US3860430A - Filming amine emulsions - Google Patents

Filming amine emulsions Download PDF

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US3860430A
US3860430A US413079A US41307973A US3860430A US 3860430 A US3860430 A US 3860430A US 413079 A US413079 A US 413079A US 41307973 A US41307973 A US 41307973A US 3860430 A US3860430 A US 3860430A
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weight
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amine
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aliphatic
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US413079A
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Jerry Lee Walker
Iii Thomas Edward Cornelius
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Calgon Corp
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Calgon Corp
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Priority to CA212,479A priority patent/CA1041284A/en
Priority to JP49126673A priority patent/JPS5075653A/ja
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting 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
    • C23F11/14Nitrogen-containing compounds
    • C23F11/141Amines; Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/02Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors

Definitions

  • ABSTRACT Filming amine emulsions employing polyoxyalkylenccontaining tertiary amines are used to protect metal piping and apparatus which are subject to corrosive attack by aqueous media which is being transported or with which they are otherwise in contact.
  • the corrosion-inhibiting composition comprises an aliphatic film-forming amine, water, and a polyoxyalkylcnc containing tertiary amine dispersing agent represented by the formula:
  • R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1 respectively, the total of all units in the chain being n, which is an integer of 3 to 100.
  • the corrosion-inhibiting composition may also include an aliphatic amine salt, particularly tallow amine acetate, and/or a neutralizing amine, particularly diethylaminoethanol.
  • This invention relates to methods and compositions for inhibiting the corrosion of metal components which are contacted by aqueous fluids. It particularly concerns the use of filming amine emulsions employing polyoxyalkylene containing tertiary amines to protect metal piping and apparatus which are subject to corrosive attack by the aqueous media which is being transported or with which they are otherwise in contact.
  • a wide variety of systems employ equeous fluids for various industrial and commercial purposes and include, among others, steam turbine systems, boiler systems, steam condensate return systems, steam distribution systems, heat transfer water systems, evaporator systems, processing water systems, wet pipe fire systems, cooling water systems, and so forth.
  • metal and metal components and apparatus is intended to include ferrous materials and alloys, non-ferrous materials and alloys such as those based on copper and nickel, and so forth; and various structures such as pipes, tanks, fittings, valves, traps, heat exchangers, deaerators, and similar devices.
  • the methods and compositions of this invention also find useful application generally to inhibiting corrosion of metal surfaces contacted by corrosive aqueous fluids which are transported, circulated and contained within the metal components. Nevertheless, the methods and compositions of the invention have proven especially beneficial in steam and steam condensate systems where it is desired to keep additives to the system at a minimum, since corrosion inhibiting results are realized in this environment when using only extremely small quantities of the compositions of this invention.
  • the corrosion which is experienced by metal exposed to aqueous fluids, particularly steam and steam condensate, is apparently due in large measure to carbon dioxide and oxygen dissolved or otherwise entrained in the aqueous fluid.
  • the corrosive action may also be caused by ammonia, hydrogen sulfide, sulfur dioxide, or other substances present in the aqueous fluid in gas, liquid, or vapor form; or by the aqueous fluid itself; or by a combination of any of these.
  • U.S. Pat. No. 2,460,259 discloses deposition of a protective, substantially mono-nuclear film of a corrosion inhibiting substance comprising, among other materials, high molecular weight amines, particularly octadecylamine. While these aliphatic amines provide adequate protection against corrosion for metal surfaces on which they are actually coated, they have confronted the art with a number of problems. For example, aliphatic amines satisfactory for corrosion inhibition are also solids at room temperature, thus requiring transformation to a liquid form to be usable.
  • compositions containing salts of aliphatic amines which are more water soluble than the amines themselves U.S. Pat. No. 2,712,531 discloses the use of a blend of octadecylamine and octadecylamine acetate as a corrosion inhibitor.
  • U.S. Pat. No. 2,767,106 discloses the use of an aliphatic amine glycolate, either alone or in combination with an aliphatic amine, as a corrosion inhibitor.
  • U.S. Pat. No. 2,649,415 discloses the use of polyalkoxylated derivatives of monocarboxylic acids, monohydric alcohols, and of alkylphenols as non-ionic dispersing agents for aliphatic amine corrosion inhibitors.
  • U.S. Pat. No. 2,956,889 discloses a corrosion inhibitor comprising an aqueous emulsion of an aliphatic amine which is stabilized by the presence of a water-soluble condensate of at least 5 moles of ethylene oxide with a high molecular weight aliphatic amine.
  • U.S. Pat. No. 3,088,796 discloses the use of polyoxyethylene tertiary amine and quaternary ammonium chloride compounds as emulsifiers for filmforming aliphatic amines to produce corrosion inhibiting compositions.
  • U.S. Pat. No. 3,239,470 discloses the combination of a primary aliphatic amine, an ethoxylated amine condensate, and a phenolic lignin sulfonate used as a corrosion inhibitor.
  • U.S. Pat. No. 3,418,253 discloses the use of an aqueous dispersion of a straight chain primary amine emulsified with a polyethoxylatcd long chain amide as a corrosion inhibitor.
  • U.S. Pat. No. 3,418,254 discloses the use of an aqueous emulsion of a primary aliphatic amine emulsified by an alkylphenoxy (ethyleneoxy) alkanol as a corrosion inhibitor.
  • U.S. Pat. No. 3,554,922 discloses the use of an aqueous dispersion of octadeeylamine and a vegetable polysaccharide gum as a corrosion inhibitor.
  • 3,717,433 discloses a steam-corrosion inhibition method employing a composition comprised of a fatty amine, an isothiouronium salt as a cationic emulsifier, and an ethoxylated straight chain aliphatic acid as an emulsion stabilizer.
  • U.S. Pat. Nos. 3,029,125 and 3,378,581 discloses the use of alkoxylated alkylene diamines and their aliphatic carboxylic acid salts as corrosion inhibitors.
  • U.S. Pat. No. 3,203,904 discloses corrosion inhibition with ethoxylated staight long chain amines emulsified by ethoxylated quaternary ammonium chloride salts.
  • Another object of this invention is to provide a corrosion inhibiting composition which is very fluid at room temperature, thus allowing easy introduction into the system to be treated.
  • Another object of this invention is to provide a corrosion inhibiting composition having excellent freezethaw characteristics.
  • Another object of this invention is to provide a corrosion inhibiting composition having incorporated therein, in addition to an aliphatic amine, a neutralizing amine.
  • Another object of this invention is to provide a corrosion inhibiting composition which is solid, preferably an extruded solid, conisting of a blend of all ingredients required to permit direct feeding, or requiring only dilution with water to the desired concentration before feeding to the system to be treated.
  • the film-forming amines useful in this invention are generally the fatty amines and this is intended to include saturated n-alkyl amines containing to 22 carbon atoms; unsaturated n-alkyl amines containing 10 to 22 carbon atoms, but with 1 or 2 unsaturated moieties present in the carbon atom chain, the remainder being saturated; branched alkyl amines containing 10-22 carbon atoms; mixtures of any or all of the above; and hydrogenated mixtures of any of the above unsaturated amines.
  • Useful fatty amines include, among others, dodecylamine; tetradecylamine; hexadecylamine; octadecylamine; tallow amines and hydrogenated tallow amines.
