipment.
The application of the antiscalant solution can include any form of application suitable for applying the antiscalant solution to the surface of the equipment to be treated. For example, the antiscalant solution can be poured, sprayed, or injected onto or into the equipment to be treated. The application of the antiscalant solution can be followed by a rinse, e.g., a water rinse, by a conventional cleaning process, e.g., a conventional clean in place process, or by the introduction of a liquid food stream to be processed by the equipment, or any combination thereof.
Unlike certain conventional liquid food processing additives, e.g., WPA 1000, which can only be added to the food stream or process lines after the food product has been filtered, the antiscalant solutions of the present invention can be applied to the liquid food source or the process lines at multiple stages in the process. That is, the antiscalant solutions of the present invention can be added to the food processing system at multiple entry points, and at multiple times.
FIG. 1 is a flow chart depicting exemplary multiple dosing points available when using the methods of the present invention in, for example, a whey processing system. For example, as shown in FIG. 1, an antiscalant solution of the present invention can be added before, after, or both before and after the filtration step.
In some aspects, the present invention provides methods for removing scale already formed on industrial food processing equipment used to process a liquid food source. The method includes applying an antiscalant solution having a soluble magnesium ion and at least one of an acidic detergent and an alkaline detergent, to the equipment. The amount of soluble magnesium ion applied to the equipment is dependent upon a variety of factors, including, but not limited to, temperature, the pH, and the equipment being treated. For example, higher temperatures may require higher amounts of the soluble magnesium ion source.
In some embodiments, the equipment to which the antiscalant solution is added may be at an elevated temperature. For instance, the temperature of the equipment may be about 25° C. to about 95° C., about 70° C. to about 95° C., or about 80° C. to about 95° C. When the antiscalant solution is added to equipment used in a pasteurization process, the temperature of the equipment is usually about 20° C. to about 120° C. When the antiscalant is added equipment used to process whey or whey permeate, the temperature of the equipment is usually about 50° C. to about 85° C. The antiscalant may also be added to an acidic detergent and used at room temperature.
EXAMPLES
The present invention is more particularly described in the following examples that are intended as illustrations only, since numerous modifications and variations within the scope of the present invention will be apparent to those skilled in the art. Unless otherwise noted, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples were obtained, or are available, from the chemical suppliers described below, or may be synthesized by conventional techniques.
In particular, the experiments of Examples 1, 2, 3, 4, and 5 were directed toward determining the effect of magnesium ions on preventing the precipitation of calcium salts and the experiment of Example 6 was directed towards determining the effect of magnesium ions on the solubility of calcium salts.
Examples 1 and 2
Calcium Phosphate Inhibition Test
Example 1 was a “cook-down” experiment designed to represent the concentrate of whey in an evaporator. Whey permeate samples from a cheese plant were collected and tested for calcium and phosphate content. Each of the whey permeate samples were placed in a separate beaker and placed in a hot water bath having a temperature of between about 190° F. and about 200° F. for several hours to evaporate most of the water from the samples. The remaining whey permeate concentrate was rinsed out of the beaker.
A plurality of antiscalant solutions were prepared that included a calcium salt inhibitor. Compositions 1, 2, 3, 4, 5, 6, 7, and 8 included a water soluble source of magnesium ions, i.e., MgCl2.6H2O, as the calcium salt inhibitor. Comparative Compositions A, B, C, D, E, F, G, and H included WPA, a known calcium salt inhibitor. Composition 1 and Comparative Composition A included about 100 ppm of calcium salt inhibitor, Composition 2 and Comparative Composition B included about 200 ppm of calcium salt inhibitor, Composition 3 and Comparative Composition C included about 300 ppm of calcium salt inhibitor, Composition 4 and Comparative Composition D included about 400 ppm of calcium salt inhibitor, Composition 5 and Comparative Composition E included about 600 ppm of calcium salt inhibitor, Composition 6 and Comparative Composition F included about 800 ppm of calcium salt inhibitor, Composition 7 and Comparative Composition G included about 1000 ppm of calcium salt inhibitor, and Composition 8 and Comparative Composition H included about 1200 ppm of calcium salt inhibitor.
The beakers were rinsed with each of the above compositions to remove any residual film. The compositions were then submitted for analysis by an analytical tool, Inductively Coupled Plasma (ICP), to measure the concentration of metal salts in solution for calcium. The concentrations of calcium salt inhibitor compositions and the resulting concentrations of calcium ions are shown in Table 1. These results are also graphically depicted in FIG. 2.











