TW201908247A - Composition and method for inhibiting corrosion and scale - Google Patents

Composition and method for inhibiting corrosion and scale Download PDF

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TW201908247A
TW201908247A TW107120455A TW107120455A TW201908247A TW 201908247 A TW201908247 A TW 201908247A TW 107120455 A TW107120455 A TW 107120455A TW 107120455 A TW107120455 A TW 107120455A TW 201908247 A TW201908247 A TW 201908247A
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馬塔 德魯尼亞克
萊爾 施泰梅
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美商Ｎｃｈ公司
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167—Phosphorus-containing compounds
    • C23F11/1676—Phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/08—Corrosion inhibition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A composition and method of inhibiting corrosion, white rust, and scale formation on components in a water system. The composition preferably comprises an amino-acid based polymer (most preferably a polyaspartic acid or a salt thereof), hydroxyphosphonoacetic acid, and a second phosphonic acid (preferably a phosphonocarboxylic acid), and does not require the use of regulated metals. The composition is effective even in the presence of biocides. A preferred method of inhibiting white rust comprises adding an amino-acid based polymer or hydroxyphosphonoacetic acid or both to the water system. A preferred method of inhibiting corrosion, white rust, and scale formation comprises adding an amino-acid based polymer, hydroxyphosphonoacetic acid, and a phosphonocarboxylic acid to the water system. Preferably the active concentrations are at least 3 ppm each of the amino-acid based polymer and hydroxyphosphonoacetic acid when added to a volume of water in the water system.

Description

抑制腐蝕和水垢的組成物及方法Composition and method for inhibiting corrosion and scale

本發明係關於用於抑制低LSI(藍氏(Langelier)飽和指數)水系統中之金屬組件上的腐蝕或白鏽，以及用於抑制高LSI水系統中水垢形成之處理組成物及方法。The present invention relates to a treatment composition and method for inhibiting corrosion or white rust on metal components in a low LSI (Langelier saturation index) water system, and for inhibiting scale formation in a high LSI water system.

各種水處理組成物係用以減少於與水系統(諸如開放式再循環系統、封閉式迴路冷卻或加熱系統、冷卻塔及鍋爐)中之水溶液接觸的金屬組件上之腐蝕、礦物水垢及白鏽形成，以及有助於保護該等系統之金屬組件。常用於該等水系統之金屬組件包括鐵金屬，包括鍍鋅鋼、鋁及其合金、銅及其合金、鉛及焊錫。許多已知腐蝕抑制劑含有受管制有毒金屬，諸如鋅、鉻酸鹽、及鉬酸鹽，其對環境有害且提高成本。鋅通常用作具有高度腐蝕性水(低LSI)之水系統中的腐蝕抑制劑。然而，因毒性問題而不希望使用彼，且其使用在許多地點面臨管制。已使用錫作為鋅之無毒替代品，但其較昂貴。Various water treatment compositions are used to reduce corrosion, mineral scale and white rust on metal components in contact with aqueous solutions in water systems such as open recirculation systems, closed loop cooling or heating systems, cooling towers and boilers Form and metal components that help protect such systems. Metal components commonly used in these water systems include ferrous metals, including galvanized steel, aluminum and its alloys, copper and its alloys, lead and solder. Many known corrosion inhibitors contain regulated toxic metals such as zinc, chromate, and molybdate, which are harmful to the environment and increase costs. Zinc is commonly used as a corrosion inhibitor in water systems with highly corrosive water (low LSI). However, the use of the other is not desirable due to toxicity issues, and its use is regulated in many locations. Tin has been used as a non-toxic alternative to zinc, but it is more expensive.

許多已知之腐蝕及水垢抑制劑的性能亦受到使用殺生物劑的負面影響，殺生物劑經常用於水系統中以控制微生物生長。使用聚天冬胺酸及單一種膦酸已於美國專利5,523,023號中揭示為有效於抑制腐蝕及水垢，當該膦酸為2-膦醯基丁烷-1,2,4-三甲酸(PBTC)時，即使存在殺生物劑亦有效。'023專利中之較佳膦酸為PBTC，但亦提及其他膦酸(包括1-羥基乙烷1,1-二膦酸及羥基膦醯基乙酸(HPA))為適用者。以使用聚天冬胺酸及PBTC為基礎之'023專利中所顯示的腐蝕速率結果優於其他腐蝕抑制劑，但仍需要更強腐蝕抑制作用，特別是於存在殺生物劑時。以使用聚天冬胺酸及PBTC為基礎之'023專利中所顯示的水垢形成結果與單獨使用PBTC所獲得之結果大約相同，表示採用'023之二組分配方在水垢抑制方面無實際改善。The performance of many known corrosion and scale inhibitors is also negatively affected by the use of biocides, which are often used in water systems to control microbial growth. The use of polyaspartic acid and a single phosphonic acid has been disclosed in U.S. Patent No. 5,523,023 as effective in inhibiting corrosion and scale. When the phosphonic acid is 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC ), It is effective even in the presence of biocides. The preferred phosphonic acid in the '023 patent is PBTC, but other phosphonic acids (including 1-hydroxyethane 1,1-diphosphonic acid and hydroxyphosphonophosphonoacetic acid (HPA)) are also mentioned as applicable. The results of the corrosion rate shown in the '023 patent based on the use of polyaspartic acid and PBTC are better than other corrosion inhibitors, but still require stronger corrosion inhibition, especially in the presence of biocides. The scale formation results shown in the '023 patent based on the use of polyaspartic acid and PBTC are approximately the same as those obtained using PBTC alone, indicating that there is no practical improvement in scale inhibition with the two-component formulation of' 023.

目前所使用之用於防止白鏽的溶液包括用碳酸鋅使金屬表面鈍化，以及控制水化學以減少白鏽形成的可能。已知之處理包括使用無機磷酸鹽、胺硫甲酸鹽、有機有機磷化合物及單寧。例如，美國專利5,407,597號及6,468,470號揭示包含有機磷化合物(包括PBTC)；鉬、鈦、鎢、或釩之鹼金屬鹽；及胺基甲酸鹽化合物或單寧化合物之組成物。美國專利6,183,649號揭示用於處理循環水系統之包含PBTC、聚丙烯酸鈉、甲苯基***鈉、鹼金屬鉬酸鹽、及鹼金屬溴化物的白鏽處理組成物。'649專利亦揭示以25磅/1,000加侖水/週的速率將1.5%之癸基硫乙基醚胺(DTEA)水溶液添加至循環水系統，然後於添加DTEA之後於十個再循環周期期間以每一周期600 ppm之速率添加白鏽處理組成物。Solutions currently used to prevent white rust include passivating metal surfaces with zinc carbonate and controlling water chemistry to reduce the possibility of white rust formation. Known treatments include the use of inorganic phosphates, amine thioformates, organic organophosphorus compounds, and tannins. For example, U.S. Patent Nos. 5,407,597 and 6,468,470 disclose compositions comprising organic phosphorus compounds (including PBTC); alkali metal salts of molybdenum, titanium, tungsten, or vanadium; and carbamate compounds or tannin compounds. U.S. Patent No. 6,183,649 discloses a white rust treatment composition comprising PBTC, sodium polyacrylate, sodium tolyltriazole, alkali metal molybdate, and alkali metal bromide for treating a circulating water system. The '649 patent also discloses that a 1.5% aqueous solution of decyl thioethyl ether amine (DTEA) is added to the circulating water system at a rate of 25 lbs / 1,000 gallons of water per week, and then after the addition of DTEA, the White rust treatment composition was added at a rate of 600 ppm per cycle.

需要可用以抑制水系統中之腐蝕、白鏽及水垢但不需要會彼此負面相互作用的分開處理之有效多合一(all-in-one)處理組成物及方法。亦需要更環境友善且能與殺生物劑組合適當執行之有效多合一處理。There is a need for effective all-in-one treatment compositions and methods that can be used to inhibit corrosion, white rust, and scale in water systems, but do not require separate treatments that negatively interact with each other. There is also a need for effective all-in-one processing that is more environmentally friendly and can be appropriately performed in combination with biocides.

根據本發明一個較佳實施態樣，經改善之腐蝕抑制劑、白鏽抑制劑、及水垢抑制劑組成物包含以胺基酸為基礎之聚合物(AAP)、羥基膦醯基乙酸(HPA)或其水溶性鹽，以及另一膦酸或其水溶性鹽。羥基膦醯基乙酸具有下示通式：According to a preferred embodiment of the present invention, the improved corrosion inhibitor, white rust inhibitor, and scale inhibitor composition includes an amino acid-based polymer (AAP), and hydroxyphosphonophosphonoacetic acid (HPA). Or a water-soluble salt thereof, and another phosphonic acid or a water-soluble salt thereof. Hydroxyphosphonium phosphonoacetic acid has the following formula:

最佳的，以胺基酸為基礎之聚合物為聚天冬胺酸或其水溶性鹽，但亦可使用其他化合物，諸如聚甘胺酸、聚麩胺酸及其鹽。最佳的，該以胺基酸為主之聚合物具有下式：Most preferably, the amino acid-based polymer is polyaspartic acid or a water-soluble salt thereof, but other compounds such as polyglycine, polyglutamic acid, and salts thereof may also be used. Most preferably, the amino acid-based polymer has the following formula:

其中，就聚天冬胺酸而言，R1=H，R2=OH，且R3=COOH以及x=1。最佳的，其他膦酸為膦醯基羧酸或者亦可使用任何有機膦酸鹽。最佳的，該膦醯基羧酸為1-羥乙烷-1,1-二膦酸(HEDP)或2-膦醯基丁烯-1,2,4-三甲酸(PBTC)或膦醯基丁二酸。較佳的，抑制劑組成物中之AAP對HPA的重量比為90:10至10:90，以及合併之AAP與HPA對其他膦酸的比係在90:10至60:40之範圍。更佳的，抑制劑組成物中之AAP對HPA的重量比範圍為80:20至80:20，以及合併之AAP與HPA對其他膦酸的比係80:20至70:30。Among them, in terms of polyaspartic acid, R1 = H, R2 = OH, and R3 = COOH and x = 1. Most preferably, the other phosphonic acid is a phosphinophosphonic acid or any organic phosphonate may be used. Most preferably, the phosphinophosphonic acid is 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or 2-phosphinofluorenylbutene-1,2,4-tricarboxylic acid (PBTC) or phosphinophosphonium Succinic acid. Preferably, the weight ratio of AAP to HPA in the inhibitor composition is 90:10 to 10:90, and the ratio of the combined AAP and HPA to other phosphonic acids is in the range of 90:10 to 60:40. More preferably, the weight ratio of AAP to HPA in the inhibitor composition ranges from 80:20 to 80:20, and the ratio of the combined AAP to HPA to other phosphonic acids is 80:20 to 70:30.

