Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—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
  • C23F11/14—Nitrogen-containing compounds
  • C23F11/141—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—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
  • 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
  • C23F11/14—Nitrogen-containing compounds
  • C23F11/141—Amines; Quaternary ammonium compounds
  • C23F11/142—Hydroxy amines
• • 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
  • C23F11/14—Nitrogen-containing compounds
  • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

Definitions

• the present invention relates to a corrosion inhibitor for suppressing the corrosion of metals used in heat exchangers and piping of boiler steam condensate systems, and particularly has excellent long-term storage stability in a high-temperature environment. It relates to a food inhibitor. The present invention also relates to a method for inhibiting corrosion using this corrosion inhibitor.
• This agent is mainly a film-forming agent that forms an anticorrosive film on a metal surface so that steam condensate containing corrosive factors such as oxygen and carbon dioxide does not directly contact the metal surface. It is roughly divided into neutralizing agents that neutralize carbon dioxide contained in water. In order to suppress corrosion more effectively, one having both a film forming function and a neutralizing function has been proposed (see Japanese Patent Publication No. 4-45590). This includes a long-chain aliphatic amine having 10 to 24 carbon atoms, an alkanolamine compound, and an aliphatic alkali metal salt having 8 to 24 carbon atoms.
• long-chain aliphatic amines have a film-forming function
• alkanolamine compounds have a neutralizing function
• aliphatic alkali metal salts have a surfactant activity that emulsifies and disperses long-chain aliphatic amines in aqueous systems. It plays the role of each agent.
• the aqueous emulsion drug having both the film forming function and the neutralizing function described above has insufficient storage stability and is not particularly suitable for long-term storage in a high-temperature environment. For this reason, in order to improve stability, some improvement proposals have been made by changing the type of surfactant and the type of amine that is a neutralizing agent (for example, JP-A-11-335878 and JP-A-2002). — 25 See publication 6462). These drugs contain a long chain aliphatic amine compound having 10 to 24 carbon atoms, an aliphatic amino alcohol compound, and a polyoxyethylene sorbitan fatty acid ester.
• a combination containing a long chain aliphatic amine compound having 10 to 24 carbon atoms, an aliphatic amino alcohol compound, and a polydaricerin ester compound containing a long chain aliphatic amine compound having 10 to 24 carbon atoms, an aliphatic amino alcohol compound, and a polydaricerin ester compound.
• These agents basically serve as corrosion inhibitors for long-chain aliphatic amine compounds, aliphatic amino alcohol compounds, and surfactants.
• Patent Document 1 Japanese Patent Publication No. 4-45590
• Patent Document 2 Japanese Patent Laid-Open No. 11 335878
• Patent Document 3 Japanese Patent Laid-Open No. 2002-256462
• aqueous emulsion corrosion inhibitor having both a film forming function and a neutralizing function
• a method for producing these improved drugs is firstly a compound of a long-chain aliphatic amine compound and an aliphatic amino alcohol compound.
• a polyglycerin ester compound, or a mixed solution of a long-chain aliphatic amine compound, an aliphatic amino alcohol compound, and a polyoxyethylene sorbitan fatty acid ester which is dropped into cold water to form an aqueous emulsion.
• This is a two-stage batch process. In such a two-stage manufacturing method, it is necessary to have multiple equipment such as reaction kettles, and the amount of washing waste liquid discharged after production is large, and this washing waste liquid contains COD such as fatty acids.
• the burden on the environment is also a problem.
• the present invention is a corrosion inhibitor having both a film forming function and a neutralizing function, and can be stably stored for a long time even in a high temperature environment, and can be easily produced in one batch.
• the object is to provide a possible corrosion inhibitor.
• the corrosion inhibitor of the present invention contains components of the following groups (A) to (C).
• This corrosion inhibitor comprises (A) a long-chain aliphatic amine, (B) a surfactant and (C) a water-soluble amine that is emulsified in an aqueous medium. Content is 0.3-2
• the surfactant content may be 2 to 4.5% by weight
• the water-soluble amine content may be 0.5 to 50% by weight.
• the surfactant may include a polyethylene glycol fatty acid ester and a propylene glycol fatty acid ester and / or a glycerin fatty acid ester.
• the corrosion inhibitor of the present invention has both a film forming function and a neutralizing function.