TABLE 1





Calcium

Ca++

Ca++ from


Salt Inhibitor

from Scale

Scale


(ppm)
Composition
(ppm)
Composition
(ppm)



















0
Control
9.61
Control
9.61


100
Composition 1
15.7
Composition A
29


200
Composition 2
20.5
Composition B
64.8


300
Composition 3
18.2
Composition C
68


400
Composition 4
17.8
Composition D
58


600
Composition 5
15.2
Composition E
30


800
Composition 6
11.7
Composition F
12.8


1000
Composition 7
11.1
Composition G
18.4


1200
Composition 8
7.89
Composition H
17.5









As can be seen from the data in Table 1, and FIG. 2, the compositions (Compositions 1-8) which contained magnesium ions resulted in less calcium than the compositions (Comparative Compositions A-H) which contained a known calcium salt inhibitor. Generally, as the level of magnesium ions in the compositions increased, less calcium precipitated out of solution. This indicates that less calcium phosphate deposited onto the walls of the beakers because it is assumed that the less calcium ions in the extraction solution, the less calcium phosphate in solution.
Example 2 was designed to determine whether the magnesium ions were simply replacing the calcium ions and to form magnesium phosphate or whether there was actual inhibition of salt formation.
Antiscalant compositions 9, 10, 11, and 12 included a water soluble source of magnesium ions as the calcium salt inhibitor. To prepare a composition having about 250 ppm of magnesium ions, about 0.1673 grams of MgCl2.6H2O was added to about 80 ml of deionized water; to prepare a composition having about 500 ppm of magnesium ions, about 0.3346 grams of MgCl2.6H2O was added to about 80 ml of deionized water; to prepare a composition having about 600 ppm of magnesium ions, about 0.5019 grams of MgCl2.6H2O was added to about 80 ml of deionized water; and to prepare a composition having about 800 ppm of magnesium ions, about 0.6692 grams of MgCl2.6H2O was added to about 80 ml of deionized water.
Comparative Compositions I, J, K, and L included WPA, a known calcium salt inhibitor. To prepare a composition having about 100 ppm of magnesium ions, about 0.25 grams of a 10% solution of 40% WPA was added to about 80 ml of deionized water; to prepare a composition having about 200 ppm of magnesium ions, about 0.5 grams of a 10% solution of 40% WPA was added to about 80 ml of deionized water; to prepare a composition having about 300 ppm of magnesium ions, about 0.75 grams of a 10% solution of 40% WPA was added to about 80 ml of deionized water; and to prepare a composition having about 400 ppm of magnesium ions, about 1 gram of a 10% solution of 40% WPA was added to about 80 ml of deionized water.
The same procedure was followed as in Example 1, except that the level of magnesium ions in the final compositions was also analyzed and recorded. Table 2 shows the concentrations of the calcium salt inhibitor in the compositions and the resulting concentrations of calcium ions and magnesium ions.