  • the preferred fatty amines for use in this invention are octadecylamine, tallow amine and hydrogenated tallow amine.
  • the aliphatic film-forming amine may be contained in the compositions of this invention in an amount of from about 1% by weight to about 90% by weight, and preferably from about 1% by weight to about by weight.
  • this invention also contemplates the use of various known salts of the aliphatic amines described.
  • Such known salts include the glycolate and acetate salts of various aliphatic amines.
  • the use of the acetate salts of the aliphatic amines described herein is especially preferred for the compositions and methods of this invention.
  • These salts of the aliphatic film-forming amines may be used in the compositions of this invention in an amount of from about 0.1% by weight to about 50% by weight, preferably from about 0.5% by weight to about 10% by weight.
  • Neutralizing amines are known in the art and function as corrosion inhibitors by neutralizing carbonic acid present in water and steam systems as the result of dissolved carbon dioxide. Any other acids present would also be neutralized. They are employed in the methods and compositions of this invention along with fatty film-forming amines and the polyoxyalkylene containing tertiary amines of this invention to give improved corrosion inhibition.
  • Examples of neutralizing amines known in the art are cyclohexylamine, morpholine and diethylaminoethanol (DEAE). Of these, diethylaminoethanol is especially preferred for use with the methods and compositions of this invention.
  • the neutralizing amine may be contained in the compositions of this invention in an amount of from about 1% by weight to about 50% by weight, preferably from about 1% by weight to about 20% by weight.
  • polyoxyalkylene-containing tertiary amines useful in this invention may be represented by the formula:
  • R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkyl ene chain of randomly distributed oxyalkylene units, the total of these units in the chain being n, which is an integer of3 to and preferably 5 to 50, said polyoxyalkylene chain consisting of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1, respectively.
  • polyoxyalkylene-containing tertiary amines of this type are described in US. Pat. No. 3,456,013, which is incorporated herein by reference.
  • Such polyoxyalkylene-containing tertiary amines are condensation products of a secondary mono-amine containing two aliphatic hydrocarbon radicals with a mixture of ethylene oxide and propylene oxide.
  • the different oxyalkylene groups are distributed randomly throughout the oxyalkylene chain and the oxyalkylene chain itself may vary in length. While this results in a varying structure, the compounds produced are characterized by the average length of the polyoxyalkylene chain and the average ratio of oxyethylene units to oxypropylene units in the polyoxyalkylene chain.
  • tertiary amines contain 5, 10, 15, 20, 30 and 50 moles of polyoxyalkylene per mole of the tallow amine component of the tertiary amine, and are designatd EO/PO (for ethylene oxide/propylene oxide) 5, 10, 15, 20, 30 and 50 respectively.
  • the tertiary amine will be present in the compositions of this invention in an amount of from about 0.1% by weight to about 10.0% by weight, preferably in an amount from about 0.2% by weight to about 5.0% by weight.
  • This invention contemplates the use of the polyoxyalkylene-containing tertiary amines just described with aliphatic film-forming amine and water to produce what is, in effect, an emulsifiable concentrate. That is, the mixture is an emulsion which is suitable to be diluted to any desired concentration and then fed directly to the system to be treated.
  • This invention further contemplates the use of one or more salts of an aliphatic film-forming amine, which are more water soluble than the amine itself, along with the mixture of the film-forming amine and polyoxyalkylene-containing tertiary amine as described above.
  • salts of aliphatic film-forming amines are well known in the art and include, for example, the acetate and glycolate salts of various aliphatic film-forming amines. ln this invention the use of tallow amine acetate is particularly preferred. This invention also contemplates the use of a neutralizing amine along with the mixture of the aliphatic film-forming amine and the polyoxyalkylenecontaining tertiary amine amine described above. in this invention the use of diethylaminoethanol (DEAE) is particularly preferred.
  • Feed solutions were prepared having 20%, and 1% by weight of solids concentrations. These feed solutions were satisfactory for introduction into a system to be treated.
  • the mixture was stirred while heating to 160F. The mixture was then removed from the heat and agitated until cool. The finished product was a uniform paste.
  • a halfgram (0.5 of the EO/PO 20, the 20 grams ofArmeen HT, the 10 grams of Armac HT, and 1()() grams of distilled water were mixed and heated with stirring to 160F. The mixture was then removed from the heat and agitated until the mixture reached 120F. Then the remaining 4.5 grams of EO/PO 20 and grams oldistilled water were added slowly to the mixture while agitation was continued. The mixture was very viscous prior to addition of the remaining EO/PO 2(1 and distilled water, but with the addition the viscosity was reduced, resulting in a very fluid. uniform product.
  • a 0.2 gram amount of the EO/P'O 20 was added to 99.8 mls. of distilled water, then the 20 grams of Ar meen and 10 grams of Armac were added, and the total mixture was heated with stirring to 160F. The mixture was removed from the heat and agitated until it reached F. The agitation was continued while the remaining amounts of the ingredients, 0.2 gram of EO/PO 20 and 69.8 of distilled water, were added slowly to the mixture. The final product was somewhat viscous but still fluid. Feed solutions of 20%. 5% and 1% by weight of solids content were prepared, and were satisfactory for introduction into a system to be treated.
  • Adogen A 5 Ingredient Amount (grants) 7: by Weight EO/PO I5 5 2.5
  • the final product was prepared as in Example 7 and proved to be uniform and viscous.
  • the final product was prepared as in Example 7 above, and proved to be fluid and uniform.
  • Amount (grams) 71 by Weight Ingredients Armeen HT 25 12.0 Armac HT 5 2.4 Pennad 150 8 3.8 EO/PO 20 1.8 1.0 Distilled Water 168 80.8
  • the mixture was heated with stirring to 160F. Agitation was continued while the mixture was cooled to 120F. The final product was uniform and viscous.
  • the mixture was heated to 180F. with mild agitation. The mixture was then removed from the heat and placed under a Heller mixer and mildly agitated until it cooled to room temperature.
  • This invention contemplates use of the corrosioninhibiting compositions described herein in solid form as well as in fluid emulsion form.
  • This solid form may simply be flakes of the corrosion-inhibiting composition produced by evaporating the water content from a thin layer of the fluid emulsion of the corrosioninhibting composition containing the desired proportions of components, disposed on any convenient surface.
  • a preferred method of preparing a solid form of the corrosion-inhibiting compositions of this invention is by extrusion ofa hot mixture of the components of the corrosion-inhibiting composition, wherein the extruding device is cooled sufficiently to induce solidification of the corrosion-inhibiting composition, which will normally be solid at room temperature. Most conveniently, this is accomplished during the manufacturing process for aliphatic amines.
  • these aliphatic amines will be in a heated condition, and thus liquid.
  • the additional components of the corrosion-inhibiting compositions of this invention can simply be incorporated into the aliphatic amine.
  • a hot mixture is prepared simply by adding to the desired amount of the aliphatic film-forming amine maintained at an elevated temperature sufficient to render it fluid, appropriate quantities of the polyoxyalkylene-containing tertiary amine dispersing agent, and such other of the additional components ofthe corrosion-inhibiting compositions described herein as may be desired.
  • the mixture is agitated to insure uniform dispersion ofall of the components.