最佳的，根據本發明較佳實施態樣之組成物為全有機且不含受管制金屬，諸如鋅、鉻酸鹽及鉬酸鹽，且其性能不受添加殺生物劑影響。最佳的，根據本發明較佳實施態樣之組成物不含錫。Most preferably, the composition according to a preferred embodiment of the present invention is all organic and free of regulated metals such as zinc, chromate and molybdate, and its performance is not affected by the addition of biocides. Most preferably, the composition according to a preferred embodiment of the present invention does not contain tin.

先前已知分開使用HPA與AAP(諸如聚天冬胺酸)二者作為腐蝕抑制劑。於'023專利中亦揭示AAP可與膦醯基羧酸一同使用以抑制腐蝕及水垢，但先前未知AAP及HPA與另一膦酸(較佳為膦醯基羧酸)或有機膦酸鹽一同使用以抑制腐蝕或水垢。It has previously been known to use both HPA and AAP (such as polyaspartic acid) separately as corrosion inhibitors. It is also disclosed in the '023 patent that AAP can be used with phosphinophosphonic acid to inhibit corrosion and scale, but it has not been previously known that AAP and HPA are used with another phosphonic acid (preferably phosphinophosphonic acid) or an organic phosphonate Use to inhibit corrosion or scale.

當添加至正在處理之水系統中的水時，用於抑制腐蝕的根據本發明之較佳組成物產生至少3 ppm活性AAP、至少3 ppm活性HPA、及至少2 ppm之其他膦酸。更佳的，當添加至正在處理之水系統中的水時，較佳組成物產生3 ppm至50 ppm AAP、3 ppm至50 ppm HPA、及2 ppm至20 ppm之其他膦酸，及最佳係介於5 ppm至30 ppm AAP、3 ppm至20 ppm HPA、及2 ppm至10 ppm之其他膦酸。另外，當添加至正在處理之水時，較佳組成物之三種組分總計產生至少8 ppm之活性腐蝕抑制劑。該等成分於低LSI水系統(LSI＜-0.5)中具有出乎意料的經改良腐蝕抑制協同效果，而不需要使用有毒金屬及不會受殺生物劑負面影響。When added to water in the water system being treated, the preferred composition according to the invention for inhibiting corrosion produces at least 3 ppm active AAP, at least 3 ppm active HPA, and at least 2 ppm other phosphonic acids. More preferably, when added to the water being treated, the preferred composition produces 3 ppm to 50 ppm AAP, 3 ppm to 50 ppm HPA, and 2 ppm to 20 ppm of other phosphonic acids, and most preferably Other phosphonic acids between 5 ppm to 30 ppm AAP, 3 ppm to 20 ppm HPA, and 2 ppm to 10 ppm. In addition, when added to the water being treated, the three components of the preferred composition together produce at least 8 ppm of an active corrosion inhibitor. These ingredients have unexpectedly improved synergistic effects in corrosion suppression in low LSI water systems (LSI <-0.5) without the need to use toxic metals and not be adversely affected by biocides.

除了對於低LSI水中之鐵金屬腐蝕抑制的出乎意料協同效果之外，同一組成物亦對於防止鍍鋅鋼上形成白鏽具有正面效果。鍍鋅鋼係由熔融至鋼基材之鋅的薄塗層組成。白鏽為對鋅之迅速、局部腐蝕攻擊，其經常呈現為膨大的白色沉積物。該迅速腐蝕會完全移除局部區域的鋅，結果導致設備壽命縮短。白鏽形成往往隨水中之鹼度水準提高而提高。單獨或組合之羥基膦醯基乙酸或以胺基酸為基礎之聚合物(諸如聚天冬胺酸)先前均未用於防止白鏽之商業產品。不受理論限制，一般認為根據本發明之組成物可於鍍鋅鋼表面形成保護層並減少白鏽形成。根據本發明為處理白鏽，較佳係使用如前文指示用於抑制腐蝕之量(當添加至正在處理之水系統中的水時的重量比與濃度二者)的羥基膦醯基乙酸、以胺基酸為基礎之聚合物、及另一膦酸，但亦發現使用以胺基酸為基礎之聚合物而無羥基膦醯基乙酸或該其他膦酸於抑制白鏽有益。根據另一個較佳實施態樣，用於處理白鏽之組成物包含以胺基酸為基礎之聚合物及羥基膦醯基乙酸，而無另一膦酸。根據本發明又另一個較佳實施態樣，用於處理白鏽之組成物包含以胺基酸為基礎之聚合物而無任何羥基膦醯基乙酸。用於白鏽之該等組分於添加至正在處理之水時的較佳濃度及範圍係與用於抑制腐蝕者相同。In addition to the unexpected synergistic effect on the corrosion suppression of ferrous metals in low LSI water, the same composition also has a positive effect on preventing the formation of white rust on galvanized steel. Galvanized steel consists of a thin coating of zinc fused to the steel substrate. White rust is a rapid, localized corrosion attack on zinc, which often appears as a swollen white deposit. This rapid corrosion completely removes zinc in local areas, resulting in reduced equipment life. White rust formation tends to increase as the level of alkalinity in the water increases. Neither hydroxyphosphinophosphonoacetic acid or amino acid-based polymers (such as polyaspartic acid), alone or in combination, have previously been used in commercial products to prevent white rust. Without being limited by theory, it is generally believed that the composition according to the present invention can form a protective layer on the surface of galvanized steel and reduce the formation of white rust. In order to treat white rust according to the present invention, it is preferred to use hydroxyphosphinofluorenylacetic acid, as indicated above, for inhibiting corrosion (both weight ratio and concentration when added to water in the water system being treated), Amino acid-based polymers, and another phosphonic acid, but the use of amino acid-based polymers without hydroxyphosphinophosphonoacetic acid or the other phosphonic acids has also been found to be beneficial in inhibiting white rust. According to another preferred embodiment, the composition for treating white rust comprises an amino acid-based polymer and hydroxyphosphonophosphonoacetic acid without another phosphonic acid. According to yet another preferred embodiment of the present invention, the composition for treating white rust contains an amino acid-based polymer without any hydroxyphosphinophosphonoacetic acid. The preferred concentrations and ranges of these components for white rust when added to the water being treated are the same as those used to inhibit corrosion.

除了該抑制劑組成物對於低LSI水中之白鏽及對於鐵金屬腐蝕抑制的出乎意料協同效果之外，同一組成物亦對於高LSI水(LSI＞1)中防止礦物水垢形成具有正面效果。礦物水垢包括碳酸鈣及碳酸鎂、磷酸鈣、硫酸鈣、及矽石。當溫度提高時，碳酸鈣及磷酸鈣之溶解度降低，導致碳酸鈣及磷酸鈣於較高溫之水系統(諸如冷卻塔)中造成更多問題。LSI係以下示公式測定：In addition to the unexpected synergistic effect of the inhibitor composition on white rust in low LSI water and corrosion suppression of ferrous metals, the same composition also has a positive effect on preventing mineral scale formation in high LSI water (LSI> 1). Mineral scales include calcium carbonate and magnesium carbonate, calcium phosphate, calcium sulfate, and silica. As the temperature increases, the solubility of calcium carbonate and calcium phosphate decreases, causing calcium carbonate and calcium phosphate to cause more problems in higher temperature water systems, such as cooling towers. LSI is determined by the following formula:

LSI=pH-pHs，其中pHs為CaCO3飽和點之pH。LSI = pH-pHs, where pHs is the pH of the CaCO3 saturation point.

LSI＞0表示形成水垢，因水垢會形成以及會發生CaCO3沉澱。LSI≤0表示不形成水垢，因無形成水垢的可能且該水會溶解CaCO3。如本領域具有通常知識者將暸解的，LSI為水垢形成之驅動力指示而非嚴格的定量指示，水垢形成將取決於水特性、溫度、及水系統操作。然而，在無水垢抑制劑的情況下，於LSI大於0.2時通常會從水沉澱出水垢。使用根據本發明較佳實施態樣之處理組成物，於LSI值為1至3時將不會形成水垢(碳酸鈣不會從水沉澱出)。LSI> 0 indicates the formation of scale, which will form and CaCO3 precipitation. LSI≤0 means that no scale is formed, because there is no possibility of scale formation and the water will dissolve CaCO3. As will be understood by those of ordinary skill in the art, LSI is a driving force indication for scale formation rather than a strict quantitative indication. Scale formation will depend on water characteristics, temperature, and water system operation. However, in the absence of scale inhibitors, scale is usually precipitated from water when the LSI is greater than 0.2. With the treatment composition according to the preferred embodiment of the present invention, scale will not be formed when the LSI value is 1 to 3 (calcium carbonate will not precipitate out of water).

當添加至正在處理之水系統中的水時，用於抑制水垢的根據本發明之較佳組成物產生至少2 ppm活性AAP、至少2 ppm活性HPA、及至少1.5 ppm之其他膦酸。更佳的，當添加至正在處理之水系統中的水時，較佳組成物產生2 ppm至50 ppm AAP、2 ppm至50 ppm HPA、及1.5 ppm至20 ppm之其他膦酸，及最佳係介於3 ppm至30 ppm AAP、2 ppm至20 ppm HPA、及1.5 ppm至10 ppm之其他膦酸。另外，當添加至正在處理之水時，較佳組成物之三種組分總計產生至少6.5 ppm之活性水垢抑制劑。該等成分於高LSI水系統(LSI＞1)中具有出乎意料的經改良腐蝕抑制協同效果，而不需要使用有毒金屬及不會受殺生物劑負面影響。When added to water in the water system being treated, the preferred composition according to the present invention for inhibiting scale produces at least 2 ppm active AAP, at least 2 ppm active HPA, and at least 1.5 ppm of other phosphonic acids. More preferably, when added to the water being treated, the preferred composition produces 2 ppm to 50 ppm AAP, 2 ppm to 50 ppm HPA, and 1.5 ppm to 20 ppm of other phosphonic acids, and most preferably Other phosphonic acids between 3 ppm to 30 ppm AAP, 2 ppm to 20 ppm HPA, and 1.5 ppm to 10 ppm. In addition, when added to the water being treated, the three components of the preferred composition together produce at least 6.5 ppm of active scale inhibitor. These ingredients have unexpectedly improved synergistic effects in corrosion suppression in high LSI water systems (LSI> 1) without the need to use toxic metals and not be adversely affected by biocides.