TABLE 2








Calcium

Mg++




Salt

from




Inhibitor
Ca++ from
scale



Composition
(ppm)
Scale (ppm)
(ppm)





















Control
0
21.7
0.912



Composition 9
200
15.4
1.13



Composition 10
400
19.7
2.78



Composition 11
600
12
1.81



Composition 12
800
9.06
1.74



Composition I
100
82.5
2.19



Composition J
200
69.2
1.87



Composition K
300
37.4
1.18



Composition L
400
18.1
1.23










As can be seen from Table 2, the antiscalant solutions (Compositions 9-12) which contained magnesium ions again produced substantially less calcium than the compositions (Compositions I-L) which contained a known calcium salt inhibitor. Generally, as the level of magnesium ions in solution increased, the level of calcium ions in solution also increased, indicating that less calcium phosphate deposited onto the walls of the beakers.
In addition, the presence of magnesium ions in the final composition indicates that there is not a replacement of calcium ions with magnesium ions with the phosphate, but that there is actual inhibition of calcium salt precipitation. The levels of magnesium ions also illustrate that there was less overall deposition of soil, not just deposition of magnesium phosphate instead of calcium phosphate.
Examples 3 and 4
Calcium Oxalate Inhibition Test
Stock solutions of a 0.1 molar ammonium oxalate solution and a 0.1 molar calcium chloride solution were first prepared. The ammonium oxalate solution was prepared by mixing about 14.21 grams of ammonium oxalate with deionized water to a final volume of one liter. The calcium chloride solution was prepared by mixing about 14.23 grams of calcium chloride with deionized water to a final volume of about one liter. The solutions were stirred for about 30 minutes.
The stock magnesium chloride solution was prepared by first adding about 10.456 grams of MgCl2.6H2O to a one liter flask. Deionized water was then added such that there was a total of about 1000 grams of 1250 ppm stock magnesium solution. The 1250 ppm stock magnesium solution was stirred for about 30 minutes. Various mixtures were then prepared from the 1250 ppm magnesium ion composition. To prepare an antiscalant solution having 100 ppm magnesium ion (Composition 13), about 180 milliliters (ml) of deionized water was added to about 20 ml of the 1250 ppm stock magnesium solution; to prepare an antiscalant solution having about 200 ppm magnesium ion (Composition 14), about 160 milliliters of deionized water was added to about 40 ml of the 1250 ppm stock magnesium solution; to prepare an antiscalant solution having about 400 ppm magnesium ion (Composition 15), about 120 milliliters of deionized water was added to about 80 ml of the 1250 ppm stock magnesium solution; to prepare an antiscalant solution having about 800 ppm magnesium ion (Composition 16), about 40 milliliters of deionized water was added to about 160 ml of the 1250 ppm stock magnesium solution; and to prepare an antiscalant solution having about 1000 ppm magnesium ion composition (Composition 18), no deionized water was added about 200 ml of the 1250 ppm stock magnesium solution. About 80 ml of each of the above antiscalant solutions were added to 6 beakers.
About 10 ml of each of the ammonium oxalate and calcium chloride stock solutions were then pre-measured and added to each of Compositions 13-17 while simultaneously being stirred. Compositions 13-17 were stirred for about 2 minutes and allowed to sit for about 20 minutes in order to allow the precipitate to settle. A syringe was then used to pull off about 50 ml samples of each of Compositions 13-17. The samples were filtered through a 0.45 micron filter and submitted for analysis by ICP to measure the amount of calcium in solution.
The concentrations of magnesium ions in the antiscalant solutions and the resulting concentrations of calcium ions are shown in Table 3. These results are also graphically depicted in FIG. 3. It was assumed that the presence of calcium ions in solution were evidence of oxalate ions in solution as well.











TABLE 3








Magnesium Ion




Composition
Concentration (ppm)
Ca++ (ppm)




