  • the extrusion itself may be performed with conventional equipment intended for this purpose, according to known extrusion techniques.
  • compositions of this invention either already exist as emulsions, or, in the case of the extruded solid compositions, may be mixed with water to produce an emulsion. These emulsions may be diluted with water to form corrosion inhibiting compositions containing from 1% to 25% by weight of solids.
  • the corrosion inhibiting compositions of this invention may be incorporated into the system to be treated in a number of ways. They may be added to a water storage tank, or fed into water being added to such a storage tank, for example.
  • the compositions of this invention may be introduced to condensate receivers, deaerating heaters, boiler feed water lines, directly to the boiler itself, or directly to the steam lines for uniform distribution. Where necessary, a piston pump capable of exceeding the internal pressure of the boiler may be used.
  • the feeding of the corrosion inhibiting composition may be continuous or at intervals.
  • the corrosion inhibiting composition may be introduced at more than one point, and the treatment may be confined to the water alone, the steam alone, or both may be treated.
  • the corrosioninhibiting composition is added in amounts sufficient to maintain a weight of composition to weight of system aqueous fluid ratio of from about 0.1 to about parts per million. with a dynamic system, such as a boiler system, the amount added is expressed in terms of pounds of steam produced.
  • the corrosion-inhibiting compositions of this invention would be added to a boiler system in an amount of from about 0.1 to about 100 pounds of product per million pounds of steam produced.
  • the aliphatic film-forming amine With the generation of steam, the aliphatic film-forming amine enters its vapor phase and thereby becomes distributed uniformly throughout the entire system.
  • the amine thereupon becomes deposited as a very thin film upon all exposed metallic interior surfaces of the system. Since this film is hydrophobic in nature, it serves to protect the metallic surfaces of the system against corrosive attack by the steam or water, or by both, contained in the system.
  • the temperature of the system must be sufficient for this purpose. When the system is under elevated pressure, as with a boiler system, or possibly under reduced pressure, the temperature required to produce vaporization of the aliphatic amine will be higher or lower, respectively, than that required at atmospheric pressure.
  • the corrosion-inhibiting compositions of this invention may be dispersed in the system to be protected in amounts sufficient to maintain a weight of composition to weight of system aqueous fluid ratio of from about 0.1 to about 100 parts per million.
  • the amounts (by weight) of corrosioninhibiting composition of this invention added to the system will preferably be in the range of from about 0.25 parts per million by weight.
  • EXAMPLE 12 Ingredient "/1 by Weight Adogen M Adogcn 140A 5 EO/PO l Distilled Water 84 Strips (coupons) of a suitable metal subject to corrosion were prepared. These were of uniform dimension: l X 3 X l/l6 inches. They were cleaned, weighed and placed in steam of the particular system being used as the test basis. In this case the system was a steam system for a steel plant. The coupons remained in place for a predetermined period of time, during which the above corrosion-inhibiting composition of this invention was introduced into the steam system. For comparison, another corrosion-inhibiting material was employed for a separate and equal test interval. This material was hydrogenated tallow amine emulsified with isopropyl alcohol.
  • test coupons were removed from the system, acid cleaned to remove the corrosion products, and again weighed.
  • the reduction in weight was then calculated on a yearly basis, noting the actual weight loss during the specific test period and the length of the predetermined time period. This yearly weight loss is expressed as milligrams per year, or mpy.
  • Example R -N we R30 21 wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1, respectively, the total of all units in the chain begin n, which is an integer of 3 to 100.
  • composition of claim 1 containing from about 1 percent by weight to about 90 percent by weight of aliphatic film-forming amine; and from about 0.1 percent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
  • composition of claim 1 additionally included water.
  • composition of claim 4 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
  • a corrosion-inhibiting composition comprising an aliphatic film-forming amine; an aliphatic amine salt; and a polyoxyalkylene-containing tertiary amine dispersing agent represented by the formula:
  • R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different, and wherein R is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1, respectively, the total of all units in the chain being n, which is an integer of 3 to 100.
  • composition of claim 6 wherein the aliphatic amine salt is tallow amine acetate.
  • composition of claim 6 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylenecontaining tertiary amine.
  • composition ofclaim 6 additionally including water.
  • composition'of claim 10 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
  • a corrosion-inhibiting composition comprising an aliphatic film-forming amine; a neutralizing amine; and a polyoxyalkylene-containing tertiary amine dispensing agent represented by the formula:
  • R and R are aliphatic hydrocarbon radicals having from 12 to carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylcne and oxypropylene units in a ratio of from 1:10 to 10:1, re' spectively, the total of all units in the chain being n, which is an integer of 3 to 100.
  • composition of claim 12 wherein the neutralizing amine is diethylamino ethanol.
  • composition of claim 12 containing from about 1 per cent by weight to about per cent by weight of aliphatic film-forming amine; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
  • composition otclaim 12 additionally including water.
  • composition of claim 16 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film'forming amine; from about 1 per cent by weight to about 50 per cent by weight 01 neutralizing amine; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
  • a corrosion-inhibiting composition comprising an aliphatic film-forming amine; an aliphatic amine salt; a neutralizing amine; and a polyoxyalkylenccontaining tertiary amine dispersing agent represented by the formula:
  • R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different, and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylenc and oxypropylene units in a ratio of from 1:10 to 10:1, respectively, the total of all units in the chain being n, which is an integer of 3 to 100.
  • composition of claim 18 containing'from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; and from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weiht to about 10.0 per cent by weight of polyoxyalkylenecontaining tertiary amine.
  • composition of claim 19 additionally including water.
  • composition of claim'20 containing from about 1 per cent by weight to about 90 by weight of aliphatic film-forming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylenc-containing tertiary amine.
  • a method of inhibiting the corrosion of metal components which are contacted by aqueous fluids comprising dispersing throughout said aqueous fluids a composition comprising an aliphatic film-forming wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1 respectively, the toal of all units in the chain being n, which is an integer of 3 to 100.
  • n is an integer of to 50.
  • composition employed therein contains from about 1 per cent by weight to about 90 per cent by weight of aliphatic filmforming amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylenecontaining tertiary amine.
  • composition employed therein additionally includes water.
  • a method of inhibiting the corrosion of metal components which are contacted by aqueous fluids comprising dispersing throughout said aqueous fluids a composition comprising an aliphatic film-forming amine; an aliphatic amine salt; and a polyoxyalkylenecontaining tertiary amine dispersing agent represented by the formula:
  • R -N +12 0 a a wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to :1, respectively, the total of all units in the chain being n, which is an integer of 3 to 100.
  • n is an integer of 5 to 50.
  • composition employed therein contains from about 1 per cent by weight to about 90 per cent by weight of aliphatic filmforming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
  • composition employed therein additionally includes water.
  • a method of inhibiting the corrosion of metal components which are contacted by aqueous fluids comprising dispersing throughout said aqueous fluids a composition comprising and aliphatic film-forming amine; a neutralizing amine; and a polyoxyalkylenecontaining tertiary amine dispersing agent represented by the formula:
  • RfN R 0 H wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1 respectively, the total of all units in the chain being 11,
  • n is an integer of 5 to 50.