根據本發明較佳實施態樣之處理組成物提供多合一處理，其能抑制諸如鐵金屬、鋁及其合金、銅及其合金、鋅及其合金、鍍鋅鋼(包括白鏽)、鉛或焊錫等金屬的腐蝕，以及防止礦物水垢形成。該等處理組成物特別可用於諸如開放式再循環系統、封閉式迴路冷卻或加熱系統、及鍋爐等在一年當中不同時間期間或在不同操作條件下(包括用於低LSI(高腐蝕水)及高LSI(高水垢傾向)水二者)會經歷腐蝕、白鏽、及水垢形成的水系統。The treatment composition according to a preferred embodiment of the present invention provides an all-in-one treatment, which can inhibit such as iron metal, aluminum and its alloys, copper and its alloys, zinc and its alloys, galvanized steel (including white rust), lead Corrosion of metals such as solder or solder, and prevention of mineral scale formation. These treatment compositions are particularly useful in applications such as open recirculation systems, closed loop cooling or heating systems, and boilers during different times of the year or under different operating conditions (including for low LSI (highly corrosive water)) And high-LSI (high scale-prone) water) water systems that experience corrosion, white rust, and scale formation.

根據其他較佳實施態樣，用於抑制腐蝕或白鏽或水垢之組成物亦包含下列成分之一或多者：中和胺；氯安定劑，諸如單乙醇胺(MEA)；二次水垢抑制劑(因該組成物本身亦作為水垢抑制劑)及分散劑，諸如聚羧酸鹽聚合物及/或羧酸酯/磺酸酯官能基共聚物(典型實例：聚丙烯酸(PAA)、聚甲基丙烯酸(PMAA)、聚順丁烯二酸(PMA)、以及丙烯酸和2-醯基醯胺基-甲基丙磺酸之共聚物(AA/AMPS)；其他水垢及腐蝕抑制劑、螯合劑；唑腐蝕抑制劑，諸如苯并***、烷基苯并***(甲苯基***)；及/或螢光染料示蹤劑，諸如1,3,6,8-芘四磺酸四鈉鹽(PTSA)。整體組成物較佳包含約2%至15%(重量計)之以胺基酸為基礎之聚合物(諸如聚天冬胺酸)、約2%至10%(重量計)之羥基膦醯基乙酸、及約2%至10%(重量計)之另一膦酸。According to other preferred embodiments, the composition for inhibiting corrosion or white rust or scale also contains one or more of the following components: a neutralizing amine; a chlorinating agent such as monoethanolamine (MEA); a secondary scale inhibitor (Because the composition itself also acts as a scale inhibitor) and dispersants, such as polycarboxylate polymers and / or carboxylate / sulfonate functional copolymers (typical examples: polyacrylic acid (PAA), polymethyl Acrylic acid (PMAA), polymaleic acid (PMA), and copolymers of acrylic acid and 2-fluorenylamido-methylpropanesulfonic acid (AA / AMPS); other scale and corrosion inhibitors, chelating agents; Azole corrosion inhibitors, such as benzotriazole, alkylbenzotriazole (tolyltriazole); and / or fluorescent dye tracers, such as 1,3,6,8-pyridine tetrasulfonic acid tetrasodium salt (PTSA). The overall composition preferably comprises about 2% to 15% by weight of an amino acid-based polymer (such as polyaspartic acid), and about 2% to 10% by weight. Hydroxylphosphonium phosphonoacetic acid, and about 2% to 10% by weight of another phosphonic acid.

根據防止金屬組件腐蝕、鍍鋅鋼組件上之白鏽、及/或水系統中之水垢的一種較佳方法，將如上述根據本發明之較佳實施態樣的處理組成物添加至該水系統。就組合上述AAP、HPA、及另一膦酸之一或多者的組成物而言，用於腐蝕及白鏽抑制之較佳方法包含，視經處理之水化學及該處理組成物中之隨意的組分之數量而定，以20 ppm至600 ppm，或更佳為100至300 ppm之處理組成物的有效進料速率將該組成物進料至水中。較佳的，將充足量之處理組成物添加至該水系統以提供有效活性量之這三種處理組分之一或多者(取決於是處理白鏽或是處理腐蝕與白鏽二者)：至少3 ppm AAP、至少3 ppm HPA、及至少2 ppm之另一膦酸，各為添加至正處理之水系統中的一定量(某體積的)水之濃度。更佳的，當添加至該水系統中之水時，處理組成物係以充足量添加以提供有效活性量之該等組分之一或多者：介於3 ppm至50 ppm AAP、介於3 ppm至50 ppm HPA、及介於2 ppm至20 ppm之另一膦酸。最佳的，當添加至該水系統中之水時，該等有效活性量為5 ppm至30 ppm AAP、3 ppm至20 ppm HPA、及2 ppm至10 ppm其他膦酸。According to a preferred method for preventing corrosion of metal components, white rust on galvanized steel components, and / or scale in water systems, the treatment composition according to the preferred embodiment of the present invention as described above is added to the water system. . With regard to a composition combining one or more of the above-mentioned AAP, HPA, and another phosphonic acid, a preferred method for corrosion and white rust suppression includes, depending on the treated water chemistry and the optional nature of the treated composition Depending on the number of components, the composition is fed into water at an effective feed rate of the treatment composition from 20 ppm to 600 ppm, or more preferably from 100 to 300 ppm. Preferably, a sufficient amount of the treatment composition is added to the water system to provide an effective active amount of one or more of the three treatment components (depending on whether to treat white rust or both corrosion and white rust): at least Each of 3 ppm AAP, at least 3 ppm HPA, and at least 2 ppm of another phosphonic acid is the concentration of a certain amount (of a volume) of water added to the water system being treated. More preferably, when water is added to the water system, the treatment composition is added in a sufficient amount to provide an effective active amount of one or more of these components: between 3 ppm to 50 ppm AAP, between 3 ppm to 50 ppm HPA, and another phosphonic acid between 2 ppm and 20 ppm. Optimally, when added to the water in the water system, the effective active amounts are 5 ppm to 30 ppm AAP, 3 ppm to 20 ppm HPA, and 2 ppm to 10 ppm other phosphonic acids.

就組合上述AAP、HPA、及另一膦酸之一或多者的組成物而言，用於水垢抑制之較佳方法包含，視經處理之水化學及該處理組成物中之隨意的組分之數量而定，以20 ppm至600 ppm，或更佳為50至300 ppm之處理組成物的有效進料速率將該組成物進料至水中。較佳的，將充足量之處理組成物添加至該水系統以提供有效活性量之這三種處理組分之一或多者：至少2 ppm AAP、至少2 ppm HPA、及至少1.5 ppm之另一膦酸，各為添加至正處理之水系統中的該定量(該體積的)水之濃度。更佳的，處理組成物係以充足量添加以提供有效活性量之這三種處理組分：2 ppm至50 ppm AAP、2 ppm至50 ppm HPA、及1.5 ppm至20 ppm之另一膦酸，各為添加至正處理之水系統中的定量水之濃度。最佳的，當添加至該水系統中之水時，處理組成物係以充足量添加以提供有效活性量之這三種組分：介於3 ppm至30 ppm AAP、介於2 ppm至20 ppm HPA、及介於1.5 ppm至10 ppm之另一膦酸。With regard to a composition combining one or more of the above-mentioned AAP, HPA, and another phosphonic acid, a preferred method for scale inhibition comprises, depending on the treated water chemistry and optional components in the treated composition Depending on the amount, the composition is fed into water at an effective feed rate of the treatment composition from 20 ppm to 600 ppm, or more preferably from 50 to 300 ppm. Preferably, a sufficient amount of the treatment composition is added to the water system to provide an effective active amount of one or more of the three treatment components: at least 2 ppm AAP, at least 2 ppm HPA, and at least 1.5 ppm of the other Phosphonic acid, each of which is the concentration (of that volume) of water concentration added to the water system being treated. More preferably, the treatment composition is added in sufficient amounts to provide effective active amounts of these three treatment components: 2 ppm to 50 ppm AAP, 2 ppm to 50 ppm HPA, and 1.5 ppm to 20 ppm of another phosphonic acid, Each is the concentration of quantitative water added to the water system being treated. Optimally, when added to the water in the water system, the treatment composition is added in sufficient amounts to provide an effective active amount of these three components: between 3 ppm to 30 ppm AAP, between 2 ppm to 20 ppm HPA, and another phosphonic acid between 1.5 ppm and 10 ppm.

進行數個實驗室試驗以測試根據本發明之各種不同組成物的有效性。根據本發明之組成物係使用旋轉器試驗評估，以模擬水系統中於金屬組件上的流動水。各旋轉器試驗設置包含具有四個金屬試片(使用軟鋼試片(C1010)及銅試片(CDA 11))之不鏽鋼水容器，於各容器中該等金屬試片係從旋轉軸懸垂之支架懸吊於該水中。該軸以147轉/分鐘旋轉不鏽鋼容器中之水中的試片，這表示流率為3至5 ft/s，其取決於試片距該旋轉軸之中心的距離。用於各旋轉器試驗之初始體積的水的特性為通常在水系統中發現之腐蝕性、低硬度水。所使用之水具有下表1所顯示的特性。Several laboratory tests were performed to test the effectiveness of the various compositions according to the invention. The composition according to the present invention was evaluated using a spinner test to simulate flowing water on a metal component in a water system. Each rotator test set includes a stainless steel water container with four metal test pieces (using a mild steel test piece (C1010) and a copper test piece (CDA 11)). In each container, the metal test pieces are brackets suspended from the rotation axis. Hang in the water. The shaft rotates the test piece in water in a stainless steel container at 147 rpm, which indicates a flow rate of 3 to 5 ft / s, depending on the distance of the test piece from the center of the rotating shaft. The characteristics of the initial volume of water used in each spinner test are corrosive, low hardness water commonly found in water systems. The water used has the characteristics shown in Table 1 below.

