US 200900692O2A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2009/0069202 A1
Stapp et al. (43) Pub. Date: Mar. 12, 2009
(54) CORROSION INHIBITION COMPOSITIONS Publication Classification
AND METHODS FORUSING THE SAME
(51) Int. Cl.
(76) Inventors: William Stapp, Santa Rosa, CA C CR
(US); Gary Westlund, Pleasanton, ( .01)
CA (US) (52) U.S. Cl. ......................................... 507/224: 507/238
Correspondence Address:
PERKINS COE LLP (57) ABSTRACT
P.O. BOX 1208
SEATTLE, WA 98111-1208 (US) Compositions and methods are described for inhibiting cor
rosion of corrodible metals present in contact with water in
21) App
(21) Appl. No.: 11A899.768
9 cooling9. water and other water storage
ge SVStems.
Sy The compo
p
sitions include concentrated Stannous salts and agents to solu
(22) Filed: Sep. 7, 2007 bilize such salts.
US 2009/0069202 A1 Mar. 12, 2009

CORROSION INHIBITION COMPOSITIONS 0011. In some embodiments, the amount of bifunctional

AND METHODS FORUSING THE SAME solubilization factor in the solution is from about 1.25% to
about 15% (wit/wt). In some embodiments, the amount of
FIELD OF THE INVENTION bifunctional solubilization factor in the solution is from about
0001. The present invention relates to methods for inhib 4% to about 6% (wt/wt). In some embodiments, the amount of
stannous salt in the solution is from about 3% to about 5%
iting corrosion of corrodible metals in contact with water, (wt/wt).
Such as boiler water or cooling water. 0012. In some embodiments, the terpolymer or copolymer
BACKGROUND OF THE INVENTION comprises carboxylate and Sulfonate functional groups.
0013. In some embodiments, the terpolymer comprises
0002 Metal surfaces in cooling water systems and boilers acrylic acid, acrylamidosulfonic acid, and terbutylacryla
are Subject to high levels of corrosion due to various factors, mide, and the copolymer comprises acrylic acid and acryla
including the high temperatures to which the metals are midosulfonic acid. In some embodiments, the Stannous solu
exposed. Heat exchanger Surface (skin) temperatures can tion additionally comprising an organic acid. In particular
reach about 200°F., which accelerates the chemical reactions embodiments, the organic acid is selected from citric acid,
resulting in corrosion. In addition, the water used in Such maleic acid, and polymaleic acid.
systems is often of moderately high alkalinity (about pH 8-9) 0014. In some embodiments, the stannous solution further
and high hardness, having very high levels (e.g. about 200 comprising an azole corrosion inhibitor compound. In some
ppm or more) of dissolved metal cations such as calcium and embodiments, the azole is present at a concentration of from
magnesium. about 2% to about 3% (wt/vol). In particular embodiments,
0003 Conventionally, cooling water in such systems is the azole is tolyltriazole.
treated with phosphate-based corrosion inhibitors, which 0015. In a related aspect, a composition is provided com
react with dissolved calcium to form calcium phosphate, prising:
which forms a precipitate/barrier deposit on the metal sur
face. Care must be taken, however, not to overfeed the phos 0016 stannous chloride at a concentration of from about
phate, as too thick a layer of calcium phosphate impairs heat 2% to about 4%, and
transfer. Typically, heat transfer degrades over time, and the 0017 a bifunctional solubilization factor selected from
affected equipment must be disassembled and cleaned peri HEDP, a terpolymer, and a copolymer. In some embodiments,
odically. the composition further comprising tolyltriazole at a concen
tration of about 2% to about 3%.
SUMMARY OF THE INVENTION 0018. In another related aspect, a concentrated composi
tion for inhibiting corrosion of corrodible metal in contact
0004. The following aspects and embodiments thereof with water in a cooling water system is provided, comprising
described and illustrated below are meant to be exemplary a stannous salt and a bifunctional solubilization factor,
and illustrative, not limiting in scope. wherein the bifunctional solubilization factor allows the stan
0005. In one aspect, a concentrated solution for adding to nous salt to be present at higher concentration than in the
cooling water to reduce corrosion and Scaling is provided, absence of the bifunctional solubilization factor and provides
comprising 1-15% stannous salts and a bifunctional Solubili additional activity as an anti-corrosion and/or anti-scaling
zation factor, wherein the bifunctional solubilization factor agent. In some embodiments, the composition provides
functions as a chelator for Stannous ions and as an anti adequate corrosion and Scaling reduction to be used in the
Scalant. In some embodiments, the solution provides absence of an additional corrosion and/or anti-scaling agent.