  • the method of claim 30 wherein for the composi tion employed therein contains from about 1 per cent by weight to about per cent by weight of aliphatic film-forming amine; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
  • a method of inhibiting the corrosion of metal components which are contacted by aqueous fluids comprising dispersing throughout :said aqueous fluids a composition comprising an aliphatic film-forming amine, an aliphatic amine salt; a neutralizing amine; and a polyoxyalkylene-containing tertiary amine dispersing agent represented by the formula:
  • R, and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1 respectively, the total of all units in the chain being n, which is an integer of 3 to 100.
  • n is an integer of 5 to 50.
  • composition employed therein contains from about 1 per cent by weight to about 90 per cent by weight of aliphatic filmforming amine; and from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
  • composition employed therein additionally includes water.

Abstract

Filming amine emulsions employing polyoxyalkylene-containing tertiary amines are used to protect metal piping and apparatus which are subject to corrosive attack by aqueous media which is being transported or with which they are otherwise in contact. The corrosion-inhibiting composition comprises an aliphatic filmforming amine, water, and a polyoxyalkylene-containing tertiary amine dispersing agent represented by the formula: WHEREIN R1 and R2 are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, and wherein R3O is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1 respectively, the total of all units in the chain being n, which is an integer of 3 to 100. The corrosion-inhibiting composition may also include an aliphatic amine salt, particularly tallow amine acetate, and/or a neutralizing amine, particularly diethylaminoethanol.

Description

Unite States Patent [191 Walker et al.
[451 Jan. 14, 1975 FlLMlNG AMINE EMULSIONS [75] Inventors: Jerry Lee Walker; Thomas Edward Cornelius, 111, both of Coraopolis, Pa.
[52] US. Cl. 106/14, 252/392 [51] Int. Cl. C09k 11/14, C09d 5/08 [58] Field of Search 106/14; 252/392 [56] References Cited UNITED STATES PATENTS 2,712,531 7/1955 Maguire 252/392 2,956,889 10/1960 Denman 106/14 3,418,254 12/1968 Bishof et al 106/14 3,456,013 7/1969 Egan 260/584 3,520,820 7/1970 l-lwa 106/14 3,718,604 2/1973 Scherf et al 106/14 Primary Examiner-Morris Liebman Assistant ExaminerS. L. Fox
Attorney, Agent, or Firm -Harry E. Westlake, J12; Raymond M. Speer I [57] ABSTRACT Filming amine emulsions employing polyoxyalkylenccontaining tertiary amines are used to protect metal piping and apparatus which are subject to corrosive attack by aqueous media which is being transported or with which they are otherwise in contact. The corrosion-inhibiting composition comprises an aliphatic film-forming amine, water, and a polyoxyalkylcnc containing tertiary amine dispersing agent represented by the formula:
wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1 respectively, the total of all units in the chain being n, which is an integer of 3 to 100. The corrosion-inhibiting composition may also include an aliphatic amine salt, particularly tallow amine acetate, and/or a neutralizing amine, particularly diethylaminoethanol.
37 Claims, No Drawings FILMING AMINE EMULSIONS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to methods and compositions for inhibiting the corrosion of metal components which are contacted by aqueous fluids. It particularly concerns the use of filming amine emulsions employing polyoxyalkylene containing tertiary amines to protect metal piping and apparatus which are subject to corrosive attack by the aqueous media which is being transported or with which they are otherwise in contact. A wide variety of systems employ equeous fluids for various industrial and commercial purposes and include, among others, steam turbine systems, boiler systems, steam condensate return systems, steam distribution systems, heat transfer water systems, evaporator systems, processing water systems, wet pipe fire systems, cooling water systems, and so forth.
Reference herein to metal and metal components and apparatus is intended to include ferrous materials and alloys, non-ferrous materials and alloys such as those based on copper and nickel, and so forth; and various structures such as pipes, tanks, fittings, valves, traps, heat exchangers, deaerators, and similar devices.
While the description of the invention concerns itself primarily with corrosion of metal components produced by contact of the metal surfaces with steam and steam condensate, the methods and compositions of this invention also find useful application generally to inhibiting corrosion of metal surfaces contacted by corrosive aqueous fluids which are transported, circulated and contained within the metal components. Nevertheless, the methods and compositions of the invention have proven especially beneficial in steam and steam condensate systems where it is desired to keep additives to the system at a minimum, since corrosion inhibiting results are realized in this environment when using only extremely small quantities of the compositions of this invention.
The corrosion which is experienced by metal exposed to aqueous fluids, particularly steam and steam condensate, is apparently due in large measure to carbon dioxide and oxygen dissolved or otherwise entrained in the aqueous fluid. However, the corrosive action may also be caused by ammonia, hydrogen sulfide, sulfur dioxide, or other substances present in the aqueous fluid in gas, liquid, or vapor form; or by the aqueous fluid itself; or by a combination of any of these.
2. Description of the Prior Art The use of aliphatic amines to inhibit the corrosion of metal and metal components taking place under the conditions described above is well known in the art. U.S. Pat. No. 2,460,259 discloses deposition of a protective, substantially mono-nuclear film of a corrosion inhibiting substance comprising, among other materials, high molecular weight amines, particularly octadecylamine. While these aliphatic amines provide adequate protection against corrosion for metal surfaces on which they are actually coated, they have confronted the art with a number of problems. For example, aliphatic amines satisfactory for corrosion inhibition are also solids at room temperature, thus requiring transformation to a liquid form to be usable. Proper utilization requires that the composition be accurately metered to and and dispersed within the system to be treated. However, the aliphatic amines useful for corrosion inhibition are also nearly water insoluble. Thus, it has been conventional to prepare compositions containing salts of aliphatic amines which are more water soluble than the amines themselves. U.S. Pat. No. 2,712,531 discloses the use of a blend of octadecylamine and octadecylamine acetate as a corrosion inhibitor. U.S. Pat. No. 2,767,106 discloses the use of an aliphatic amine glycolate, either alone or in combination with an aliphatic amine, as a corrosion inhibitor. It has also been conventional to prepare dilute aqueous dispersions of aliphatic amines by combining them with dispersing aids or emulsifiers. U.S. Pat. No. 2,649,415 discloses the use of polyalkoxylated derivatives of monocarboxylic acids, monohydric alcohols, and of alkylphenols as non-ionic dispersing agents for aliphatic amine corrosion inhibitors. U.S. Pat. No. 2,956,889 discloses a corrosion inhibitor comprising an aqueous emulsion of an aliphatic amine which is stabilized by the presence of a water-soluble condensate of at least 5 moles of ethylene oxide with a high molecular weight aliphatic amine. U.S. Pat. No. 3,088,796 discloses the use of polyoxyethylene tertiary amine and quaternary ammonium chloride compounds as emulsifiers for filmforming aliphatic amines to produce corrosion inhibiting compositions. U.S. Pat. No. 3,239,470 discloses the combination of a primary aliphatic amine, an ethoxylated amine condensate, and a phenolic lignin sulfonate used as a corrosion inhibitor. U.S. Pat. No. 3,418,253 discloses the use of an aqueous dispersion of a straight chain primary amine emulsified with a polyethoxylatcd long chain amide as a corrosion inhibitor. U.S. Pat. No. 3,418,254 discloses the use of an aqueous emulsion of a primary aliphatic amine emulsified by an alkylphenoxy (ethyleneoxy) alkanol as a corrosion inhibitor. U.S. Pat. No. 3,554,922 discloses the use of an aqueous dispersion of octadeeylamine and a vegetable polysaccharide gum as a corrosion inhibitor. U.S. Pat. No. 3,717,433 discloses a steam-corrosion inhibition method employing a composition comprised of a fatty amine, an isothiouronium salt as a cationic emulsifier, and an ethoxylated straight chain aliphatic acid as an emulsion stabilizer.