• This corrosion inhibitor can be stored stably for a long period of time without property changes such as gelation (thickening) even in a high temperature environment.
• This corrosion inhibitor is a long-chain aliphatic amine, a surfactant, and a water-soluble amine placed in a production kettle and heated to stir to make a homogeneous solution. Water is then added to emulsify and gradually stirred. By cooling, it can be easily produced in one batch. With this manufacturing method, only one manufacturing pot is sufficient, and the amount of waste liquid discharged is greatly reduced.
• the corrosion inhibitor of the present invention contains components of the following groups (A) to (C).
• component (A) Long chain aliphatic amine having 10 to 22 carbon atoms (hereinafter sometimes referred to as “component (A)”)
• component (B) Surfactant containing polyethylene glycol fatty acid ester (hereinafter sometimes referred to as “component (B)”)
• component (C) One or more water-soluble amines selected from the group consisting of 2-amino-2-methylmonopropanol, morpholine, and monoisopropanolamine (hereinafter sometimes referred to as “component (C)”. )
• the long chain aliphatic amine having 10 to 22 carbon atoms of the component (A) is a component for forming a film for suppressing corrosion by water on the metal surface.
• the long chain aliphatic group has 10 to 22 carbon atoms, preferably 12 to 20 carbon atoms. If this carbon number is less than 10, In contrast, there is a possibility that a film will be formed, and the corrosion inhibiting function may be insufficient. On the other hand, when the number of carbon atoms exceeds 22, the corrosion inhibitor emulsions become gelled and the stability may be impaired.
• the long chain aliphatic group constituting the long chain aliphatic amine may contain an unsaturated bond! /.
• the hydrogen portion may be appropriately substituted with a hydrocarbon group such as a methyl group or an ethyl group.
• the long chain aliphatic amine may be a fatty acid salt.
• examples of the fatty acid constituting the fatty acid salt include oleic acid, lauric acid, and stearic acid.
• long-chain aliphatic amines of component (A) preferred are, for example, dodecylamine, tridecylamine, tetradecylamine, heptadecylamine, hexadecylamine, octadecinoreamine, nonadecinoreamine , Saturated aliphatic amines such as eicosinoreamine, docosinoreamine, oleylamine, ricinoleinamine, linoleinoleamine, unsaturated aliphatic amines such as linoleylamine, mixed oils such as coconut oil amine and hardened beef tallow amine This force S is possible. Two or more types of long chain aliphatic amines may be used in combination.
• octadecylamine is approved as an additive for boiler water in the U.S. FDA standards.When it is used as component (A), steam generated from the boiler leaks and comes into contact with food. However, there is no problem in terms of safety, so it has the advantage that it can be used in the food manufacturing industry.
• the surfactant of component (B) contains a polyethylene glycol fatty acid ester, and preferably comprises a combination of a polyethylene glycol fatty acid ester and a propylene glycol fatty acid ester and / or a glycerin fatty acid ester.
• a polyethylene glycol fatty acid ester preferably comprises a combination of a polyethylene glycol fatty acid ester and a propylene glycol fatty acid ester and / or a glycerin fatty acid ester.
• the surfactant it is possible to use only polyethylene glycol fatty acid ester, but in order to realize a corrosion inhibitor with excellent storage stability, polyethylene glycol fatty acid ester and propylene glycol fatty acid ester and / or glycerin are used. It is preferable to use in combination with a fatty acid ester.
• the fatty acid of the polyethylene glycol fatty acid ester is preferably a fatty acid having 8 to 24 carbon atoms, particularly 10 to 22 carbon atoms. Specifically, oleic acid, lauric acid, stearic acid, coconut oil fatty acid, tall oil fatty acid, etc. Is mentioned.
• Suitable polyethylene glycol includes PEG400 (average molecular weight is 400), PEG600 (average molecular weight is 600), PEG3000 (average molecular weight is 3000), and the like.
• the polyethylene glycol fatty acid ester has an HLB of 6-18, preferably 8-14, specifically PEG400 dioleic acid ester, PEG400 coconut oil fatty acid ester ester, PEG600 tonole oil lunar lunar acid ester ester, Examples include PEG400 monolaurate ester, PEG600 monolaurate, PEG400 monooleate, PEG600 monooleate, PEG400 monostearate, PEG600 stearate, PE G3000 monostearate. These polyethylene glycol fatty acid esters may be used alone or in combination of two or more.