adequate corrosion and Scaling reduction to be used in the 0019. In some embodiments, the bifunctional solubiliza
absence of an additional corrosion and/or anti-scaling agent. tion factor is HEDP. In some embodiments, the bifunctional
0006. In some embodiments, the bifunctional solubiliza solubilization factor is a terpolymer or copolymer. In some
tion factor is selected from 1-hydroxyethylidene-1,1-diphos embodiments, the final pH of the composition is greater than
phonic acid (HEDP) or its water soluble salts, a terpolymer, or about 5.
a copolymer. In some embodiments, the bifunctional solubi 0020. In another aspect, a method for preparing a concen
lization factor is HEDP or a water soluble salt, thereof. trated Stannous salt composition is provided, comprising
0007. In some embodiments, the concentrated stannous 0021 adding acid to water,
Solution comprising a bifunctional Solubilization agent is
adjusted to a final pH of greater that 5. In preferred embodi 0022 adding a stannous salt to the acidified water,
ments, the pH is adjusted using potassium hydroxide (KOH). 0023 adding a bifunctional solubilization factor to the
0008. In some embodiments, the amount of HEDP in the acidified water comprising a stannous solution, and
solution is from about 1.25% to about 15% (wt/wt). In some 0024 adjusting the pH to between 2.6 and 9.
embodiments, the amount of HEDP in the solution is about 0025. In some embodiments, the final pH of the concen
4% to about 6% (wt/wt). In some embodiments, the amount of trated Stannous salt composition is greater than about 5.
HEDP in the solution is about 4.8% (wit/wt). In some embodi 0026. In some embodiments, the stannous salt is stannous
ments, the amount of Stannous salt in the solution is from chloride and the bifunctional solubilization factor is 1-hy
about 3% to about 5% (wit/wt). droxyethylidene-1,1-diphosphonic acid (HEDP) or its water
0009. In other embodiment, the bifunctional solubiliza soluble salts.
tion factor is selected from a terpolymer and a copolymer. 0027. In some embodiments, the stannous salt is stannous
0010. In some embodiments, the concentrated stannous chloride and the bifunctional solubilization factor is a ter
Solution comprising a bifunctional Solubilization agent is polymer or copolymer comprising acrylic acid and acrylami
adjusted to a final pH of greater that 5. In preferred embodi dosulfonic acid. In particular embodiments, the composition
ments, the pH is adjusted using potassium hydroxide (KOH). further comprises citric acid, maleic acid, or polymaleic acid.
US 2009/0069202 A1 Mar. 12, 2009

0028. In a related aspect, a method for preparing a con 0041. A “concentration of stannous salt which corre
centrated Stannous salt composition is provided, comprising sponds to a concentration of tin' in a given concentration
adding a bifunctional Solubilization factor to water, and add range is determined from the relative molecular weights of
ing a Stannous salt to the water containing the bifunctional the components. For example, 1.0 parts per million (ppm) tin
solubilization factor. corresponds to approx. 1.8 ppm SnSO 1.6 ppm SnCl2 or 2.3
0029. In some embodiments, the final pH of the concen ppm SnBr.
trated Stannous salt composition is greater than about 5. 0042. As used herein, “cooling water refers broadly to
0030. In some embodiments, the stannous salt is stannous recirculated water used to cool equipment, boiler water, water
chloride and the bifunctional solubilization factor is 1-hy in storage tanks, sprinkler systems, etc. While the present
droxyethylidene-1,1-diphosphonic acid (HEDP) or its water compositions and methods are well Suited to treating high
soluble salts. temperature water in contact with corrodible surfaces, they
0031. In some embodiments, the stannous salt is stannous are also suitable for treating water at room temperature or
chloride and the bifunctional solubilization factor is a ter below.
polymer or copolymer comprising acrylic acid and acrylami 0043. As used herein, “treatment' or “treating refers to
dosulfonic acid. adding the concentrate to a Subject body or Volume of water to
0032. In some embodiments, the stannous salt is stannous reduce corrosion of corrodible metals.
chloride and the bifunctional solubilization factor is a ter 0044 As used herein, a “concentrate' is a solution or
polymer or copolymer comprising a linear alkyl-aryl Sul Suspension of agents that is diluted in a body or Volume of
fonate and weak acid carboxylate. water to achieve a preselected final concentration of the
0033. In particular embodiments, the terpolymer is agents. Ideal concentrates have the minimum amount of
ACCUMER 3100 and the copolymer is ACCUMER 2100. water necessary to solubilize the agents or maintain the agents
0034. In some embodiments, the composition further in Suspension Such that, upon dilution, the agents are solubi
lized.
comprises citric acid, maleic acid, or polymaleic acid. 0045. As used herein, the expression “providing adequate
0035. These and other objects and features of the invention corrosion and Scaling reduction to be used in the absence of an
are made more fully apparent in the following detailed additional corrosion and/or anti-scaling agent,” means pro
description of the invention. viding a level of corrosion and Scaling reduction characteris
DETAILED DESCRIPTION OF THE INVENTION
tic of a corrosion inhibitor and a separate anti-scaling agent.