In addition to the fatty amines described'above, other amine compounds have found use as corrosion inhibitors. U.S. Pat. Nos. 3,029,125 and 3,378,581 discloses the use of alkoxylated alkylene diamines and their aliphatic carboxylic acid salts as corrosion inhibitors. U.S. Pat. No. 3,203,904 discloses corrosion inhibition with ethoxylated staight long chain amines emulsified by ethoxylated quaternary ammonium chloride salts.
SUMMARY OF THE INVENTION It is an object of this invention to provide a method and composition for inhibiting the corrosion of metal surfaces exposed to corrosive aqueous fluids.
It is a further object of this invention to provide a corrosion inhibiting composition which permits preparation of feed solutions having from 0.1% active amine up to any practical maximum concentration.
Another object of this invention is to provide a corrosion inhibiting composition which is very fluid at room temperature, thus allowing easy introduction into the system to be treated.
Another object of this invention is to provide a corrosion inhibiting composition having excellent freezethaw characteristics.
Another object of this invention is to provide a corrosion inhibiting composition having incorporated therein, in addition to an aliphatic amine, a neutralizing amine.
Another object of this invention is to provide a corrosion inhibiting composition which is solid, preferably an extruded solid, conisting of a blend of all ingredients required to permit direct feeding, or requiring only dilution with water to the desired concentration before feeding to the system to be treated.
It is another object of this invention to provide a corrosion inhibiting composition which employs emulsifiers which are themselves film-forming materials that aid in corrosion inhibition. 1
Other objects of this invention will become apparent from the additional description of the invention set out herein. However, it is intended that the description of the invention should not limit the invention, but merely indicate the preferred embodiments thereof, since various modifications within the scope of this invention will become apparent to those skilled in the art.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The film-forming amines useful in this invention are generally the fatty amines and this is intended to include saturated n-alkyl amines containing to 22 carbon atoms; unsaturated n-alkyl amines containing 10 to 22 carbon atoms, but with 1 or 2 unsaturated moieties present in the carbon atom chain, the remainder being saturated; branched alkyl amines containing 10-22 carbon atoms; mixtures of any or all of the above; and hydrogenated mixtures of any of the above unsaturated amines. Useful fatty amines include, among others, dodecylamine; tetradecylamine; hexadecylamine; octadecylamine; tallow amines and hydrogenated tallow amines. The preferred fatty amines for use in this invention are octadecylamine, tallow amine and hydrogenated tallow amine. The aliphatic film-forming amine may be contained in the compositions of this invention in an amount of from about 1% by weight to about 90% by weight, and preferably from about 1% by weight to about by weight.
In addition to the aliphatic film-forming amines described, this invention also contemplates the use of various known salts of the aliphatic amines described. Such known salts include the glycolate and acetate salts of various aliphatic amines. The use of the acetate salts of the aliphatic amines described herein is especially preferred for the compositions and methods of this invention. These salts of the aliphatic film-forming amines may be used in the compositions of this invention in an amount of from about 0.1% by weight to about 50% by weight, preferably from about 0.5% by weight to about 10% by weight.
Neutralizing amines are known in the art and function as corrosion inhibitors by neutralizing carbonic acid present in water and steam systems as the result of dissolved carbon dioxide. Any other acids present would also be neutralized. They are employed in the methods and compositions of this invention along with fatty film-forming amines and the polyoxyalkylene containing tertiary amines of this invention to give improved corrosion inhibition. Examples of neutralizing amines known in the art are cyclohexylamine, morpholine and diethylaminoethanol (DEAE). Of these, diethylaminoethanol is especially preferred for use with the methods and compositions of this invention. The neutralizing amine may be contained in the compositions of this invention in an amount of from about 1% by weight to about 50% by weight, preferably from about 1% by weight to about 20% by weight.
The polyoxyalkylene-containing tertiary amines useful in this invention may be represented by the formula:
wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkyl ene chain of randomly distributed oxyalkylene units, the total of these units in the chain being n, which is an integer of3 to and preferably 5 to 50, said polyoxyalkylene chain consisting of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1, respectively.
polyoxyalkylene-containing tertiary amines of this type are described in US. Pat. No. 3,456,013, which is incorporated herein by reference.
Such polyoxyalkylene-containing tertiary amines are condensation products of a secondary mono-amine containing two aliphatic hydrocarbon radicals with a mixture of ethylene oxide and propylene oxide. The different oxyalkylene groups are distributed randomly throughout the oxyalkylene chain and the oxyalkylene chain itself may vary in length. While this results in a varying structure, the compounds produced are characterized by the average length of the polyoxyalkylene chain and the average ratio of oxyethylene units to oxypropylene units in the polyoxyalkylene chain. Several particular polyoxyalkylene-eontaining tertiary amines were used in preparing formulations according to this invention, as will be described later. These tertiary amines contain 5, 10, 15, 20, 30 and 50 moles of polyoxyalkylene per mole of the tallow amine component of the tertiary amine, and are designatd EO/PO (for ethylene oxide/propylene oxide) 5, 10, 15, 20, 30 and 50 respectively. The tertiary amine will be present in the compositions of this invention in an amount of from about 0.1% by weight to about 10.0% by weight, preferably in an amount from about 0.2% by weight to about 5.0% by weight.
This invention contemplates the use of the polyoxyalkylene-containing tertiary amines just described with aliphatic film-forming amine and water to produce what is, in effect, an emulsifiable concentrate. That is, the mixture is an emulsion which is suitable to be diluted to any desired concentration and then fed directly to the system to be treated. This invention further contemplates the use of one or more salts of an aliphatic film-forming amine, which are more water soluble than the amine itself, along with the mixture of the film-forming amine and polyoxyalkylene-containing tertiary amine as described above. These salts of aliphatic film-forming amines are well known in the art and include, for example, the acetate and glycolate salts of various aliphatic film-forming amines. ln this invention the use of tallow amine acetate is particularly preferred. This invention also contemplates the use of a neutralizing amine along with the mixture of the aliphatic film-forming amine and the polyoxyalkylenecontaining tertiary amine amine described above. in this invention the use of diethylaminoethanol (DEAE) is particularly preferred. These various aspects of this invention will now be further described by way of illustrative examples which disclose the preparation of representative formulations that may be utilized in accordance with the teachings of the present invention. 5
EXAMPLE I The following ingredients were mixed together:
Ingredient Amount (grams) /1 by Welght Armeen HT 30 15 (hydrogenated tallow amine) EO/PO 20 4 2 Distilled Water 166 83 The mixture was heated to 150F. and then agitated. The agitation continued while the mixture was re moved from the source of heat, and was maintained until the mixture was cold. The finished product was a uniform paste.
The mixture was not heated, but was simply agitated vigorously. The resultant product was foamy, but fluid. Feed solutions were prepared having 20%, and 1% by weight of solids concentrations. These feed solutions were satisfactory for introduction into a system to be treated.