於各旋轉器試驗期間，該水係經曝氣並維持於120F之固定溫度及固定體積(當水位降至低於感測器水準時自動添加去離子水來補償任何蒸發)。標準試驗期間為48小時。During each spinner test, the water system was aerated and maintained at a fixed temperature and fixed volume of 120F (deionized water is automatically added to compensate for any evaporation when the water level drops below the sensor level). The standard test period is 48 hours.

使用該旋轉器試驗設置，比較無任何添加之鋅或錫的根據本發明較佳實施態樣之組成物(包括AAP、HPA、及另一膦酸-HEDP之實施例編號1至3)(如表2所示)與僅使用鋅之組成物(比較例4)、僅使用錫之組成物(比較例5)、僅使用AAP之組成物(比較例6)、僅使用HPA之組成物(比較例7)、HPA與錫組合之組成物(比較例8)、及AAP與錫組合之組成物(比較例9)(均如表3所示)作為主要抑制劑。各種處理之ppm濃度為添加至旋轉器試驗容器中之定量水中時的濃度。比較具有鋅或錫之組成物與不具鋅或錫之組成物。鋅通常用作具有高度腐蝕性水(低LSI)之水系統中的腐蝕抑制劑。然而，因毒性問題而不希望使用彼，且其使用在許多地點面臨管制。錫已經推展並獲得專利作為鋅之無毒替代品，但其較昂貴。除了表2及3中所列之主要腐蝕抑制劑組分以外，全部試驗均於存在4 ppm活性AA/AMPS共聚物及4 ppm活性TTA之下進行。該等成分係添加至各旋轉器試驗設置之水中以提供該等濃度水準。於不同抑制劑存在之旋轉器試驗之後的軟鋼試片之腐蝕及孔蝕水準係表示於圖1。Use this rotator test setup to compare the composition according to the preferred embodiment of the present invention (including AAP, HPA, and another phosphonic acid-HEDP embodiment numbers 1 to 3) without any added zinc or tin (such as Table 2) with a composition using only zinc (Comparative Example 4), a composition using only tin (Comparative Example 5), a composition using only AAP (Comparative Example 6), and a composition using only HPA (Comparative Example 7), a combination of HPA and tin (Comparative Example 8), and a combination of AAP and tin (Comparative Example 9) (all shown in Table 3) were used as main inhibitors. The ppm concentration of each treatment is the concentration when it is added to the quantitative water in the spinner test container. Compare compositions with or without zinc or tin. Zinc is commonly used as a corrosion inhibitor in water systems with highly corrosive water (low LSI). However, the use of the other is not desirable due to toxicity issues, and its use is regulated in many locations. Tin has been developed and patented as a non-toxic alternative to zinc, but it is more expensive. With the exception of the major corrosion inhibitor components listed in Tables 2 and 3, all tests were performed in the presence of 4 ppm active AA / AMPS copolymer and 4 ppm active TTA. These ingredients are added to the water in each spinner test setup to provide these levels of concentration. Corrosion and pitting levels of mild steel test pieces after rotator tests with different inhibitors are shown in Figure 1.

旋轉器試驗係用各組成物以等於約3ft/sec之流率以及以等於約5ft/sec之流率進行。亦進行無任何處理之控制組試驗以供比較。圖1顯示使用控制組及實施例組成物編號1至9之各旋轉器試驗之後的代表軟鋼試片之照片。試片上之腐蝕及孔蝕數量係顯示於照片中。可看出，控制組試片顯示廣泛的腐蝕(照片上之深區區域)。使用根據本發明較佳實施態樣之組成物(實施例編號2至3)之試片，顯示少許(若有任何腐蝕或孔蝕的話)腐蝕或孔蝕(照片上非常少數的深色區域)。使用含有根據本發明較佳實施態樣之全部三種組分以供腐蝕抑制但只含有2.5 ppm HPA(低於至少3 ppm之更佳量)的實施例編號1之試片顯示比控制組及比較例(比較例編號4至9)改善的結果，但顯示比使用5 ppm之HPA的實施例編號2至3略高的腐蝕。使用比較例(比較例編號4至9)之試片明顯優於控制組，但確實顯示大於使用實施例編號1至3之腐蝕及孔蝕跡象。根據該等結果，看來AAP、HPA、及另一膦酸(該等實例中為HEDP)之組合協同地相互作用以提供經改良之腐蝕控制，而不需要使用鋅、錫或其他受管制金屬。The spinner test was performed with each composition at a flow rate equal to about 3 ft / sec and at a flow rate equal to about 5 ft / sec. Control group tests without any treatment were also performed for comparison. FIG. 1 shows a photograph of a representative soft steel test piece after each of the spinner tests using the control group and the composition numbers of the examples. The amount of corrosion and pitting on the test piece is shown in the photo. It can be seen that the test piece of the control group showed extensive corrosion (deep area on the photo). Test pieces using the composition according to the preferred embodiment of the present invention (Example Nos. 2 to 3) showed little (if any corrosion or pitting) corrosion or pitting (very few dark areas on the photo) . The test piece of Example No. 1 using the test piece of Example No. 1 containing all three components for corrosion inhibition according to the preferred embodiment of the present invention but containing only 2.5 ppm of HPA (a better amount of less than at least 3 ppm) was shown and compared Examples (Comparative Examples Nos. 4 to 9) showed improved results but showed slightly higher corrosion than Examples Nos. 2 to 3 using 5 ppm of HPA. The test pieces using the comparative examples (comparative example numbers 4 to 9) were significantly better than the control group, but did show signs of corrosion and pitting corrosion that were greater than those using the example numbers 1 to 3. Based on these results, it appears that the combination of AAP, HPA, and another phosphonic acid (HEDP in these examples) interact synergistically to provide improved corrosion control without the use of zinc, tin, or other regulated metals .

一些先前技術水處理腐蝕抑制組成物於同一系統中使用氧化性殺生物劑以防止生物生長時未提供有效保護。最廣泛使用之氧化性殺生物劑為氯及經安定溴。在經安定溴殺生物劑組成物(市售之Chem-Aqua 42171)存在下使用實施例組成物編號2及3並與比較例組成物編號4(只有鋅)及7(只有HPA)比較而進行額外的旋轉器腐蝕試驗。因實施例組成物4及7於比較例之旋轉器試驗中顯示最佳結果，故選擇實施例組成物4及7。比較例編號4及7二者於低LSI水中均表現得相當好，但如下文討論，當添加殺生物劑時明顯惡化。再者，比較例編號4以鋅為主，因毒性顧慮之故，其不受歡迎。如先前試驗，該等試驗係於4 ppm活性AA/AMPS共聚物及4 ppm活性TTA存在下進行。各旋轉器試驗開始時(於添加腐蝕抑制組成物且試驗開始之後)添加40 ppm殺生物劑之瞬間劑量(slug dose)以產生約1 ppm FHR(游離鹵素殘留物)。Some prior art water treatment corrosion inhibiting compositions do not provide effective protection when organisms are used in the same system to prevent biological growth. The most widely used oxidizing biocides are chlorine and diazepam. Example composition numbers 2 and 3 were used in the presence of a stable brominated biocide composition (commercially available Chem-Aqua 42171) and compared with comparative example composition numbers 4 (only zinc) and 7 (only HPA). Additional spinner corrosion test. Since the composition of Examples 4 and 7 showed the best results in the spinner test of the Comparative Example, the compositions of Examples 4 and 7 were selected. Both Comparative Examples Nos. 4 and 7 performed quite well in low LSI water, but as discussed below, they deteriorated significantly when biocides were added. Furthermore, Comparative Example No. 4 is mainly zinc, which is unwelcome due to toxicity concerns. As previously tested, these tests were performed in the presence of 4 ppm active AA / AMPS copolymer and 4 ppm active TTA. At the beginning of each rotator test (after the corrosion inhibitor composition was added and the test was started), an instant slug dose of 40 ppm biocide was added to produce approximately 1 ppm FHR (free halogen residue).

圖2顯示於殺生物劑存在下使用實施例組成物之各旋轉器試驗之後的代表性軟鋼試片之照片。可看出，使用根據本發明較佳實施態樣之組成物(實施例編號2至3)的試片顯示少許(若有任何腐蝕或孔蝕的話)腐蝕或孔蝕，表示根據本發明之較佳組成物的功能不受殺生物劑負面影響。使用比較例(比較例編號4及7)之試片顯示比使用實施例編號2至3實質上更嚴重之腐蝕。注意到比較例編號7係使用HPA及HEDP，無任何AAP，其在無殺生物劑的情況下顯示良好結果，但於添加殺生物劑時發生明顯更嚴重的腐蝕。具有AAP及HEDP而無任何HPA之對照組成物(比較例編號6)在無殺生物劑的情況下表現很差(圖1上)，因預期結果會比圖1中更差，故其未用殺生物劑進行試驗。根據該等結果，顯示AAP、HPA、及另一膦酸之組合一起協同地相互作用，以即使於存在殺生物劑時亦提供經改良腐蝕控制以及顯示優於單獨使用HPA之經改良結果。Figure 2 shows a photograph of a representative mild steel test piece after each spinner test using the composition of the example in the presence of a biocide. It can be seen that the test pieces using the composition according to the preferred embodiment of the present invention (Example Nos. 2 to 3) show a little (if there is any corrosion or pitting) corrosion or pitting, indicating that the comparison according to the present invention The function of the optimal composition is not negatively affected by the biocide. The test pieces using Comparative Examples (Comparative Example Numbers 4 and 7) showed substantially more severe corrosion than those using Example Numbers 2 to 3. Note that Comparative Example No. 7 uses HPA and HEDP without any AAP, which shows good results without biocide, but significantly more severe corrosion occurs when biocide is added. The control composition with AAP and HEDP without any HPA (Comparative Example No. 6) performed poorly without biocide (on Fig. 1) and was not used because the expected result would be worse than in Fig. 1 Biocides are tested. Based on these results, it was shown that the combination of AAP, HPA, and another phosphonic acid interacted synergistically to provide improved corrosion control even in the presence of biocides and to show improved results superior to using HPA alone.