The protection need not be absolute, only consistent with that
I. Definitions provided by a typical combination of corrosion and Scaling
agents.
0.036 “Corrosion of a metal in contact with water, as used II. Stannous Salt Concentrates for Corrosion
herein, refers to degradation of the metal due to chemical Inhibition
reaction with its environment, in this case, water and Sub
stances present in the water, including air. Such corrosion 0046. As noted above, metal surfaces in cooling water
ultimately leads to dissolution or dispersion of the metal or systems are subject to high levels of corrosion due to various
metal compound in the water, observed as a loss of mass of the factors, including the high temperatures to which the metals
metal. are exposed. Heat exchanger Surface (skin) temperatures can
0037 A“non-carbon acid is an acid containing no carbon reach about 200°F., which accelerates the chemical reactions
atoms, e.g. hydrochloric, Sulfuric, phosphoric, or nitric acid. resulting in corrosion. Bulk water temperature of cooling
0038. As used herein, an “aqueous solution” refers to a water in contact with Such surfaces typically reaches about
composition in water. The composition may include an acid, 140°F.
e.g. HCl, HSO or HNO to promote dissolution of the 0047. The present compositions provide a water treatment
Stannous salt. There are no other components in any appre concentrate comprising a stannous salt and a bifunctional
ciable concentration, including organic molecules that can solubilization factor (herein, “solubilization factor). The
serve as a carbon Source for microorganisms. Stannous salt is selected from, e.g., Stannous chloride, stan
0039. A “composition consisting essentially of a stan nous bromide, Stannous fluoride, Stannous iodide, Stannous
nous salt of a non-carbon acid (or aqueous Solution) refers to oxide, Stannous phosphates, and Stannous Sulfate. In particu
the Stannous salt, or aqueous solution, in combination with lar embodiments the Stannous salt is stannous chloride. The
one or more optional components which do not materially concentration of the Stannous salt in the concentrate is from
affect the metal corrosion inhibiting characteristic(s) of the about 1% to about 15% (wit/wt), from about 2% to about 15%,
composition. Such components would typically be Sub from about 3% to about 10%, or even from about 3% to about
stances added to a distributive water stream for purposes other 5%, with a final diluted concentration of from about 0.05 to
than inhibition of corrosion, as defined above. For example, about 75 ppm, and preferably from about 0.1 to about 20 ppm,
dispersing or chelating agents, such as Soluble anionic poly in the water to be treated.
mers (e.g. polyacrylates or acrylate copolymers), or nonionic 0048 Preferred stannous salt concentrates are near satu
or ionic Surfactants, may be employed to reduce scale forma ration to maximize the benefit of the compositions and meth
tion on solid surfaces; biocides may be added to reduce ods. However, stability and storage requirements may require
microbial growth. that the Stannous concentrate is safely below Saturation to
0040. A similar definition applies to compositions “con prevent precipitation.
sisting essentially of a stannous salt of a non-carbon acid (or 0049. Without being limited to theory, it is believed that
aqueous solution) and an alkali metal phosphate. Such com certain agents, such as HEDP and terpolymers/copolymers,
positions may also include components present for purposes function as bifunctional solubilization factors to solubilize
other than inhibition of corrosion. the Stannous salts and hold them in Suspension by chelation,
US 2009/0069202 A1 Mar. 12, 2009

thereby permitting the preparation of a concentrated Stannous about 0.1 to about 25 ppm. The structures of PBTCA and
Solution, in Some cases at a pH higher than that at which HEDP are shown, below:
Stannous ions normally precipitate, i.e. >2.5. Upon dilution
in cooling water, the Stannous salts dissociate from the solu O CH-COOH OH
bilization factors, becoming available to treat the water.
0050. In addition to solubilizing stannous ions, these HO-P-C-COOH (HO)P-C-P(OH)
bifunctional solubilization factors also provide and additional OH l CH
benefit, for example, anti-scaling, anti-corrosion, or dispers
ant activity that is independent of the presence of Stannous CH-COOH HEDP
1O.S.