EXAMPLE 3 The following ingredients were mixed together:
Ingredient Amount (grams) "/1 by Weight Armeen HT 25 12.5 Adogen 140A 5 2.5 EO/PO 2.5 1.2 Distilled Water 167.5 83.8
The mixture was stirred while heating to 160F. The mixture was then removed from the heat and agitated until cool. The finished product was a uniform paste.
EXAMPLE 4 The following ingredients were mixed together:
EXAMPLE 5 The following total amounts of ingredients were used:
A halfgram (0.5 of the EO/PO 20, the 20 grams ofArmeen HT, the 10 grams of Armac HT, and 1()() grams of distilled water were mixed and heated with stirring to 160F. The mixture was then removed from the heat and agitated until the mixture reached 120F. Then the remaining 4.5 grams of EO/PO 20 and grams oldistilled water were added slowly to the mixture while agitation was continued. The mixture was very viscous prior to addition of the remaining EO/PO 2(1 and distilled water, but with the addition the viscosity was reduced, resulting in a very fluid. uniform product.
EXAMPLE 6 The following total amounts of ingredients were used:
A 0.2 gram amount of the EO/P'O 20 was added to 99.8 mls. of distilled water, then the 20 grams of Ar meen and 10 grams of Armac were added, and the total mixture was heated with stirring to 160F. The mixture was removed from the heat and agitated until it reached F. The agitation was continued while the remaining amounts of the ingredients, 0.2 gram of EO/PO 20 and 69.8 of distilled water, were added slowly to the mixture. The final product was somewhat viscous but still fluid. Feed solutions of 20%. 5% and 1% by weight of solids content were prepared, and were satisfactory for introduction into a system to be treated.
In the following Examples, the use of a neutralizing amine in addition to the aliphatic film-forming amine and polyoxyaIkylene-containing tertiary amine is illustrated.
EXAMPLE 7 The following total amounts of ingredients were used:
Ingredient Amount (grams) by Weight Armeen HT 25 12.5 0
Adogen A 5 Ingredient Amount (grants) 7: by Weight EO/PO I5 5 2.5
Distilled Water 16.5 8 Armeen HT 10 5 Armac HT 6 3 Pen nad 15() (DEAE or 36 18 The mixture was heated to F. with stirring. The 5 g I U 5 mixture was then removed from the heat and agitated Distilled Wuler 147 735 until its temperature reached 100F. The resultant product was thick but still pourable initially at 100F.
EXAMPLE 8 The following total amounts of ingredients were used:
Ingredient Amount (grams) "/1 by Weight Armeen HT 4.8 Armac HT 2 1.0 Pennad 150 36 17.2 EO/PO 20 0.6 0.3 Distilled Water 160 76.7
The final product was prepared as in Example 7 and proved to be uniform and viscous.
EXAMPLE 9 The following total amounts of ingredients were used:
lngredient Amount (grams) by Weight Armeen HT 20 10.0 Armac HT 4 2.0 Pennad 150 4 2.0 EO/PO 20 1.5 0.8 Distilled Water 170 85.2
The final product was prepared as in Example 7 above, and proved to be fluid and uniform.
EXAMPLE 10 The following ingredients were mixed together:
Amount (grams) 71 by Weight Ingredients Armeen HT 25 12.0 Armac HT 5 2.4 Pennad 150 8 3.8 EO/PO 20 1.8 1.0 Distilled Water 168 80.8
The mixture was heated with stirring to 160F. Agitation was continued while the mixture was cooled to 120F. The final product was uniform and viscous.
EXAMPLE 11 The following ingredients were mixed together:
Ingredients Amount (grams) 7: by Weight Adogen 140 3 1.5 Pennad 150 15 7.5 EO/PO 50 2 1.0 Distilled Water 80 40.0
The mixture was heated to 180F. with mild agitation. The mixture was then removed from the heat and placed under a Heller mixer and mildly agitated until it cooled to room temperature.
This invention contemplates use of the corrosioninhibiting compositions described herein in solid form as well as in fluid emulsion form. This solid form may simply be flakes of the corrosion-inhibiting composition produced by evaporating the water content from a thin layer of the fluid emulsion of the corrosioninhibting composition containing the desired proportions of components, disposed on any convenient surface. However, a preferred method of preparing a solid form of the corrosion-inhibiting compositions of this invention is by extrusion ofa hot mixture of the components of the corrosion-inhibiting composition, wherein the extruding device is cooled sufficiently to induce solidification of the corrosion-inhibiting composition, which will normally be solid at room temperature. Most conveniently, this is accomplished during the manufacturing process for aliphatic amines. Immediately fol lowing their manufacture, these aliphatic amines will be in a heated condition, and thus liquid. At this point, the additional components of the corrosion-inhibiting compositions of this invention can simply be incorporated into the aliphatic amine. Alterntively, a hot mixture is prepared simply by adding to the desired amount of the aliphatic film-forming amine maintained at an elevated temperature sufficient to render it fluid, appropriate quantities of the polyoxyalkylene-containing tertiary amine dispersing agent, and such other of the additional components ofthe corrosion-inhibiting compositions described herein as may be desired. The mixture is agitated to insure uniform dispersion ofall of the components. The extrusion itself may be performed with conventional equipment intended for this purpose, according to known extrusion techniques.
The compositions of this invention either already exist as emulsions, or, in the case of the extruded solid compositions, may be mixed with water to produce an emulsion. These emulsions may be diluted with water to form corrosion inhibiting compositions containing from 1% to 25% by weight of solids.
the corrosion inhibiting compositions of this invention may be incorporated into the system to be treated in a number of ways. They may be added to a water storage tank, or fed into water being added to such a storage tank, for example. For boiler systems, the compositions of this invention may be introduced to condensate receivers, deaerating heaters, boiler feed water lines, directly to the boiler itself, or directly to the steam lines for uniform distribution. Where necessary, a piston pump capable of exceeding the internal pressure of the boiler may be used. The feeding of the corrosion inhibiting composition may be continuous or at intervals. The corrosion inhibiting composition may be introduced at more than one point, and the treatment may be confined to the water alone, the steam alone, or both may be treated. Desirably, the corrosioninhibiting composition is added in amounts sufficient to maintain a weight of composition to weight of system aqueous fluid ratio of from about 0.1 to about parts per million. with a dynamic system, such as a boiler system, the amount added is expressed in terms of pounds of steam produced. Thus, the corrosion-inhibiting compositions of this invention would be added to a boiler system in an amount of from about 0.1 to about 100 pounds of product per million pounds of steam produced. Once the corrosion-inhibiting composition has been added, it becomes evenly dispersed in the water of the system and subsequently, because of its hydrophobic nature, becomes deposited on metal surfaces with which it comes in contact. With the generation of steam, the aliphatic film-forming amine enters its vapor phase and thereby becomes distributed uniformly throughout the entire system. The amine thereupon becomes deposited as a very thin film upon all exposed metallic interior surfaces of the system. Since this film is hydrophobic in nature, it serves to protect the metallic surfaces of the system against corrosive attack by the steam or water, or by both, contained in the system. Where vaporization of the aliphatic film-forming amine occurs, the temperature of the system must be sufficient for this purpose. When the system is under elevated pressure, as with a boiler system, or possibly under reduced pressure, the temperature required to produce vaporization of the aliphatic amine will be higher or lower, respectively, than that required at atmospheric pressure.