軟鋼試片之腐蝕速率係從試片之重量損失測量及計算。無添加殺生物劑及添加殺生物劑二者之旋轉器試驗的結果係彙總於表4。關於腐蝕模式之資訊，特別是存在孔蝕(其於許多應用中相當重要，以及已知一些腐蝕抑制劑(包括單獨使用之HPA)為不良的抗孔蝕保護劑)亦包括於表4。最佳的，即使於存在殺生物劑的情況下，根據本發明實施態樣之腐蝕抑制劑組成物獲致就腐蝕而言為3 MPY或更低之腐蝕速率。The corrosion rate of the mild steel test piece is measured and calculated from the weight loss of the test piece. The results of the spinner tests without biocide and biocide are summarized in Table 4. Information on corrosion modes, in particular the presence of pitting corrosion (which is important in many applications, and some known corrosion inhibitors (including HPA used alone) as poor anti-pitting protection agents) are also included in Table 4. Optimally, even in the presence of a biocide, the corrosion inhibitor composition according to embodiments of the present invention results in a corrosion rate of 3 MPY or less in terms of corrosion.

根據本發明較佳實施態樣之組成物含有來自HPA及來自該等實施例中所使用的其他膦酸(HEDP)之有機磷酸鹽。於殺生物劑存在下，有機磷酸鹽經常回復成正磷酸鹽，其於防止腐蝕或水垢方面不太良好，以及亦會造成形成磷酸鈣水垢的問題。當使用AAP、HPA、及HEDP(或另一膦酸)之組合作為根據本發明較佳實施態樣的腐蝕抑制劑時，實驗上未偵測到有機磷酸鹽回復成正磷酸鹽。於混合組成物時，以及於48小時之後再次測試來自組成物實施例編號2及3以及比較例編號7之樣本中正磷酸鹽的存在。結果列於下表5。使用AAP、HPA、及HEDP(以及如上述含有AA/AMPS及TTA)之實施例編號2及3顯示在48小時期間內正磷酸鹽增加非常少，但含有HPA及HEDP(以及如上述含有AA/AMPS及TTA)但無AAP之比較例編號7顯示大幅增加。The composition according to a preferred embodiment of the present invention contains organic phosphates from HPA and other phosphonic acids (HEDP) used in these examples. In the presence of biocides, organophosphates often return to orthophosphate, which is not very good at preventing corrosion or scale, and it also causes the problem of calcium phosphate scale formation. When a combination of AAP, HPA, and HEDP (or another phosphonic acid) is used as a corrosion inhibitor in accordance with a preferred embodiment of the present invention, it is experimentally not detected that the organic phosphate returns to orthophosphate. While mixing the composition, and again after 48 hours, the samples from Composition Examples 2 and 3 and Comparative Example 7 were tested for the presence of orthophosphate. The results are shown in Table 5 below. Example numbers 2 and 3 using AAP, HPA, and HEDP (and containing AA / AMPS and TTA as described above) show very little orthophosphate increase over a 48 hour period, but containing HPA and HEDP (and containing AA / as described above) AMPS and TTA) but Comparative Example No. 7 without AAP showed a significant increase.

根據另一個較佳實施態樣，如表6所列之水處理組成物(其與前文測試之實施例2相同)於廣範圍之LSI值(-2.5至＞3)中及於殺生物劑存在下於水系統中有效抑制腐蝕及水垢。According to another preferred embodiment, the water treatment composition as listed in Table 6 (which is the same as Example 2 previously tested) is in a wide range of LSI values (-2.5 to> 3) and is present in the biocide It can effectively inhibit corrosion and scale in the water system.

較佳亦將NaOH及/或KOH添加至根據本發明一實施態樣之組成物。該等成分通常添加至水處理調配物以中和酸及使最終組成物的pH達到所希望水準。大部分該組成物將具有pH＞8，一些具有pH＞12。於使用TTA之組成物(如採用根據本發明組成物之較佳實施態樣)中，希望該組成物具有較高pH(＞11)以確保TTA之溶解度，TTA於較低pH下的溶解度非常差。Preferably, NaOH and / or KOH is also added to the composition according to an embodiment of the present invention. These ingredients are usually added to water treatment formulations to neutralize acids and bring the pH of the final composition to the desired level. Most of this composition will have a pH> 8, and some will have a pH> 12. In the composition using TTA (such as the preferred embodiment of the composition according to the present invention), it is desirable that the composition has a higher pH (> 11) to ensure the solubility of TTA, and the solubility of TTA at lower pH is very difference.

進行於低LSI水中之額外旋轉器試驗以測試各種濃度之根據本發明較佳實施態樣用於抑制腐蝕的處理組成物之有效性。將上述相同旋轉器試驗參數及低LSI水(表1)用於該等測試。於添加至旋轉器試驗水時該等成分之濃度以及該等試驗之結果係於下文示於表7。圖3顯示於試驗完成後每一組成物之測試試片(以3 ft/sec之流率測試)的照片。An additional spinner test in low LSI water was performed to test the effectiveness of the treatment composition for inhibiting corrosion at various concentrations according to the preferred embodiment of the present invention. The same spinner test parameters and low LSI water (Table 1) described above were used for these tests. The concentrations of these ingredients when added to the spinner test water and the results of these tests are shown in Table 7 below. Figure 3 shows a photograph of a test piece (tested at a flow rate of 3 ft / sec) of each composition after the test was completed.

比較例10、13、及15使用AAP、HPA、及HEDP但數量少於較佳濃度。該等實例顯示於低抑制劑含量時腐蝕增加(以及比較例10顯示中度孔蝕)。根據本發明較佳實施態樣之實施例編號11至12、14、及16在不同隨意的組分及變化濃度以及AAP對HPA之比顯示良好性能(低腐蝕速率及無孔蝕)。該等實例亦顯示從HEDP改成PBTC(實施例16)以及二次螯合物減少不影響根據本發明較佳實施態樣之組成物的腐蝕抑制性能。實施例編號17使用AAP及HPA而無第二膦酸，與'023專利中所述之組成物相似。其顯示於低LSI水中控制腐蝕有改良結果，但不如根據本發明較佳實施態樣之實施例般良好。Comparative Examples 10, 13, and 15 used AAP, HPA, and HEDP but the amount was less than the preferred concentration. These examples show increased corrosion at low inhibitor content (and Comparative Example 10 shows moderate pitting). The embodiment numbers 11 to 12, 14, and 16 according to the preferred embodiment of the present invention show good performance (low corrosion rate and no pitting corrosion) at different optional components and varying concentrations and the ratio of AAP to HPA. These examples also show that the change from HEDP to PBTC (Example 16) and the reduction of secondary chelates do not affect the corrosion inhibition performance of the composition according to the preferred embodiment of the present invention. Example No. 17 uses AAP and HPA without a second phosphonic acid, similar to the composition described in the '023 patent. It shows improved results in controlling corrosion in low LSI water, but not as good as the embodiment according to the preferred embodiment of the present invention.

進行額外的旋轉器試驗以比較如'023專利中所揭示使用AAP及PBTC之組成物與根據本發明較佳實施態樣之組成物。試驗設置係與上述相同，使用低LSI水、軟鋼(C1010)試片、及3 ft/sec流率。結果係示於下表8。An additional spinner test was performed to compare the composition using AAP and PBTC as disclosed in the '023 patent with a composition according to a preferred embodiment of the present invention. The test setup was the same as above, using low LSI water, mild steel (C1010) test pieces, and a flow rate of 3 ft / sec. The results are shown in Table 8 below.

可看出，採用AAP、HPA、及第二膦酸(HEDP或PBTC)之根據本發明較佳實施態樣之實例(實施例編號20、21、及12)顯示的腐蝕抑制結果遠優於僅使用AAP及PBTC(無任何HPA)之比較例。亦注意到，即使使用20 ppm總抑制劑(AAP及PBTC)，比較例編號18至19亦造成大於3 MPY之腐蝕速率，其高於使用實質上較少總抑制劑之根據本發明較佳組成物可獲致的腐蝕速率，諸如實施例編號11，其僅使用13.5 ppm總抑制劑(AAP、HPA、HEDP)，腐蝕速率為2.3 MPY，以及實施例編號16，其僅使用12.6 ppm總抑制劑(AAP、HPA、PBTC)，腐蝕速率為2.1 MPY。另外，比較例編號18至19之腐蝕速率與比較例編號13及15中之腐蝕速率相當，比較例編號13及15使用AAP、HPA、及第二膦酸，但獲致比較例編號18至19中之結果所需的抑制劑總量(總共20 ppm)遠高於編號13及15中所需的抑制劑總量(分別為總共10.76及15.76 ppm)。該等實驗的結果顯示添加第二膦酸組合上AAP及HPA會提供即使使用較少總抑制劑以及即使存在殺生物劑時亦改善腐蝕抑制之出乎意料的協同效果。It can be seen that the examples (Example Nos. 20, 21, and 12) according to the preferred embodiment of the present invention using AAP, HPA, and a second phosphonic acid (HEDP or PBTC) show much better corrosion suppression results than only Comparative example using AAP and PBTC (without any HPA). It is also noted that even with the use of 20 ppm total inhibitors (AAP and PBTC), Comparative Examples Nos. 18 to 19 caused corrosion rates greater than 3 MPY, which is higher than the preferred composition according to the invention using substantially less total inhibitors Corrosion rates that can be obtained, such as Example No. 11, which uses only 13.5 ppm total inhibitors (AAP, HPA, HEDP), a corrosion rate of 2.3 MPY, and Example No. 16, which uses only 12.6 ppm total inhibitors ( AAP, HPA, PBTC), the corrosion rate is 2.1 MPY. In addition, the corrosion rates of Comparative Examples Nos. 18 to 19 are comparable to those of Comparative Examples Nos. 13 and 15. Comparative Examples Nos. 13 and 15 used AAP, HPA, and the second phosphonic acid, but obtained Comparative Examples Nos. 18 to 19 As a result, the total amount of inhibitor required (total of 20 ppm) is much higher than the total amount of inhibitor required for Nos. 13 and 15 (total of 10.76 and 15.76 ppm, respectively). The results of these experiments show that the addition of AAP and HPA on the combination of a second phosphonic acid provides an unexpected synergistic effect of improving corrosion inhibition even with less total inhibitors and even in the presence of biocides.