PBTCA
0051. The concentrated stannous salt compositions are
effective, at relatively low concentrations, to inhibit corrosion 0058. The solubilization factor can also be an organophos
of metals under conditions of high temperature, as noted phorous carboxylic acids. Suitable organophosphorous car
above, and do not precipitate on the Surface, as do conven boxylic acids have the following general structure, where
tional phosphate based inhibitors. The compositions are wherein R and Ro are, independently, hydrogen, C1-C5
effective to inhibit corrosion of ferrous metals, such as carbon alkyl, or C1-C5 alkyl substituted by an amine, carboxylic acid
steel, as well as other metals such as copper, lead, and brass. group, or ester group. In use, since the final composition is
The Stannous Salt compositions may also operate to remove alkaline, the compound will typically be present as an alkali
existing corrosion product from steel Surfaces, as Stannous or alkaline earth metal salt or C1-C5 alkyl ester:
ion reduces ferric ion (Fe") to ferrous ion (Fe"). In some
embodiments, the aqueous Stannous salt compositions do not O
contain any organic solvents or other organic components,
and thus do not promote growth of microorganisms.
Hoal-OH
0.052 Particular bifunctional solubilization factors for use
in preparing Stannous salt concentrates are described, below. R-- CEO
0053 A. Phosphorous-Containing Solubilization Factors O
H
0054. In some embodiments, the bifunctional solubiliza
tion factor is one or more organic phosphorous compounds,
which include phosphonates and organophosphorous car 0059. In preferred embodiments, the concentration of the
boxylic acids and their salts. These agents function as crystal phosphonate or organophosphorous carboxylic acid is from
modifiers to reduce precipitations of water-borne contami about 1.25% to about 15% (wit/wt), from about 2% to about
nants, and are used as anti-scaling agents (anti-scalants). 10%, from about 3% to about 7%, or from about 4% to about
0055 Suitable phosphonates have the following general 6% in the concentrate, with a final diluted concentration of
structure, where wherein Rs is C1-C5 alkyl or substituted from about 0.03 to about 60 ppm, or even 0.1 to about 25 ppm.
alkyl, including an amine Substituted alkyl and phosphonic 0060. Where the solubilization factor is HEDP about 1.26
acid substituted alkyl: g HEDP is sufficient to solubilize 1 g of stannous salts. How
ever, the compositions and methods may provide an excess of
HEDP, to avoid stannous salt precipitation under different
storage conditions, to increase the shelf life of the concen
trate, and/or to provide additional anti-scaling activity. For
P-Rs example, an up to 3:1 HEDP:stannous salt ratio is expected to
HO provide similar results. Additional HEDP (i.e. >3:1) is
unlikely to provide further benefit at increased cost and phos
phate levels. Note that HEDP may be provided as a solution
0056 Exemplary phosphonates, include aminomethyl with a specified activity, in which case the actual wit/wt
enephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic amount of total HEDP may be greater to account for the
acid (PBTCA; Shandong Taihe, China), aminotrimethylene less-than-100% activity. Other phosphonates or organophos
phosphonic acid (ATMP), ethylenediaminetetra(methylene phorous carboxylic acids may be provided at a similar excess.
phosphonic acid) sodium (EDTMPS), 2-hydroxyphosphono 0061 Stannous chloride typically precipitates at a pH
carboxylic acid (HPAA), 1-hydroxyethylidene-1,1-diphos >2.5. For example, a method for precipitating tin from solu
phonic acid (HEDP; Solutia, St. Louis, Mo., USA; Buckman tion involves increasing the pH of a solution from about 2.0 to
Labs., Memphis, Tenn., USA; Parchem Trading, Ltd., CAC about 3.5, which results in precipitation of over 99% of tin
SHANGHAI, Inc.), phosphinopolycarboxylic acid (PCA: from solution (U.S. Patent Pub. No. 200201 19085).
e.g., Acumer 4161, (Rohm and Haas), polyaminopolyether 0062. In some embodiments, the final pH of the present
methylene phosphonate (PAPEMP), and their water soluble concentrated Stannous Solution comprising a solubilization
salts. factor is adjusted to be between about 2.6 and 9. In some
embodiments, the pH is greater than about 5. Providing a
0057. In particular embodiments the solubilization factor concentrate at close to neutral pH simplifies handling and
is HEDP or a salt, thereof. In another particular embodiment, avoids changing the pH of the cooling water upon addition of
the solubilization factor is PBTCA or a salt, thereof. The final the concentrate. An exemplary pH range for the final Stannous
diluted concentration of HEDP or PCTCA should be from salt concentrate is from about 5 to about 9, or even from about
US 2009/0069202 A1 Mar. 12, 2009

pH 6 to about pH 7. Exemplary pH values are 5.0, 5.5, 6.0, 6.5, 0069. The use of a terpolymer or copolymer may be pref
7.0. 7.5, and 8.0. Potassium hydroxide is used to adjust pH. erable to the use of a phosphonate (e.g., HEDP), where the
0063. Using one or more bifunctional solubilization fac presence of phosphates in the cooling water is undesirable.
tors to prepare a Stannous salt concentrate provides several For example, the use of phosphonates and similar compounds
advantages over conventional stannous solutions, including is typically avoided when significant levels of calcium are
the ability to prepare a concentrated Stannous salt composi present in the cooling water. Calcium is known to precipitate
tion, optionally at near neutral pH, and having anti-scaling phosphonates, including HEDP.