As indicated previously, the corrosion-inhibiting compositions of this invention may be dispersed in the system to be protected in amounts sufficient to maintain a weight of composition to weight of system aqueous fluid ratio of from about 0.1 to about 100 parts per million. However, when the system being treated is a steam system, the amounts (by weight) of corrosioninhibiting composition of this invention added to the system will preferably be in the range of from about 0.25 parts per million by weight.
The corrosion-inhibiting method and corrosioninhibiting properties of the compositions of this invention will be further illustrated by way of examples disclosing the usefulness of the method and compositions of this invention.
EXAMPLE 12 Ingredient "/1 by Weight Adogen M Adogcn 140A 5 EO/PO l Distilled Water 84 Strips (coupons) of a suitable metal subject to corrosion were prepared. These were of uniform dimension: l X 3 X l/l6 inches. They were cleaned, weighed and placed in steam of the particular system being used as the test basis. In this case the system was a steam system for a steel plant. The coupons remained in place for a predetermined period of time, during which the above corrosion-inhibiting composition of this invention was introduced into the steam system. For comparison, another corrosion-inhibiting material was employed for a separate and equal test interval. This material was hydrogenated tallow amine emulsified with isopropyl alcohol. After the predetermined period, the test coupons were removed from the system, acid cleaned to remove the corrosion products, and again weighed. The reduction in weight was then calculated on a yearly basis, noting the actual weight loss during the specific test period and the length of the predetermined time period. This yearly weight loss is expressed as milligrams per year, or mpy. The comparative results observed for the test procedure just described are summarized below.
Corrosion Rates in Mils Per Year Condensate Lines: A ll Hydrogenated Tallow Amine Emulsit'ied with lsopropyl Alcohol Composition of this 2.4 6.2 7.0 Example EXAMPLE 13 The following composition of this invention was employed in two different systems, utilizing the same test procedure as outlined above in Example 12, to establish its corrosion-inhibiting properties:
Ingredient Z by Weight Adogen o Pennad (DEAE) l5 EO/PO 50 2 Distilled Water 77 The systems used as the test bases were both steam systems; one located in a textile finishing plant and the second located on a naval base. The comparative results observed for the test procedure are summarized below.
Corrosion Rates in Mils Per Year 1. Textile Finishing Plant Condensate Lines l5 Hydrogenated Tallow [L0 7.5 Amine Emulsified with lsopropyl Alcohol Composition of this 7.5 l..'l Example 2. Naval Base Condensate Lines A B Hydrogenated Tallow Amine Emulsified with 28 (ill lsopropyl Alcohol Composition of this I2 25 Example R -N we R30 21 wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1, respectively, the total of all units in the chain begin n, which is an integer of 3 to 100.
2. The composition of claim 1 wherein n is an integer of 5 to 50.
3. The composition of claim 1 containing from about 1 percent by weight to about 90 percent by weight of aliphatic film-forming amine; and from about 0.1 percent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
4. The composition of claim 1 additionally included water.
5. The composition of claim 4 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
6. A corrosion-inhibiting composition comprising an aliphatic film-forming amine; an aliphatic amine salt; and a polyoxyalkylene-containing tertiary amine dispersing agent represented by the formula:
f2 R -N R30 4 H wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different, and wherein R is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1, respectively, the total of all units in the chain being n, which is an integer of 3 to 100.
7. The composition of claim 6 wherein n is an integer of 5 to 50.
8. The composition of claim 6 wherein the aliphatic amine salt is tallow amine acetate.
9. The composition of claim 6 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylenecontaining tertiary amine.
10. The composition ofclaim 6 additionally including water.
11. The composition'of claim 10 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
12. A corrosion-inhibiting composition comprising an aliphatic film-forming amine; a neutralizing amine; and a polyoxyalkylene-containing tertiary amine dispensing agent represented by the formula:
Il -N +R 0); H
wherein R and R are aliphatic hydrocarbon radicals having from 12 to carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylcne and oxypropylene units in a ratio of from 1:10 to 10:1, re' spectively, the total of all units in the chain being n, which is an integer of 3 to 100.
13. The composition of claim 12 wherein n is an integer of 5 to 50.
14. The composition of claim 12 wherein the neutralizing amine is diethylamino ethanol.
15. The composition of claim 12 containing from about 1 per cent by weight to about per cent by weight of aliphatic film-forming amine; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
16. The composition otclaim 12 additionally including water.
17. The composition of claim 16 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film'forming amine; from about 1 per cent by weight to about 50 per cent by weight 01 neutralizing amine; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
18. A corrosion-inhibiting composition comprising an aliphatic film-forming amine; an aliphatic amine salt; a neutralizing amine; and a polyoxyalkylenccontaining tertiary amine dispersing agent represented by the formula:
wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different, and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylenc and oxypropylene units in a ratio of from 1:10 to 10:1, respectively, the total of all units in the chain being n, which is an integer of 3 to 100.
19. The composition of claim 18 containing'from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; and from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weiht to about 10.0 per cent by weight of polyoxyalkylenecontaining tertiary amine.
20. The composition of claim 19 additionally including water.
21. The composition of claim'20 containing from about 1 per cent by weight to about 90 by weight of aliphatic film-forming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylenc-containing tertiary amine.
22. A method of inhibiting the corrosion of metal components which are contacted by aqueous fluids, comprising dispersing throughout said aqueous fluids a composition comprising an aliphatic film-forming wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1 respectively, the toal of all units in the chain being n, which is an integer of 3 to 100.
23. The method of claim 22 wherein for the composition employed therein n is an integer of to 50.
24. The method of claim 22 wherein the composition employed therein contains from about 1 per cent by weight to about 90 per cent by weight of aliphatic filmforming amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylenecontaining tertiary amine.
25. The method of claim 22 wherein the composition employed therein additionally includes water.
26. A method of inhibiting the corrosion of metal components which are contacted by aqueous fluids, comprising dispersing throughout said aqueous fluids a composition comprising an aliphatic film-forming amine; an aliphatic amine salt; and a polyoxyalkylenecontaining tertiary amine dispersing agent represented by the formula:
R -N +12 0 a a wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to :1, respectively, the total of all units in the chain being n, which is an integer of 3 to 100.
27. The method of claim 26 wherein for the composition employed therein n is an integer of 5 to 50.
28. The method of claim 26 wherein the composition employed therein contains from about 1 per cent by weight to about 90 per cent by weight of aliphatic filmforming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
29. The method of claim 26 wherein the composition employed therein additionally includes water.
30. A method of inhibiting the corrosion of metal components which are contacted by aqueous fluids, comprising dispersing throughout said aqueous fluids a composition comprising and aliphatic film-forming amine; a neutralizing amine; and a polyoxyalkylenecontaining tertiary amine dispersing agent represented by the formula:
RfN R 0); H wherein R and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1 respectively, the total of all units in the chain being 11,
which is an integer of 3 to 100.