Control
0
3.61



Composition 13
100
10



Composition 14
200
16.1



Composition 15
400
22.3



Composition 16
800
36.8



Composition 17
1000
41.9










As can be seen from the data in Table 3, as the level of magnesium ions in solution increased, the level of calcium ions in solution also increased. The higher concentration of calcium ions in solution indicates that there was an increase in the concentration of calcium ions and oxalate ions remaining in the solution that did not precipitate into solution. The higher the level of calcium ions, the less calcium oxalate in solution. Thus, the level of calcium oxalate that precipitated into solution decreased with the addition of magnesium ions.
In Example 4, additional tests were performed to determine whether the pH of the antiscalant solutions including a magnesium ion source affected the ability of the magnesium ions to inhibit the formation of calcium salts. A first set of antiscalant compositions (Compositions 18-22) was prepared using deionized water such that the resulting composition had a substantially neutral pH, a second set of antiscalant compositions (Compositions 23-27) was prepared using sulfuric acid such that the resulting compositions had a pH of about 3.6, and a third set of antiscalant compositions (Compositions 28-32) was prepared using sodium hydroxide such that the resulting compositions had a pH of about 9.5.
In addition, the concentrations of magnesium ions expected to be present in the resulting compositions were also determined. The expected concentration of magnesium ions is based on the solubility constant of the composition in water. For example, at about 20° C., magnesium oxalate has a solubility of 0.138 g/100 ml with a predicted total ppm of 1380 and a predicted metal ion ppm of 261. This general concept was used to determine the predicted level of magnesium ions in solution. Table 4 illustrates the concentration of the magnesium ion in the antiscalant solutions compositions, the pHs of the compositions before addition of the solutions including a magnesium ion source, the resulting concentrations of calcium ions, and the actual and predicted concentrations of magnesium ions.












TABLE 4






Initial







Magnesium Ion


Actual Mg++
Predicted Mg++


Composition
Present (ppm)
pH
Ca++ (ppm)
(ppm)
(ppm)




