activity without the addition of an additional discrete anti 0070 Terpolymers and copolymers may be combined
Scaling agent. with organic acids, such as carboxylic acids and Sulphonic
0064 B. Terpolymer and Copolymer Solubilization Fac acids, to provide additional anti-scaling activity while avoid
tOrs ing phosphate-containing compounds. Organic acids include
0065. In some embodiments, the solubilization factor is monocarboxylic acids, and dicarboxylic acids, polycarboxy
one or more terpolymers or copolymers. Terpolymers or lic acids, monosulphonic acids, and disulphonic acids.
copolymers are known in the art and described, in e.g., U.S. Examples of Suitable organic acids include citric acid, oxalic
Pat. Nos. 4,756,881, 5,030,748, 5,112,905, and 5,601,754. In acid, malonic acid, propionic acid, tartaric acid, lactic acid,
Some embodiments, one or more terpolymers or copolymers Succinic acid, glutaric acid, adipic acid, pimelic acid,
may be used in combination with an organic acid, Such as octanedioic acid, tartaric acid, malic acid, glutamic acid,
citric acid or polymaleic acid. maleic acid, polymaleic acid (PMA), fumaric acid, acrylic
0066 Exemplary terpolymers or copolymers are listed in acid, ethyl acrylate, methacrylic acid, Sulphonic acid, similar
the following table. (meth)polyacrylates, and 2-phosphonobutane-1,2,4-tricar

Polymer Components Example(s)

PAA polyacrylic acid GOOD-RITEK-732 (B. F. Goodrich)
PMA polymaleic acid BELCLENE 200 (BWA)
MASS maleic acid styrene Sulfonic Versa TL-4 (National Starch)
acid
AAAMPS acrylic acid, acrylamidosulfonic TRC-233 HS (), Belclene 400
acid (BioLabs),
ACCUMER 2100 (Rohm and
Haas)
AAMANI acrylic acid maleic acid/non- AQUATREAT AR-980 (Alco)
ionic Surfactant
AASPMENI acrylic acid AQUATREAT AR-540 and
Sulfophenylmethallyl AR550 (Alco)
ether non-ionic Surfactant
AAAMPS/TBAM acrylic acid acrylamidosulfonic ACCUMER 3100 (Rohm and
acid/terbutylacrylamide Haas)
AAAMPSSS acrylic acid acrylamidosulfonic GOOD-RITEK-798 (B. F. Goodrich)
acid styrene Sulfonic acid
MAEAWA maleic anhydrid ethyl BELCLENE 283 (BWA)
acrylate? vinyl acrylate
AAAMPSSSS acrylic acid/AMPSisulfonated GOOD-RITEK-797 and K-798
Sodium styrene. (B. F. Goodrich)

0067. The terpolymer or copolymer is preferably present boxylic Acid (PBTCA). Such organic acids may be employed
at about 2% to about 15% (wit/wt), from about 3% to about as free acids or as their alkali metal or alkaline earth metal
10%, or even from about 3% to about 5%, in the concentrate. salts.
Preferred terpolymers are a combination of linear alkyl-aryl 0071. Several organic acids, exemplified by citric acid,
Sulfonates with weak acid carboxylates, and Surfactants. Pre reduce chlorine induced corrosion and limescale formation.
ferred copolymers are a combination of linear alkyl-aryl Sul
fonates with weak acid carboxylates. Examples of such ter Citric acid, polymaleic acid, and PBTCA are crystal modifi
polymers and copolymers are ACCUMER 3100 and ers with respect to certain salts, such as calcium carbonate.
ACCUMER 2100, respectively (Rohm and Haas). Other Polymaleic acid (below) is available from, e.g., KELIEN
examples are provided in the foregoing table and known in the Chemical Co., Ltd. and CCS. Chem. Co., Ltd. (China) and
art. Terpolymers/copolymers comprising Sulfonated Styrene Chemos GmbH and Connect Chemicals GmbH (Germany).