本領域具有通常知識者將暸解在本發明範疇內，其他適用或等效化學化合物以及其他處理化合物(包括其他腐蝕抑制劑)可取代上述成分之任一者或添加至上述成分之任一者。根據本發明實施態樣之組成物於廣範圍LSI值(包括LSI＜0)內有效抑制水系統中之金屬組件上的腐蝕，且不需要使用受管制有毒金屬。該等組成物也於在水系統中通常發現的較高pH值(7至9)下有效，諸如冷卻塔及鍋爐，然而一些先前技術抑制劑於此種pH水準時無效或其有效性降低(例如聚天冬胺酸/二價錫鹽處理只於pH 5至7有效)。該等根據本發明之組成物亦防止有機磷酸鹽回復成正磷酸鹽以在殺生物劑存在下維持有效性。Those having ordinary skill in the art will understand that within the scope of the present invention, other applicable or equivalent chemical compounds and other treatment compounds (including other corrosion inhibitors) may replace or be added to any of the aforementioned ingredients. The composition according to the embodiment of the present invention effectively inhibits corrosion on metal components in water systems within a wide range of LSI values (including LSI <0), and does not require the use of regulated toxic metals. These compositions are also effective at higher pH values (7 to 9) commonly found in water systems, such as cooling towers and boilers, however some prior art inhibitors are ineffective or less effective at such pH levels ( For example, polyaspartic acid / divalent tin salt treatment is only effective at pH 5 to 7). These compositions according to the present invention also prevent organic phosphates from returning to orthophosphate to maintain effectiveness in the presence of biocides.

進行使用電化學方法之其他實驗以測試根據本發明之組成物的白鏽防止。下表9中之結果顯示組合HPA及AAP(無另一膦酸)相較於使用每一個別組分(單獨HPA及單獨AAP)於減少白鏽形成之協同效果。使用鋅電極於0.1 M碳酸鈉溶液中進行循環伏安法試驗。氧化之量度為在觀察到之氧化曲線峰下方的區域；該區域愈低則發生愈少氧化，意指較低腐蝕速率。結果係具有標準差之6至10個實驗的平均值。Other experiments using electrochemical methods were performed to test the white rust prevention of the composition according to the present invention. The results in Table 9 below show the synergistic effect of combining HPA and AAP (without another phosphonic acid) in reducing white rust formation compared to the use of each individual component (HPA and AAP alone). Cyclic voltammetry was performed using a zinc electrode in a 0.1 M sodium carbonate solution. The measure of oxidation is the area below the peak of the observed oxidation curve; the lower the area, the less oxidation occurs, meaning a lower corrosion rate. Results are the average of 6 to 10 experiments with standard deviation.

於不鏽鋼容器中於已知在鍍鋅表面上形成白鏽之高鹼度水中進行額外的旋轉器腐蝕試驗，以測試根據本發明較佳實施態樣之組成物對於防止白鏽形成的有效性。該等試驗中之水化學、高鹼度合成水的特性係於下表10中詳細列出。將四個尺寸為1.0x4.0x0.02in之熱浸鍍鋅鋼試片(HDG G70)安裝於各容器中於從旋轉軸懸垂之支架上，該旋轉軸係以147轉/分鐘，這表示流率為3至5 ft/s，此係視試片距旋轉軸中心之距離而定。在試驗期間該水係經曝氣並維持於120F之固定溫度及固定體積(當水位降至低於感測器水準時自動添加DI水來補償任何蒸發)。標準試驗期間為48小時。在兩個比較例及三個根據本發明較佳組成物之實施例中所使用的活性成分以及腐蝕速率一起列於表11。An additional spinner corrosion test was performed in a stainless steel container in high alkalinity water known to form white rust on galvanized surfaces to test the effectiveness of the composition according to the preferred embodiment of the present invention to prevent the formation of white rust. The characteristics of water chemistry and high-basicity synthetic water in these tests are detailed in Table 10 below. Four hot-dip galvanized steel test pieces (HDG G70) with a size of 1.0x4.0x0.02in were installed in each container on a support hanging from a rotating shaft, which was 147 rpm, which indicates the flow The rate is 3 to 5 ft / s, depending on the distance of the test piece from the center of the rotation axis. During the test, the water system was aerated and maintained at a fixed temperature and fixed volume of 120F (DI water was automatically added to compensate for any evaporation when the water level dropped below the sensor level). The standard test period is 48 hours. The active ingredients used in two comparative examples and three examples of preferred compositions according to the present invention are shown in Table 11 together with the corrosion rates.

為了使用重量損失法計算腐蝕速率，根據標準製程將來自該等試驗之鍍鋅試片浸入濃乙酸銨中並予以沖洗來清潔該等試片。圖4顯示使用表12中所述之組成物進行旋轉器試驗之後的鍍鋅試片在清潔之前與清潔之後二者情況的照片。於清潔之前該等試片上的可見白色沉積物為白鏽。於清潔之後該等試片上可見到因腐蝕所致之鍍鋅層損壞，顯示為深色斑點。空白(比較例22-無處理)試片完全覆蓋白色沉積物，且於清潔之後大部分鍍鋅層係以可見的軟鋼腐蝕被移除。經HPA及HEDP而無以胺基酸為基礎之聚合物處理的試片(比較例23)顯示大量白鏽形成，但比起控制組(比較例22)仍然大幅改善。明顯較佳結果係採用實施例24至26中之組成物獲得。採用使用AAP、大於3 ppm之HPA及第二膦酸(HEDP)的實施例24獲致最佳結果。雖然使用HPA於抑制軟鋼腐蝕相當重要，但使用其於白鏽處理是隨意的。從實施例26可看出，使用AAP及HEDP而無HPA的結果幾乎與三者組合一樣良好。因此，根據本發明用於處理白鏽之較佳組成物包含2至15%之以胺基酸為基礎之聚合物、0至10%之HPA、及0至10%之第二膦酸。較佳的，根據本發明之處理組成物中活性的以胺基酸為基礎之聚合物數量為至少3 ppm，更佳為3 ppm至50 ppm，及最佳為5 ppm至30 ppm，全為添加至正處理之水系統中的一定量水之濃度。更佳的，AAP係與至少3 ppm，更佳為3 ppm至50 ppm，及最佳為約3 ppm至20 ppm之量的HPA及/或至少2 ppm，更佳為2 ppm至20 ppm，及最佳為約2 ppm至10 ppm之量的另一膦酸合併使用。To calculate the corrosion rate using the weight loss method, the galvanized test pieces from these tests were immersed in concentrated ammonium acetate and rinsed to clean the test pieces according to standard procedures. FIG. 4 shows photographs of the galvanized test piece after the spinner test using the composition described in Table 12 before and after cleaning. The visible white deposits on the test pieces before cleaning were white rust. After cleaning, damage to the galvanized layer due to corrosion was seen on these test pieces, which appeared as dark spots. The blank (Comparative Example 22-no treatment) test piece was completely covered with white deposits, and most of the galvanized layer was removed after cleaning with visible mild steel corrosion. A test piece (Comparative Example 23) treated with HPA and HEDP without an amino acid-based polymer showed a large amount of white rust formation, but still significantly improved compared to the control group (Comparative Example 22). Obviously better results were obtained using the compositions of Examples 24 to 26. Best results were obtained using Example 24 using AAP, HPA greater than 3 ppm, and second phosphonic acid (HEDP). Although the use of HPA to suppress corrosion of mild steel is important, its use in white rust treatment is arbitrary. It can be seen from Example 26 that the results using AAP and HEDP without HPA are almost as good as the combination of the three. Therefore, a preferred composition for treating white rust according to the present invention comprises 2 to 15% of an amino acid-based polymer, 0 to 10% of HPA, and 0 to 10% of a second phosphonic acid. Preferably, the amount of the active amino-based polymer in the treatment composition according to the present invention is at least 3 ppm, more preferably 3 ppm to 50 ppm, and most preferably 5 ppm to 30 ppm, all being The concentration of a certain amount of water added to the water system being treated. More preferably, AAP is associated with at least 3 ppm, more preferably 3 ppm to 50 ppm, and most preferably about 3 ppm to 20 ppm of HPA and / or at least 2 ppm, more preferably 2 ppm to 20 ppm, And another phosphonic acid, preferably in an amount of about 2 ppm to 10 ppm, is used in combination.

根據本發明為了處理白鏽，較佳係以前文指示之重量範圍，使用羥基膦醯基乙酸與以胺基酸為基礎之聚合物二者，及更佳係與第二膦酸併用，但亦已發現使用以胺基酸為基礎之聚合物或羥基膦醯基乙酸而無該其他者係於抑制白鏽時是有利的。In order to treat white rust according to the present invention, it is preferred to use the weight range previously indicated, using both hydroxyphosphonophosphonoacetic acid and an amino acid-based polymer, and more preferably in combination with a secondary phosphonic acid, It has been found advantageous to use amino acid-based polymers or hydroxyphosphinophosphonoacetic acid without the other being tied to inhibiting white rust.

亦進行使用根據本發明較佳實施態樣之組成物的先導冷卻塔水垢試驗以測試抑制高LSI水(LSI＞1)中的水垢形成能力。該冷卻塔水垢試驗的目的係測定該塔可操作而無水垢的循環次數以及於隨著循環次數增加具有形成水垢特性之典型水中的處理之LSI極限。冷卻塔先導試驗使用四個熱傳表面棒以及於800瓦操作之DATS(沉積物累積測試系統)。濃縮倍數(COC)的數目係計算為冷卻塔水中之任何離子的濃度對補充(起始)水中之同種離子的濃度之比。傳導率亦可用以計算COC。希望於儘可能高之COC下操作以減少用水量。通常，藉由測量水傳導率，當傳導率提高超過設定極限時使該系統排水且添加更多補充水而使冷卻塔中之COC維持在某水準。冷卻塔先導試驗中所使用之水的初始體積為冷卻塔水系統中常用之具有100 ppm鹼度(以CaCO3計)及100 ppm鈣硬度(以CaCO3計)的高LSI水之特性。所使用之水具有下表12所顯示的特性。A pilot cooling tower scale test using a composition according to a preferred embodiment of the present invention was also performed to test the ability to suppress scale formation in high LSI water (LSI> 1). The purpose of the cooling tower scale test is to determine the number of cycles in which the tower can be operated without scale and the LSI limit in the treatment of typical water with scale formation characteristics as the cycle times increase. The cooling tower pilot test used four heat transfer surface rods and a DATS (Sediment Accumulation Test System) operating at 800 watts. The number of concentration multiples (COC) is calculated as the ratio of the concentration of any ion in the cooling tower water to the concentration of the same ion in the makeup (starting) water. Conductivity can also be used to calculate COC. It is desirable to operate at the highest possible COC to reduce water consumption. Generally, by measuring the water conductivity, when the conductivity increases beyond a set limit, the system is drained and more makeup water is added to keep the COC in the cooling tower at a certain level. The initial volume of water used in the cooling tower pilot test is the characteristic of high LSI water with 100 ppm alkalinity (calculated as CaCO3) and 100 ppm calcium hardness (calculated as CaCO3) commonly used in cooling tower water systems. The water used has the characteristics shown in Table 12 below.