Control
0
8.1
1.6
0
0


Composition 18
100
7.31
4.85
84
94


Composition 19
200
6.95
8.28
185
187


Composition 20
400
6.54
16
374
375


Composition 21
800
6.19
25.3
757
750


Composition 22
1000
5.98
30.6
940
937


Control
0
3.6
1.97
0
0


Composition 23
100
3.6
6.32
79.8
94


Composition 24
200
3.6
7.76
168
187


Composition 25
400
3.6
14.8
343
375


Composition 26
800
3.6
25.6
667
750


Composition 27
1000
3.6
29.4
856
937


Control
0
9.5
1.34
0
0


Composition 28
100
9.5
4.53
78.2
94


Composition 29
200
9.5
6.69
172
187


Composition 30
400
9.5
51.6
343
375


Composition 31
800
9.5
21.8
681
750


Composition 32
1000
9.5
26.6
878
937









The results in Table 4 indicate that magnesium ions are effective at controlling the precipitation of calcium salts over a wide range of pH values. Calcium oxalate is known to have very low solubility in water. For example, at about 20° C., calcium oxalate has a solubility of 0.000653 g/100 ml with a predicted total ppm of 6.53 and a predicted metal ion ppm of 2.04. This general concept was used to determine the predicted level of calcium ions in solution. The controls (no magnesium ions) matched the predicted levels of calcium ions in solution based on the solubility constant. Regardless of the pH, as the level of magnesium ions increased, more calcium ions were measured in the solutions. This indicates the calcium salt precipitation inhibition properties and/or increased solubility properties of magnesium ions.
As can also be seen in Table 4, the actual levels of magnesium ions in solution were also comparable to the predicted levels of magnesium ions in solution. This is also graphically depicted in FIG. 4. This indicates that the magnesium ions were not replacing the calcium ions to precipitate out magnesium
Example 5
Calcium Carbonate Inhibition Test
Stock solutions of a 0.1 molar sodium carbonate solution and a 0.1 molar calcium chloride solution were first prepared. The sodium carbonate solution was prepared by mixing about 10.6 grams of sodium carbonate with deionized water to a final volume of one liter. The calcium chloride solution was prepared by mixing about 14.23 grams of calcium chloride with deionized water to a final volume of about one liter. The solutions were stirred for about 30 minutes.
The stock magnesium chloride solution was prepared by first adding about 10.456 grams of MgCl2.6H2O to a one liter flask. Deionized water was then added such that there was a total of about 1000 grams of a 1250 ppm stock magnesium solution. The 1250 ppm stock magnesium solution was stirred for about 30 minutes. Various antiscalant solutions were then prepared from the 1250 ppm stock magnesium solution. To prepare an antiscalant composition including about 100 ppm magnesium ion (Composition 33), about 270 milliliters (ml) of deionized water was added to about 30 ml of the 1250 ppm stock magnesium solution; to prepare an antiscalant composition including about 200 ppm magnesium ion (Composition 34), about 240 milliliters of deionized water was added to about 60 ml of the 1250 ppm stock magnesium solution; to prepare an antiscalant composition including about 400 ppm magnesium ion (Composition 35), about 180 milliliters of deionized water was added to about 120 ml of the 1250 ppm stock magnesium solution; to prepare an antiscalant composition including about 800 ppm magnesium ion (Composition 36), about 60 milliliters of deionized water was added to about 240 ml of the 1250 ppm stock magnesium solution; and to prepare an antiscalant composition including about 1000 ppm magnesium ion (Composition 37), no deionized water was added about 300 ml of the 1250 ppm stock magnesium solution. About 80 ml of each of the above magnesium ion compositions were added to 6 beakers.
About 10 ml of each of the ammonium oxalate and calcium chloride stock solutions were then pre-measured and added to each of the antiscalant compositions while simultaneously stirring. The compositions were stirred for about 2 minutes and allowed to sit for about 20 minutes in order to allow the precipitate to settle. A syringe was then used to pull off 50 ml samples of the compositions. The samples were then filtered through a 0.45 micron filter and submitted for analysis by ICP for calcium and magnesium in the compositions.
In addition to measuring the concentration of calcium ions present in the resulting composition, the pH levels of the antiscalant compositions before and after the addition of the calcium chloride solution and sodium carbonate solution were also measured. An increase in pH indicates an increase of carbonate ions in solution. As the level of carbonate ions in solution increases, it is assumed that the level of calcium ions in solution also increases.
The initial concentration of magnesium ions in the antiscalant compositions, the resulting concentration of calcium ions and magnesium ions, the mole ratio of calcium ions to magnesium ions deficit, the initial pH of the composition, the final pH of the composition, and any observations are shown in Table 5. These results are also graphically depicted in FIG. 5.