maleic anhydride are also expected to produce satisfactory 0072. In particular embodiments, an organic acid such as
results. citric acid or PMA is used to prepare a stannous salt concen
0068 Suitable nonionic (NI) surfactants include polysor trate, which additionally possesses anti-fouling activity
bate esters, alcohol ethoxylates, and nonyl phenol ethoxy owing to the present of the organic acid. In some embodi
lates. Suitable anionic Surfactants include Sulfonated Surfac ments, the amount of organic acid used to solubilize the
tants, such as sodium octane-1-sulfate (e.g., BIOTERGE stannous salts is from about 1.25% to about 15% (wit/wt),
PAS-8S, Stepan Co., Northfield, Ill., USA) and sodium 2-eth from about 2% to about 10%, from about 3% to about 7%, or
ylhexylsulfate (e.g., RHODAPON BOS, Rhodia Inc., Cran from about 4% to about 6% in the concentrate, with a final
bury, N.J., USA). Nonionic and anionic surfactants are used diluted concentration of from about 0.03 to about 60 ppm, or
to couple triazoles and clarify the solution. even 0.1 to about 25 ppm.
US 2009/0069202 A1 Mar. 12, 2009

0073 C. Additional Agents premixed dry stannous salt and solubility factor. As above, the
0.074 Concentrated Stannous compositions comprising a aqueous solution may be neutralized prior to adding other,
bifunctional solubilization factor may further include addi optional agents.
tional agents to reduce corrosion and scale. For example, in
Some embodiments, concentrated Stannous compositions fur IV. Exemplary Composition and Methods of Use
ther includes an azole corrosion inhibitor compound, Such as
tolyltriazole, benzotriazole, or mercaptobenzothiazol. In pre I0082 In support of the present compositions and methods,
ferred embodiments, the concentration of azole in the con an exemplary composition was prepared and used to treat
centrate is from about 1% to about 4%, with a final concen water in a cooling tower located at the Park Central Office
tration of from about 0.1 to about 15 ppm in the treated water. Building in Denver, Colo., USA. A concentrate consisting of
The solubility of the azole compound may depend on the pH stannous chloride (3.5%), HEDP (4.8%), and tolyltriazole
of the Stannous Salt concentrate and coupling characteristics (2.3%) (i.e., referred to as AS-8310) was compared to a con
of further optional additional Surfactant agents. AZole can be vention phosphonate inhibitor for the ability to control carbon
used in combination with terpolymers, copolymers, organic steel corrosion. Removable mild steel coupons were used to
acids, and/or HEDP. monitor corrosion, which was measured as the amount of
0075 Additional agents that can optionally be added to the material lost (i.e., decrease in thickness) measured in mil (i.e.,
concentrate include but are not limited to detergent builders, /1,000 inch). The coupons were pre-treated (passivated) with
anti-foaming agents, dispersants, anti-microbial agents (bio the respective corrosion inhibitor prior to being placed in the
cides or biostats), odor neutralizers, fragrances, dyes, thick cooling tower. The Stannous concentrate was added to the
ening agents, bleaches, buffers, and enzymes. Further addi cooling at a rate of 100 ppm based on blowdown. The treat
tives include boron, molybdenum, titanium, tungsten, and ment dosage was determined by measuring the levels of phos
Vanadium compounds, as well as alkali metal salts. In par phonate. The target range was about 7-8 ppm phosphonate,
ticular, the addition of boron and molybdenum may produce which provided a tin concentration of about 3 ppm. Raw data
synergistic effects, and/or may be used as tracers. are shown in the Table, below.

III. Preparation of Aqueous Scaling Agent-Stannous

Salt Concentrates Date. In Date Out Days Exposed CR* Inhibitor
Jul. 9, 2003 Oct. 8, 2003 91 1.8 Phosphonate
0076. The present methods relate to preparing a water Oct. 8, 2003 Jan. 27, 2004 111 1.8 Phosphonate
treatment concentrate, as described, herein. Jan. 27, 2004 Jun. 2, 2004 127 1 Phosphonate
Jun. 2, 2004 Sep. 24, 2004 114 0.88 Phosphonate
0077. In some embodiments, the methods contemplate Sep. 24, 2004 Nov. 3, 2004 40 2.01 Phosphonate
adding a Stannous salt to acidified water containing the Jan. 5, 2005 May. 4, 2005 119 0.58 Phosphonate
bifunctional solubilization factor, and then adjusting the pH Aug. 3, 2005 Jan. 4, 2006 154 1.47 Phosphonate
of the solution as desired. The solubilization factor need not Feb. 15, 2007 Mar. 29, 2007 42 O.29 AS-831O
Mar. 29, 2007 Apr. 27, 2007 29 O651 AS-831O
be present in acidified waterprior to adding Stannous salts but Apr. 27, 2007 May. 24, 2007 27 O.339 AS-8310
is present before adjusting the pH of the concentrate. Potas May. 24, 2007 Jun. 28, 2007 35 O3S AS-8310
sium hydroxide is preferred for adjusting pH, in view of its CR* = corrosion rate in mils per year (i.e., 0.001"/year)
solubility characteristics and non-association with the stan
nous system. I0083. The presence of the stannous salt-HEDP inhibitor
0078. In other embodiments, the methods contemplate provided better protection against corrosion than the conven
adding a bifunctional Solubilization factor to water, and then tional phosphonate treatment, demonstrating the efficacy of
adding a stannous salt to water containing the solubilization the present compositions and methods. In particular, the cor
factor. Acidification of the water in not required. The resulting rosion rate of mild steel was about 0.3-0.65 mils per year in
concentrate can be used as is or adjusted to a desired pH. As the presence of the stannous salt-HEDP inhibitor, compared
above, potassium hydroxide is preferred for adjusting pH: to 0.58-2.0 mils per year using phosphonate. The Stannous
0079. In example of these embodiments, a molar ratio of at salt-HEDP inhibitor appeared to provide about 3 to about
least 1.26 parts HEDP: 1-part stannous ion produced good 6-fold better protection that phosphonate.