水垢顯示在當HTR(熱傳阻力)突然提高至高於穩定水準且超過12x10-6 ℃m2 /W及/或加熱器乾淨%降至低於97%(從熱傳係數結垢(UF)及乾淨(UC)值測定，其中UF=1/HTR形成水垢+UC，而乾淨度%=UF/UC x 100)的時間點。LSI極限(於將會形成水垢時的LSI測量)亦可藉由監測水化學之變化、水濁度及目視觀察水垢形成來測定。基於HTR及水化學數據，發現根據表6之組成物在100 ppm濃度(當添加至先導冷卻塔系統中之水時)使冷卻塔之操作極限提高至6 COC及3.2之LSI。先導冷卻塔於開始形成水垢之前係操作7天。試驗係以高形成水垢性水、LSI約1開始，並循環至6 COC，其於水垢開始形成之前LSI提高至3.2。The scale is displayed when the HTR (heat transfer resistance) suddenly rises above the stable level and exceeds 12x10 -6 ℃ m 2 / W and / or the heater clean% decreases to less than 97% (from the heat transfer coefficient scaling (UF) and Cleanliness (UC) value determination, where UF = 1 / HTR forms scale + UC, and cleanliness% = UF / UC x 100). The LSI limit (measurement of LSI when scale will form) can also be determined by monitoring changes in water chemistry, water turbidity, and visual observation of scale formation. Based on HTR and water chemistry data, it was found that the composition according to Table 6 increased the operating limit of the cooling tower to 6 COC and 3.2 LSI at a concentration of 100 ppm (when added to the water in the pilot cooling tower system). The pilot cooling tower was operated for 7 days before the scale started to form. The test was started with highly scale-forming water, LSI of about 1, and circulated to 6 COC, which increased to 3.2 before scale started to form.

為了進行比較，典型先前技術水垢處理，諸如同樣為100 ppm濃度之Chem-Aqua 31155(其含有PBTC、甲苯基***鈉、聚丙烯酸鈉、聚順丁烯二酸(鈉鹽)及氫氧化鈉)允許冷卻塔操作僅為3 COC(為於僅2.6之LSI極限)。即使Chem-Aqua 31155之處理濃度加倍(200 ppm)，冷卻塔中之COC僅能提高至3.4，LSI極限為2.85，其遠低於使用本發明組成物之較佳實施態樣所獲致的COC提高及LSI極限。在使用50 ppm(當添加至先導冷卻塔系統中之水時)前面先導冷卻塔水垢試驗中所使用之相同處理組成物的其他實驗中，於水垢開始形成之前該系統達到4.3 COC且LSI為2.84。該等結果進一步表示該三組分配方在水垢防止方面遠優於先前技術之含有PBTC的配方，即使是當該等先前技術配方係以2至4倍濃度使用時亦然。藉由根據本發明之處理組成物，相較於先前技術處理，水系統(諸如冷卻塔)中之水可於開始形成水垢之前循環/再循環更多次。因排放較少及添加至該水系統之補充水較少之故，此大量節省用水。For comparison, typical prior art scale treatments, such as Chem-Aqua 31155 (which also contains PBTC, sodium tolyltriazole, sodium polyacrylate, polymaleic acid (sodium salt), and sodium hydroxide, also at a concentration of 100 ppm ) Allows cooling tower operation to be only 3 COC (for the LSI limit of only 2.6). Even if the treatment concentration of Chem-Aqua 31155 is doubled (200 ppm), the COC in the cooling tower can only be increased to 3.4, and the LSI limit is 2.85, which is far lower than the COC increase obtained by using the preferred embodiment of the composition of the present invention. And LSI limits. In other experiments using 50 ppm (when added to the pilot cooling tower system) of the same treatment composition used in the previous pilot cooling tower scale test, the system reached 4.3 COC and LSI was 2.84 before scale formation began . These results further indicate that the three-component formulation is far superior to the prior art PBTC-containing formulations in scale prevention, even when the prior art formulations are used at 2 to 4 times the concentration. With the treatment composition according to the present invention, the water in a water system, such as a cooling tower, can be circulated / recycled more times than before the scale is formed compared to the prior art treatment. This results in significant water savings due to less emissions and less make-up water added to the water system.

根據防止金屬組件腐蝕及/或鍍鋅鋼組件上之白鏽及/或水系統中形成礦物水垢之一種較佳方法，將如上述根據本發明之處理組成物以有效進料速率添加至該水系統。就組合上述AAP、HPA、及另一膦酸之一或多者的組成物而言，用於腐蝕及白鏽抑制之較佳方法包含，視經處理之水化學及該處理組成物中之隨意的組分之數量而定，以20 ppm至600 ppm，或更佳為100至300 ppm之處理組成物的有效進料速率將該組成物進料至水中。較佳的，將充足量之處理組成物添加至該水系統以提供有效活性量之這三種處理組分之一或多者(取決於是要處理白鏽或是要處理腐蝕與白鏽二者)：至少3 ppm AAP、至少3 ppm HPA、及至少2 ppm之另一膦酸，各為添加至正處理之水系統中的該定量水之濃度。更佳的，當添加至該水系統中之水時，處理組成物係以充足量添加以提供有效活性量之該等組分之一或多者：介於3 ppm至50 ppm AAP、介於3 ppm至50 ppm HPA、及介於2 ppm至20 ppm之另一膦酸。最佳的，當添加至該水系統中之水時，該等有效活性量為5 ppm至30 ppm AAP、3 ppm至20 ppm HPA、及2 ppm至10 ppm其他膦酸。就處理白鏽而言，隨意地使用HPA，因此根據本發明較佳方法中所使用之處理組成物可包含AAP而無任何HPA，且添加量足以提供正處理之水系統中的相同AAP濃度範圍。According to a preferred method of preventing corrosion of metal components and / or white scale on galvanized steel components and / or formation of mineral scale in water systems, the treatment composition according to the invention as described above is added to the water at an effective feed rate. system. With regard to a composition combining one or more of the above-mentioned AAP, HPA, and another phosphonic acid, a preferred method for corrosion and white rust suppression includes, depending on the treated water chemistry and the optional nature of the treated composition Depending on the number of components, the composition is fed into water at an effective feed rate of the treatment composition from 20 ppm to 600 ppm, or more preferably from 100 to 300 ppm. Preferably, a sufficient amount of the treatment composition is added to the water system to provide an effective active amount of one or more of the three treatment components (depending on whether to treat white rust or both corrosion and white rust) : At least 3 ppm AAP, at least 3 ppm HPA, and at least 2 ppm of another phosphonic acid, each being the concentration of the quantitative water added to the water system being treated. More preferably, when water is added to the water system, the treatment composition is added in a sufficient amount to provide an effective active amount of one or more of these components: between 3 ppm to 50 ppm AAP, between 3 ppm to 50 ppm HPA, and another phosphonic acid between 2 ppm and 20 ppm. Optimally, when added to the water in the water system, the effective active amounts are 5 ppm to 30 ppm AAP, 3 ppm to 20 ppm HPA, and 2 ppm to 10 ppm other phosphonic acids. For the treatment of white rust, HPA is used arbitrarily, so the treatment composition used in the preferred method according to the present invention may contain AAP without any HPA and is added in an amount sufficient to provide the same AAP concentration range in the water system being treated .

就組合上述AAP、HPA、及另一膦酸之一或多者的組成物而言，用於水垢抑制之較佳方法包含，視經處理之水化學及該處理組成物中之隨意的組分之數量而定，以20 ppm至600 ppm，或更佳為50至300 ppm之處理組成物的有效進料速率將該組成物進料至水中。較佳的，將充足量之處理組成物添加至該水系統以提供有效活性量之這三種處理組分之一或多者：至少2 ppm AAP、至少2 ppm HPA、及至少1.5 ppm之另一膦酸，各為添加至正處理之水系統中的該定量水之濃度。更佳的，處理組成物係以充足量添加以提供有效活性量之這三種處理組分：2 ppm至50 ppm AAP、2 ppm至50 ppm HPA、及1.5 ppm至20 ppm之另一膦酸，各為添加至正處理之水系統中的該定量水之濃度。最佳的，當添加至該水系統中之水時，處理組成物係以充足量添加以提供有效活性量之這三種組分：介於3 ppm至30 ppm AAP、介於2 ppm至20 ppm HPA、及介於1.5 ppm至10 ppm之另一膦酸。With regard to a composition combining one or more of the above-mentioned AAP, HPA, and another phosphonic acid, a preferred method for scale inhibition comprises, depending on the treated water chemistry and optional components in the treated composition Depending on the amount, the composition is fed into water at an effective feed rate of the treatment composition from 20 ppm to 600 ppm, or more preferably from 50 to 300 ppm. Preferably, a sufficient amount of the treatment composition is added to the water system to provide an effective active amount of one or more of the three treatment components: at least 2 ppm AAP, at least 2 ppm HPA, and at least 1.5 ppm of the other Phosphonic acid, each is the concentration of the quantitative water added to the water system being treated. More preferably, the treatment composition is added in sufficient amounts to provide effective active amounts of these three treatment components: 2 ppm to 50 ppm AAP, 2 ppm to 50 ppm HPA, and 1.5 ppm to 20 ppm of another phosphonic acid, Each is the concentration of the quantitative water added to the water system being treated. Optimally, when added to the water in the water system, the treatment composition is added in sufficient amounts to provide an effective active amount of these three components: between 3 ppm to 30 ppm AAP, between 2 ppm to 20 ppm HPA, and another phosphonic acid between 1.5 ppm and 10 ppm.