TABLE 5






Calcium Salt


Mole ratio of






Inhibitor
Ca++
Mg++
Ca++ to Mg++
pH
pH


Composition
(ppm)
(ppm)
(ppm)
deficit
Start
Final
Observations






















Control
0
18.8
0
N/A
8.1
9.09
Precipitate stuck to









bottom of beaker









most


Composition 33
100
44.6
76.5
1.14
7.3
9.1
Precipitate stuck to









bottom of beaker









mid


Composition 34
200
53.8
170
1.08
6.95
9.38
Precipitate stuck to









bottom of beaker









slight


Composition 35
400
81.5
347
0.92
6.54
10.06
Loose precipitate


Composition 36
800
238
734
2.57
6.19
9.96
Loose precipitate


Composition 37
1000
314
918
2.30
5.98
10
Loose precipitate









As can be seen from the data in Table 5, there is a relationship between the concentration of magnesium ions in the antiscalant composition and the amount of calcium carbonate precipitation. In particular, as the level of magnesium ions in solution increased, the level of calcium ions in solution also increased. This indicates that higher levels of magnesium ions resulted in less precipitation of calcium carbonate. Thus, the level of calcium carbonate precipitated from solution decreased with the addition of magnesium ions.
The pH levels of the initial and final compositions provide further evidence that carbonate ions were present in the final compositions and that the amount of carbonate ions present in the final compositions increased as the level of magnesium ions in solution increased. The pH of the compositions generally increased by a greater percentage as the amount of magnesium ions in the initial antiscalant composition increased. This indicates that the amount of carbonate ions, and thus calcium ions, in solution increased with increasing levels of magnesium ions. As the concentrations of calcium ions and carbonate ions in solution increase, the amount of calcium ions and carbonate ions available to form a salt and precipitate from solution decreases. Thus, less calcium carbonate precipitated in solution with increased levels of magnesium ions.
As also shown in the last column of Table 5, at higher levels of magnesium ions, there was less calcium carbonate that precipitated from solution. In particular, at a concentration of about 400 ppm, the compositions resulted in a loose precipitate that did not stick to the bottom of the beaker. At concentrations of less than about 400 ppm, the compositions had varying levels of calcium carbonate precipitate stuck to the bottom of the beaker.
Example 6
Calcium Oxalate Solubility Test
Stock solutions of a 0.1 molar ammonium oxalate solution and a 0.1 molar calcium chloride solution were first prepared. The ammonium oxalate solution was prepared by mixing about 14.21 grams of ammonium oxalate with deionized water to a final volume of one liter. The calcium chloride solution was prepared by mixing about 14.23 grams of calcium chloride with deionized water to a final volume of about one liter. The solutions were stirred for about 30 minutes and covered. About 250 ml of each solution was poured into a beaker and stirred for about 10 minutes. The solutions were then allowed to sit to allow any precipitate to settle. The liquid was decanted and the precipitate was filtered and washed with deionized water. The precipitate was then filtered and dried overnight in an oven at about 85° C.
To prepare an antiscalant composition including about 250 ppm of magnesium ions (Composition 38), about 0.1673 grams of MgCl2.6H2O was added to about 80 ml of deionized water; to prepare an antiscalant composition including about 500 ppm of magnesium ions (Composition 39), about 0.3346 grams of MgCl2.6H2O was added to about 80 ml of deionized water; and to prepare an antiscalant composition including about 1000 ppm of magnesium ions (Composition 40), about 0.6692 grams of MgCl2.6H2O was added to about 80 ml of deionized water.
About 0.1 grams of dry calcium oxalate were added to each composition and stirred for 20 minutes at room temperature. The mixtures were then allowed to settle for 10 minutes. A syringe was then used to pull off 50 ml samples of the compositions. The samples were then filtered through a 0.45 micron filter and submitted for analysis by ICP for calcium and magnesium in the compositions.
The concentrations of magnesium ion in the initial antiscalant compositions, the resulting concentrations of calcium ions and magnesium ions, the magnesium ion deficit, and the mole ratio of calcium ions to magnesium ions deficit are shown in Table 6. The amount of calcium (ppm) in solution versus the concentration of magnesium added (ppm) is also graphically depicted in FIG. 6. It was assumed that the presence of calcium ions in solution were evidence of oxalate ions in solution as well.