results. Lower ratios produce turbid solutions and/or cause I0084 Observations in a related study using artificially
precipitation of the Stannous salt. Higher ratios result in a elevated levels of calcium chloride, sodium bicarbonate,
more stable solution at higher cost. Similar ratios of terpoly magnesium sulfate, and silica, indicated that corrosion of
mers (e.g., Sulfonate/carboxylate/nonionic) and copolymers steel coupons in the presence of a stannous salt-HEDP inhibi
(e.g., Sulfonate/carboxylate) produce similar results. tor was limiting to etching, with reduced gouging and pitting
0080 Additional agents required or desired for function compared to phosphonate (not shown). Observations also
and performance of the water treatment in cooling water Suggested that corrosion in the presence of the Stannous salt
applications can be added upon neutralization of the aqueous HEDP inhibitor followed a different profile (or curve) than
Solution with a base. Alternatively, additional agents may be corrosion in the presence of phosphonate. Protection in the
added to the acidified water or stannous solution, provided presence of the stannous salt-HEDP inhibitor appeared to
that they do not interfere with the solubility of the stannous increase following an initial period of limited corrosion, Sug
salt. gesting that the use of the stannous salt-HEDP inhibitor
0081 Alternatively, the present compositions may be pre would afford greater protection in long term studies/applica
pared by adding acidified water to dry stannous salt or to tions.
US 2009/0069202 A1 Mar. 12, 2009

0085. The substitution of a terpolymer, optionally in com 16. The solution of claim 15, wherein the amount of stan
bination with citric acid, for HEDP is expected to produce nous salt in the solution is from about 3% to about 5% (wt/wt).
similar results using similar amounts of the Stannous salt and 17. The solution of claim 11, wherein the terpolymer or
the optional azole compound. copolymer comprises carboxylate and Sulfonate functional
groups.
V. Utility 18. The solution of claim 17, wherein the terpolymer com
I0086. The ability to prepare concentrated stannous solu prises acrylic acid, acrylamidosulfonic acid, and terbuty
tions for water treatment means that an end user is required to lacrylamide, and the copolymer comprises acrylic acid and
add a smaller Volume to a given Volume of water. This is an acrylamidosulfonic acid.
advantage where access to the water Supply is difficult, where 19. The solution of claim 18, additionally comprising an
water must be drained from the Supply prior to adding the organic acid.
concentrate, or where addition of a larger Volume of a water 20. The solution of claim 19, wherein the organic acid is
treatment composition is undesirable. In addition, concen selected from citric acid, maleic acid, and polymaleic acid.
trated water treatment compositions requires less storage 21. The composition of claim 1, further comprising an
space, use less packaging material, and are easier to transport. azole corrosion inhibitor compound.
0087. The ability to prepare concentrated stannous solu 22. The composition of claim 21, wherein the azole is
tions for water treatment at neutral or near neutral pH further present at a concentration of from about 2% to about 3%
simplifies handling of the concentrate and avoids adding an (wt/vol).
acid solution to cooling water, thereby reducing its pH. 23. The composition of claim 22, wherein the azole is
0088. The use of an anti-scaling agent, anti-flocculating tolyltriazole.
agent, or crystal modifier to prepare a concentrated Stannous 24. A composition comprising:
solution provides the additional benefits of such compounds stannous chloride at a concentration of from about 2% to
without adding an additional or discrete anti-scaling agent, about 4%, and
anti-flocculating agent, or crystal modifier. a bifunctional solubilization factor selected from HEDP, a
0089. One skilled in the art will recognize further embodi terpolymer, and a copolymer.
ments and uses for the present composition and methods in 25. The composition of claim 24, further comprising tolyl
view of the disclosure. triazole at a concentration of about 2% to about 3%.