根據另一較佳實施態樣，添加至水系統之組成物(用於處理腐蝕、白鏽及/或水垢)包含螢光示蹤劑，因此可測量及監測於該水系統中之組成物含量。根據示蹤劑測量，視需要添加額外的處理組成物至該水系統以維持該水系統中有效處理量。According to another preferred embodiment, the composition added to the water system (for treating corrosion, white rust and / or scale) contains a fluorescent tracer, so the content of the composition in the water system can be measured and monitored . According to the tracer measurement, additional treatment composition is added to the water system as needed to maintain an effective treatment amount in the water system.

本文所述之實例試驗中之各種處理的全部ppm濃度係添加至旋轉器試驗中之水時的濃度，以與當添加至正在處理之水系統中的水時之濃度相關。除非明確排除，否則如本領域具有通常知識者所理解，本文及申請專利範圍中所有提及的酸包括該酸的水溶性鹽。本領域具有通常知識者於閱讀本說明書(包括本文所含之實例)時亦將理解可在本發明範疇內對該組成物之較佳實施態樣以及使用該組成物以處理水之方法作修改及變化，且希望本文所揭示之本發明範疇僅由發明人合法授權之附錄申請專利範圍的最廣泛解釋限定。The total ppm concentration of each treatment in the example tests described herein is the concentration when added to the water in the spinner test to correlate with the concentration when added to the water in the water system being treated. Unless explicitly excluded, as understood by those of ordinary skill in the art, all acids mentioned herein and in the scope of the patent application include water-soluble salts of the acids. Those with ordinary knowledge in the art will also understand that when reading this specification (including the examples contained herein), it is possible to modify the preferred embodiment of the composition and the method of using the composition to treat water within the scope of the present invention. And changes, and it is hoped that the scope of the invention disclosed herein is limited only by the broadest interpretation of the scope of the patent application appendix legally authorized by the inventor.

關於下列圖式進一步說明及解釋本發明之組成物及方法，其中： 　　圖1含有顯示以3英尺/秒(ft/sec)及5ft/sec之流率的旋轉器試驗之後於鋼試片上的腐蝕水準之照片； 　　圖2含有顯示以3ft/sec及5ft/sec之流率於殺生物劑存在下進行的旋轉器試驗之後於鋼試片上的腐蝕水準之照片； 　　圖3含有顯示以3ft/sec之流率的旋轉器試驗之後於鋼試片上的腐蝕水準之照片；以及 　　圖4含有顯示於旋轉器試驗之後於鍍鋅試片上的白鏽水準之照片。The following figures further illustrate and explain the composition and method of the present invention, in which: Figure 1 contains corrosion on steel test pieces showing a spinner test at flow rates of 3 ft / sec (ft / sec) and 5 ft / sec. Photo of the level; Figure 2 contains a photo showing the level of corrosion on a steel test piece after a spinner test in the presence of a biocide at a flow rate of 3 ft / sec and 5 ft / sec; Figure 3 contains a A photo of the corrosion level on the steel test piece after the flow rate spinner test; and FIG. 4 contains a photo showing the level of white rust on the galvanized test piece after the spinner test.

Claims (14)

一種處理水系統以在水LSI值為-2.5至3之範圍內抑制腐蝕或抑制水垢之方法，該方法包含將有效量之以胺基酸為基礎之聚合物、羥基膦醯基乙酸(hydroxyphosphonoacetic acid)、及第二膦酸添加至該水系統中的水。A method for treating a water system to inhibit corrosion or scale in a water LSI value of -2.5 to 3, the method comprising an effective amount of an amino-based polymer, hydroxyphosphonoacetic acid ), And a second phosphonic acid is added to the water in the water system. 如申請專利範圍第1項之方法，其中該第二膦酸為膦醯基羧酸，且水之LSI大於0.2。For example, the method of claim 1 in which the second phosphonic acid is a phosphinophosphonic acid, and the LSI of water is greater than 0.2. 如申請專利範圍第1項之方法，其中該有效量為當添加至該水系統中之一定量水中時，於該水系統中提供活性濃度為至少2 ppm之該以胺基酸為基礎之聚合物、至少2 ppm之該羥基膦醯基乙酸、及至少1.5 ppm之該膦醯基羧酸之量。The method according to item 1 of the patent application, wherein the effective amount is to provide the amino acid-based polymerization in the water system at an active concentration of at least 2 ppm when added to a certain amount of water in the water system. Of the phosphonium phosphonoacetic acid and at least 2 ppm of the phosphonophosphonoacetic acid, and at least 1.5 ppm of the phosphonophosphonocarboxylic acid. 如申請專利範圍第3項之方法，其中該有效量為當添加至該水系統中之該定量水中時，提供活性濃度為2 ppm至50 ppm之該以胺基酸為基礎之聚合物、活性濃度為2 ppm至50 ppm之該羥基膦醯基乙酸、及活性濃度為1.5 ppm至20 ppm之該膦醯基羧酸的量。The method of claim 3, wherein the effective amount is to provide the amino acid-based polymer with an active concentration of 2 ppm to 50 ppm when added to the quantitative water in the water system. The amount of the hydroxyphosphonium phosphonoacetic acid at a concentration of 2 ppm to 50 ppm, and the phosphonium phosphonocarboxylic acid at an active concentration of 1.5 ppm to 20 ppm. 如申請專利範圍第3項之方法，其中該有效量為當添加至該水系統中之該定量水中時，提供活性濃度為3 ppm至30 ppm之該以胺基酸為基礎之聚合物、活性濃度為2 ppm至20 ppm之該羥基膦醯基乙酸、及活性濃度為1.5 ppm至10 ppm之該膦醯基羧酸之量。The method according to item 3 of the patent application, wherein the effective amount is to provide the amino acid-based polymer having an active concentration of 3 ppm to 30 ppm when added to the quantitative water in the water system. The amount of the phosphonophosphonoacetic acid at a concentration of 2 ppm to 20 ppm and the phosphinophosphonic acid at an active concentration of 1.5 ppm to 10 ppm. 如申請專利範圍第2項之方法，其中該有效量之以胺基酸為基礎之聚合物、羥基膦醯基乙酸、及膦醯基羧酸為當添加至該水系統中之一定量水中時，於該水系統中提供組合活性濃度為至少6.5 ppm之該以胺基酸為基礎之聚合物、羥基膦醯基乙酸、及膦醯基羧酸之量。The method of claim 2 in which the effective amount of the amino-based polymer, hydroxyphosphinophosphonoacetic acid, and phosphinophosphonocarboxylic acid is when added to a certain amount of water in the water system The amount of the amino acid-based polymer, hydroxyphosphinophosphonoacetic acid, and phosphinophosphonocarboxylic acid is provided in the water system with a combined active concentration of at least 6.5 ppm. 如申請專利範圍第1項之方法，其中該以胺基酸為基礎之聚合物為聚天冬胺酸。For example, the method of claim 1, wherein the amino acid-based polymer is polyaspartic acid. 如申請專利範圍第2項之方法，其中於添加至該水系統之前將該以胺基酸為基礎之聚合物、及羥基膦醯基乙酸、及膦醯基羧酸、及示蹤劑組合成處理組成物，以及其中該方法進一步包含： 　　基於該示蹤劑之測量，定期測量之該水系統中的處理組成物之量。For example, the method of claim 2 in which the amino acid-based polymer, hydroxyphosphinophosphonoacetic acid, and phosphinophosphonocarboxylic acid, and a tracer are combined before adding to the water system. The treatment composition, and wherein the method further comprises: 定期 periodically measuring the amount of the treatment composition in the water system based on the measurement of the tracer. 如申請專利範圍第6項之方法，其進一步包含視需要添加另外的處理組成物以維持該以胺基酸為基礎之聚合物的濃度為至少2 ppm及該羥基膦醯基乙酸的濃度為至少2 ppm，其中此等濃度係於添加至該水系統中之一定量水中時的濃度。The method of claim 6, further comprising adding an additional treatment composition as needed to maintain the concentration of the amino acid-based polymer of at least 2 ppm and the concentration of the hydroxyphosphonium phosphonoacetic acid at least 2 ppm, where these concentrations are those when added to a metered amount of water in the water system. 如申請專利範圍第2項之方法，其中該膦醯基羧酸為1-羥乙烷-1,1-二膦酸(HEDP)、2-膦醯基丁烯-1,2,4-三甲酸(PBTC)或二者。The method according to item 2 of the patent application, wherein the phosphinophosphonic acid is 1-hydroxyethane-1,1-diphosphonic acid (HEDP), 2-phosphinofluorenylbutene-1,2,4-tris Formic acid (PBTC) or both. 如申請專利範圍第2項之方法，其中該水系統中之水含有殺生物劑。The method of claim 2 in which the water in the water system contains a biocide. 如申請專利範圍第2項之方法，其中該水系統中之水的pH大於7。For example, the method of claim 2 of the patent application range, wherein the pH of the water in the water system is greater than 7. 如申請專利範圍第1項之方法，其係用以抑制在曝露於LSI＞2.0之水的該水系統中之表面上形成礦物水垢，該方法進一步包含於添加步驟之後使水的LSI相較於無水垢形成之該添加步驟之前的LSI提高；以及 　　其中該添加步驟包含添加2 ppm至50 ppm之該以胺基酸為基礎之聚合物、2 ppm至50 ppm之該羥基膦醯基乙酸、及1.5 ppm至20 ppm之該膦醯基羧酸，各者均為當添加至該水系統中之該定量水中時的活性濃度。For example, the method of applying for the first item of the patent scope is to suppress the formation of mineral scale on the surface of the water system exposed to water of LSI> 2.0, and the method further includes comparing the LSI of water with The LSI is improved before the adding step without scale formation; and wherein the adding step includes adding 2 ppm to 50 ppm of the amino acid-based polymer, 2 ppm to 50 ppm of the hydroxyphosphinofluoracetic acid, and From 1.5 ppm to 20 ppm of the phosphinophosphonic acid, each is the active concentration when added to the quantitative water in the water system. 如申請專利範圍第13項之方法，其中該第二膦酸為膦醯基羧酸以及該以胺基酸為基礎之聚合物為聚天冬胺酸。For example, the method of claim 13 in which the second phosphonic acid is a phosphinophosphonic acid and the amino acid-based polymer is polyaspartic acid.
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