TABLE 6









Mole



Mg++
Ca++
Mg++ deficit
ratio of Ca++


Composition
(ppm)
(ppm)
(ppm)
to Mg++ deficit



















Control
0
2.15
0
0


Composition 19
236
10.3
14
2.24


Composition 20
477
14.6
23
2.59


Composition 21
946
21.9
54
4.06









As shown in Table 6, the solubility of calcium oxalate increases as the level of magnesium ions in solution increases. The concentration of calcium ions in solution indicates that at least some of the calcium oxalate that was present in solution dissolved into calcium ions and oxalate ions. The higher the level of calcium ions, the lower the amount of precipitated calcium oxalate from solution. The fact that the concentration of calcium ions increased as the concentration of magnesium ions increased showed that the presence of magnesium ions contributed to the solubility of calcium oxalate.
Example 7
Evaluation of Calcium Carbonate Scale Inhibition Using Mg++
A laboratory scale stainless steel heat exchange coil will be used to simulate heat exchange surfaces in dairy processing equipment. Whey UF permeate from a cheese production plant will be circulated through the inside of a stainless steel coiled tube. Steam heat will be applied to the outside of the coil so that the temperature of the outgoing whey permeate is about 40-50 degrees Fahrenheit higher than the incoming whey permeate. The heated solution will be discharged into a sump with a cooling jacket. The intake for the pump shall be in this sump.
The solution will be circulated for 4-6 hours, and rinsed by pumping 1 gallon of deionized water through the coil. The solution will then be drained.
The coil will be cleaned with 2 liters of 10% Nitric Acid solution for 1 hour. The Calcium, Magnesium and Phosphorus content of the acid solution before and after cleaning will be analyzed. This will give the quantity of scale deposited into the coil.
Multiple runs of this experiment with and without Magnesium salts added to the solution will be performed. The amount scale deposited in treated and non-treated runs will be compared.
Example 8
Solubility of Slightly Soluble Calcium Salts Under Clean in Place Cleaning Conditions
A study was carried out to determine the effect on the solubility of calcium oxalate when a water soluble magnesium ion source was added to a solution including calcium oxalate under Clean In Place (CIP) conditions. Eight solutions were prepared. Four of the solutions included 2% NaOH to stimulate cleaning under alkaline conditions, and four of the solutions included a 2% solution of an acidic cleaner that included 11.8% phosphoric acid, and 43.5% nitric acid, to stimulate cleaning under acidic conditions. To each of these eight solutions varying amounts of MgCl2.6H2O was added. The eight solutions prepared, and the pH of each before and after the experiment, are shown in the table below.











TABLE 7







Sample
pH Start
pH final




















Acidic cleaner and no Mg2+
1.35
1.34



(control)



Acidic cleaner and 200 ppm
1.28
1.26



Mg2+



Acidic cleaner and 400 ppm
1.22
1.19



Mg2+



Acidic cleaner and 800 ppm
1.18
1.19



Mg2+



2% NaOH and no Mg2+
13.43
13.34



(control)



2% NaOH and 200 ppm
13.41
13.35



Mg2+



2% NaOH and 400 ppm
13.4
13.36



Mg2+



2% NaOH and 800 ppm
13.4
13.32



Mg2+










Calcium oxalate (0.1 grams) was added to each of the eight solutions. The solutions were stirred for 20 minutes at room temperature. The solutions were allowed to settle for 10 minutes, and then filtered with 0.45 micron filter into a sampling tube. The samples were then tested for Mg2+ and Ca2+ levels using ICP analysis. The table below shows the results of this analysis.











TABLE 8







Sample
Ca2+ (ppm)
Mg2+ (ppm)




















Acidic cleaner and no Mg2+
178
0



(control)



Acidic cleaner and 200 ppm
178
189



Mg2+



Acidic cleaner and 400 ppm
186
376



Mg2+



Acidic cleaner and 800 ppm
188
746



Mg2+



2% NaOH and no Mg2+
15.4
0



(control)



2% NaOH and 200 ppm
15.2
0



Mg2+



2% NaOH and 400 ppm
18.9
0



Mg2+



2% NaOH and 800 ppm
14.6
0



Mg2+










As can be seen from this table, an increase in the amount of Mg2+ present in solution resulted in an increase in the amount of calcium ions in solution. This indicates that higher levels of magnesium ions resulted in less precipitation of calcium oxalate, i.e., an increase in the solubility of calcium oxalate.
A similar experiment was also carried out at elevated temperatures. 1.15 grams of calcium oxalate was added to varying amounts of DI water. The mixtures were heated to 66° C. on a hot plate with watch glasses on top. The solutions were stirred at 300 rpms. Varying amounts of a 10% MgCl2 solution were added to each of the four solutions, to provide Mg2+ ions at varying levels (10 ppm, 50 ppm, 100 ppm, and 200 ppm). The solutions were stirred for 30 minutes. After 30 minutes, the solutions were taken of the hot plate. Each solution was filtered with a 1 mm glass fiber filter while the solutions were still hot. The filtered solutions were analyzed using ICP to determine the amount of Ca2+ and Mg2+ in each. The results are shown in the table below.