1. A concentrated solution for adding to cooling water to 26. A concentrated composition for inhibiting corrosion of
reduce corrosion and Scaling, comprising 1-15% stannous corrodible metal in contact with water in a cooling water
salts and a bifunctional solubilization factor, wherein the system, comprising a stannous salt and a bifunctional solubi
bifunctional solubilization factor functions as a chelator for lization factor, wherein the bifunctional solubilization factor
Stannous ions and as an anti-scalant. allows the Stannous salt to be present at higher concentration
2. The solution of claim 1, wherein the solution provides than in the absence of the bifunctional solubilization factor
adequate corrosion and Scaling reduction to be used in the and provides additional activity as an anti-corrosion and/or
absence of an additional corrosion and/or anti-scaling agent. anti-Scaling agent.
3. The solution of claim 1, wherein the bifunctional solu 27. The composition of claim 26, wherein the composition
bilization factor is selected from 1-hydroxyethylidene-1,1- provides adequate corrosion and Scaling reduction to be used
diphosphonic acid (HEDP) or its water soluble salts, a ter in the absence of an additional corrosion and/or anti-scaling
polymer, or a copolymer. agent.
4. The solution of claim 1, wherein the bifunctional solu 28. The composition of claim 26, wherein the bifunctional
bilization factor is HEDP or a water soluble salt, thereof. Solubilization factor is HEDP.
5. The solution of claim 4, having a pH of greater than 5. 29. The composition of claim 26, wherein the bifunctional
6. The solution of claim 5, wherein the pH is adjusted using solubilization factor is a terpolymer or copolymer.
potassium hydroxide (KOH). 30. The composition of claim 26, wherein the final pH of
7. The solution of claim 4, wherein the amount of HEDP in the composition is greater than about 5.
the solution is from about 1.25% to about 15% (wit/wt). 31. A method for preparing a concentrated Stannous salt
8. The solution of claim 4, wherein the amount of HEDP in composition, comprising
the solution is about 4% to about 6% (wit/wt). adding acid to water,
9. The solution of claim 4, wherein the amount of HEDP in
the solution is about 4.8% (wit/wt). adding a stannous Salt to the acidified water,
10. The solution of claim 7, wherein the amount of stan adding a bifunctional solubilization factor to the acidified
nous salt in the solution is from about 3% to about 5% (wt/wt). water comprising a stannous Solution, and
11. The solution of claim 1, wherein the bifunctional solu adjusting the pH to between 2.6 and 9.
bilization factor is selected from a terpolymer and a copoly 32. The method of claim 31, wherein the final pH of the
C. concentrated Stannous salt composition is greater than about
12. The solution of claim 11, having a pH of greater than 5. 5.
13. The solution of claim 12, wherein the pH is adjusted 33. The method of claim 31, wherein the stannous salt is
using potassium hydroxide (KOH). stannous chloride and the bifunctional solubilization factor is
14. The solution of claim 11, wherein the amount of bifunc 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) or its
tional solubilization factor in the solution is from about water soluble salts.
1.25% to about 15% (wit/wt). 34. The method of claim 31, wherein the stannous salt is
15. The solution of claim 11, wherein the amount of bifunc stannous chloride and the bifunctional solubilization factor is
tional solubilization factor in the solution is from about 4% to a terpolymer or copolymer comprising acrylic acid and acry
about 6% (wit/wt). lamidosulfonic acid.
US 2009/0069202 A1 Mar. 12, 2009

35. The method of claim 34, wherein the composition 39. The method of claim 36, wherein the stannous salt is
further comprises citric acid, maleic acid, or polymaleic acid. stannous chloride and the bifunctional solubilization factor is
36. A method for preparing a concentrated Stannous salt a terpolymer or copolymer comprising acrylic acid and acry
composition, comprising lamidosulfonic acid.
adding a bifunctional Solubilization factor to water, and 40. The method of claim 36, wherein the stannous salt is
adding a stannous salt to the water containing the bifunc stannous chloride and the bifunctional solubilization factor is
tional solubilization factor. a terpolymer or copolymer comprising a linear alkyl-aryl
37. The method of claim 36, wherein the final pH of the Sulfonate and weak acid carboxylate.
concentrated Stannous salt composition is greater than about 41. The method of claim 40, wherein the terpolymer is
5. ACCUMER 3100 and the copolymer is ACCUMER 2100.
38. The method of claim 36, wherein the stannous salt is 42. The method of claim 40, wherein the composition
stannous chloride and the bifunctional solubilization factor is further comprises citric acid, maleic acid, or polymaleic acid.
1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) or its
water soluble salts. c c c c c