31. The method of claim 30 wherein for the composi tion employed therein n is an integer of 5 to 50.
32. The method of claim 30 wherein for the composi tion employed therein contains from about 1 per cent by weight to about per cent by weight of aliphatic film-forming amine; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
33. The method of Claim 30 wherein the composition employed therein additionally includes water.
34. A method of inhibiting the corrosion of metal components which are contacted by aqueous fluids, comprising dispersing throughout :said aqueous fluids a composition comprising an aliphatic film-forming amine, an aliphatic amine salt; a neutralizing amine; and a polyoxyalkylene-containing tertiary amine dispersing agent represented by the formula:
wherein R, and R are aliphatic hydrocarbon radicals having from 12 to 20 carbon atoms, which can be the same or different; and wherein R 0 is a polyoxyalkylene chain of randomly distributed oxyethylene and oxypropylene units in a ratio of from 1:10 to 10:1 respectively, the total of all units in the chain being n, which is an integer of 3 to 100.
35. The method of claim 34 wherein for the composition employed therein n is an integer of 5 to 50.
36. The method of claim 34 wherein the composition employed therein contains from about 1 per cent by weight to about 90 per cent by weight of aliphatic filmforming amine; and from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
37. The method of claim 34 wherein the composition employed therein additionally includes water.
l l= =l=

Claims (37)

1. A CORROSION-INHIBITING COMPOSITION COMPRISING AN ALIPHATIC FILM-FORMING AMINE; AND A POLYOXYALKYLENE-CONTAINING TETIARY AMINE DISPERSING AGENT REPRESENTED BY THE FORMULA:
2. The composition of claim 1 wherein n is an integer of 5 to 50.
3. The compoSition of claim 1 containing from about 1 percent by weight to about 90 percent by weight of aliphatic film-forming amine; and from about 0.1 percent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
4. The composition of claim 1 additionally included water.
5. The composition of claim 4 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
6. A corrosion-inhibiting composition comprising an aliphatic film-forming amine; an aliphatic amine salt; and a polyoxyalkylene-containing tertiary amine dispersing agent represented by the formula:
7. The composition of claim 6 wherein n is an integer of 5 to 50.
8. The composition of claim 6 wherein the aliphatic amine salt is tallow amine acetate.
9. The composition of claim 6 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
10. The composition of claim 6 additionally including water.
11. The composition of claim 10 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
12. A corrosion-inhibiting composition comprising an aliphatic film-forming amine; a neutralizing amine; and a polyoxyalkylene-containing tertiary amine dispensing agent represented by the formula:
13. The composition of claim 12 wherein n is an integer of 5 to 50.
14. The composition of claim 12 wherein the neutralizing amine is diethylamino ethanol.
15. The composition of claim 12 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
16. The composition of claim 12 additionally including water.
17. The composition of claim 16 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to aBout 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
18. A corrosion-inhibiting composition comprising an aliphatic film-forming amine; an aliphatic amine salt; a neutralizing amine; and a polyoxyalkylene-containing tertiary amine dispersing agent represented by the formula:
19. The composition of claim 18 containing from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; and from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weiht to about 10.0 per cent by weight of polyoxyalkylenecontaining tertiary amine.
20. The composition of claim 19 additionally including water.
21. The composition of claim 20 containing from about 1 per cent by weight to about 90 by weight of aliphatic film-forming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; from about 1 per cent by weight to about 99 per cent by weight of water; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
22. A method of inhibiting the corrosion of metal components which are contacted by aqueous fluids, comprising dispersing throughout said aqueous fluids a composition comprising an aliphatic film-forming amine; and a polyoxyalkyl-ene-containing tertiary amine dispersing agent represented by the formula:
23. The method of claim 22 wherein for the composition employed therein n is an integer of 5 to 50.
24. The method of claim 22 wherein the composition employed therein contains from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
25. The method of claim 22 wherein the composition employed therein additionally includes water.
26. A method of inhibiting the corrosion of metal components which are contacted by aqueous fluids, comprising dispersing throughout said aqueous fluids a composition comprising an aliphatic film-forming amine; an aliphatic amine salt; and a polyoxyalkylene-containing tertiary amine dispersing agent represented by the formula:
27. The method of claim 26 wherein for the composition employed therein n is an integer of 5 to 50.
28. The method of claim 26 wherein the compositioN employed therein contains from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
29. The method of claim 26 wherein the composition employed therein additionally includes water.
30. A method of inhibiting the corrosion of metal components which are contacted by aqueous fluids, comprising dispersing throughout said aqueous fluids a composition comprising and aliphatic film-forming amine; a neutralizing amine; and a polyoxyalkylene-containing tertiary amine dispersing agent represented by the formula:
31. The method of claim 30 wherein for the composition employed therein n is an integer of 5 to 50.
32. The method of claim 30 wherein for the composition employed therein contains from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
33. The method of Claim 30 wherein the composition employed therein additionally includes water.
34. A method of inhibiting the corrosion of metal components which are contacted by aqueous fluids, comprising dispersing throughout said aqueous fluids a composition comprising an aliphatic film-forming amine, an aliphatic amine salt; a neutralizing amine; and a polyoxyalkylene-containing tertiary amine dispersing agent represented by the formula:
35. The method of claim 34 wherein for the composition employed therein n is an integer of 5 to 50.
36. The method of claim 34 wherein the composition employed therein contains from about 1 per cent by weight to about 90 per cent by weight of aliphatic film-forming amine; and from about 0.1 per cent by weight to about 50.0 per cent by weight of aliphatic amine salt; from about 1 per cent by weight to about 50 per cent by weight of neutralizing amine; and from about 0.1 per cent by weight to about 10.0 per cent by weight of polyoxyalkylene-containing tertiary amine.
37. The method of claim 34 wherein the composition employed therein additionally includes water.
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EP0410202A1 (en) * 1989-07-25 1991-01-30 Friedrich Sprügel Additive for liquifiedgas-fuel
US5071574A (en) * 1989-04-10 1991-12-10 Ceca, S.A. Process and compositions for reducing the corrosiveness of oxygenated saline solutions by stripping with acidic gases
US5283006A (en) * 1992-11-30 1994-02-01 Betz Laboratories, Inc. Neutralizing amines with low salt precipitation potential
US5427699A (en) * 1992-11-06 1995-06-27 Halliburton Company Low viscosity acid-in-oil emulsions and methods
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US5071574A (en) * 1989-04-10 1991-12-10 Ceca, S.A. Process and compositions for reducing the corrosiveness of oxygenated saline solutions by stripping with acidic gases
EP0410202A1 (en) * 1989-07-25 1991-01-30 Friedrich Sprügel Additive for liquifiedgas-fuel
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US20070048181A1 (en) * 2002-09-05 2007-03-01 Chang Daniel M Carbon dioxide nanosensor, and respiratory CO2 monitors
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US7948041B2 (en) 2005-05-19 2011-05-24 Nanomix, Inc. Sensor having a thin-film inhibition layer
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US20130119303A1 (en) * 2010-05-18 2013-05-16 Bk Giulini Gmbh Medium for improving the heat transfer in steam generating plants
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WO2013160101A1 (en) * 2012-04-26 2013-10-31 Basf Se Novel vapor space anticorrosive composition
US9228127B2 (en) 2012-04-26 2016-01-05 Basf Se Vapor space anticorrosive composition
US9505969B2 (en) 2012-04-26 2016-11-29 Basf Se Vapor space anticorrosive composition
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