TABLE 9








Magnesium




Sample
(ppm)
Calcium (ppm)




















5750 ppm CaC2O4•H2O,
11.1
7.46



10 ppm Mg



5750 ppm CaC2O4•H2O,
48.6
10.3



50 ppm Mg



5750 ppm CaC2O4•H2O,
11.1
7.42



100 ppm Mg



5750 ppm CaC2O4•H2O,
182
23.6



200 ppm Mg










As can be seen from this table, the addition of Mg2+ ions helped to solubilize the already formed calcium oxalate. For every ppm of Mg2+ present, almost 0.1 ppm of Ca2+ was dissolved.
Example 9
Solubility of Calcium Phosphate in the Presence of Mg2+ Ions in an Acidic Environment
A study was carried out to determine if the solubility of calcium phosphate could be increased in acid solutions with varying amounts of magnesium ions present. 100 gram samples of an approximate 1% acid solution was prepared with and without varying levels of magnesium. The concentrated acid solution used included 4.67% phosphoric acid, and 54.94% nitric acid, and water. The samples were super saturated with excess amounts of calcium phosphate. Varying levels of MgCl2 were added to each solution at room temperature. The solutions were stirred for 5-10 minutes. About 40 milliliters of each sample was filtered using a 1 micron filter. The filtered samples were then analyzed for calcium levels using ICP analysis. The exact concentrations of acids are listed and varied from 0.90% to 0.99%. The mole ratio of total acid to dissolved calcium was also calculated. The results are shown in the table below.











TABLE 10







Sample
Ca (ppm)
Acid:Ca mole ratio









0.99% acid solution
1640
1.51



and no Mg2+



0.98% acid solution
1740
1.41



and 3 ppm Mg2+



0.94% acid solution
1890
1.24



and 12 ppm Mg2+



0.90% acid solution
1740
1.28



and 23 ppm Mg2+










As can be seen from the table, the acidic solution with 12 ppm Mg2+ included had the highest increase of calcium solubility (a 15% increase from baseline) and the lowest acid to soluble calcium mole ratio (18% decrease from baseline). The samples that had 3 and 23 ppm Mg2+, each showed an increase of 6% in the calcium solubility and an acid to soluble calcium mole ratio decrease from 7% to 15%, respectively as compared to the baseline. Overall, it was shown that even at very low levels of Mg2+ ions added, in an acidic environment the addition of Mg2+ increases the solubility of calcium in solution.
Other Embodiments
It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate, and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims.
In addition, the contents of all patent publications discussed supra are incorporated in their entirety by this reference.
It is to be understood that wherever values and ranges are provided herein, all values and ranges encompassed by these values and ranges, are meant to be encompassed within the scope of the present invention. Moreover, all values that fall within these ranges, as well as the upper or lower limits of a range of values, are also contemplated by the present application.

## Claims

1. A method for removing scale from industrial equipment used to process a liquid food source during a cleaning process comprising:
applying a composition comprising an acidic detergent and an antiscalant solution comprising about 10 ppm to about 200 ppm of a water soluble source of magnesium ion selected from the group consisting of magnesium chloride, magnesium sulfate, and mixtures thereof to the surface, wherein the composition increases the solubility of the scale present on the surface by at least about 5%.

2. The method of claim 1, wherein the composition comprises about 0.25 wt% to about 10 wt% of the acidic detergent.

3. The method of claim 1, wherein the acidic detergent comprises at least one of phosphoric acid, nitric acid, sulfuric acid, lactic acid, acetic acid, hydroxyacetic acid, glutamic acid, glutaric acid, and citric acid.

4. The method of claim 1, wherein the acidic detergent comprises a combination of nitric acid, and phosphoric acid.

5. The method of claim 1, wherein the scale comprises a water insoluble calcium salt.

6. The method of claim 5, wherein the water insoluble calcium salt is selected from the group consisting of calcium oxalate, calcium phosphate, calcium apatite, and mixtures thereof.

7. The method of claim 1, wherein the composition increases the solubility of the scale present on the surface by at least about 15%.