• propylene glycol fatty acid ester HLB is !!-9, preferably 2-6, and the same fatty acid as exemplified as the fatty acid of polyethylene glycol fatty acid ester.
• examples include esters.
• the glycerin fatty acid ester include esters of glycerin having an HLB of 1 to 9, preferably 2 to 8, and fatty acids similar to those exemplified as the fatty acid of the polyethylene glycol fatty acid ester.
• Propylene glycol fatty acid ester and glycerin fatty acid ester may be used alone or in combination of two or more.
• one or more of propylene dallicol fatty acid ester and one or more of glycerin fatty acid ester may be used in combination.
• the water-soluble amine of component (C) is a component for neutralizing carbon dioxide contained in water.
• As the water-soluble amine 2-amino-2-methyl-propanol, morpholine, and monoisopropanolamine, which are US FDA standard products, are preferable, but not limited thereto.
• water-soluble amines may be used alone or in combination of two or more.
• the corrosion inhibitor of the present invention comprises the components (A), (B) and (C) in an aqueous medium such as water. It is provided as an emulsified composition.
• the content of the long-chain aliphatic amine as component (A) in such a corrosion inhibitor is 0.3 to 2.0% by weight, particularly 0.5 to 1.0% by weight. It is preferable. If the long-chain aliphatic amine content of component (A) is less than 0.3% by weight, it may be difficult to form a required film for preventing corrosion on metals.
• the amount of corrosion inhibitor used to form a film is excessive and uneconomical, and the stability of the corrosion inhibitor itself, particularly the emulsion stability, may be impaired.
• the corrosion inhibitor tends to gel, making it difficult to form the required film on the metal member, and possibly closing a narrow metal pipe. is there.
• the corrosion inhibitor is likely to be phase-separated and the emulsion stability may be reduced.
• the content of the component (B) surfactant in the corrosion inhibitor is 2 to 4.5% by weight, particularly 2.5 to
• the content of the component (B) surfactant is less than 2% by weight, the storage stability of the corrosion inhibitor is insufficient, and if it is more than 4.5% by weight, an improvement in the effect can be obtained. However, the amount of the surfactant used is increased, which is uneconomical.
• a polyethylene glycol fatty acid ester in combination with a propylene glycol fatty acid ester and / or a glycerin fatty acid ester.
• the content of the water-soluble amine of the component (C) in the corrosion inhibitor is 0.5 to 50% by weight, particularly 20 to
• the corrosion inhibitor of the present invention comprises (A) a long-chain aliphatic amine, (B) a surfactant, and (C) a water-soluble amine in a production kettle. Heat and stir to about 70 ° C to make a uniform solution, and then add a predetermined amount of water to this while keeping the production kettle at 40-60 ° C; stir for about ⁇ 8 hours, then By gradually cooling to room temperature while stirring, it can be easily prepared in one production kettle.
• the corrosion inhibitor of the present invention may optionally contain, in addition to the above-described components (A) to (C), conventional components of corrosion inhibitors and other auxiliary additive components as necessary.
• auxiliary additives include solubilizers such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and glycerin, sequestering agents, and antifreeze agents.
• the corrosion inhibitor of the present invention is continuously or intermittently added to the feed water or steam so as to have a concentration of 0.;! To 200 mg / L, preferably 1 to 100 mg / L. Corrosion of metal parts can effectively suppress corrosion of metal parts.
• Components (A) to (C) or other components having the composition shown in Table 1 were charged into a production kettle and heated to 60 to 70 ° C with stirring to dissolve uniformly. Next, water was added in the amount shown in Table 1, and the production kettle was kept at 45-50 ° C and stirred for 3-4 hours. Then, gradually cooled to room temperature with stirring
• the drugs prepared in each example were stored in a constant temperature bath at 25 ° C or 45 ° C, taken out in a timely manner, examined for changes in viscosity over time, and the results are shown in Table 2.
• the corrosion inhibitor of the present invention is stable when stored at 45 ° C, and the viscosity hardly changes and is excellent in stability.
• the corrosion inhibitor of the comparative example has a temperature of 45 ° C. It is clear that thickening and storage properties change upon storage.
• Soft water was supplied to a steam generator with pressure IMPa, and the test piece made of mild steel was immersed in steam condensed water, and the corrosion rate after 48 hours was examined.
• a steam generator was also added with an oxygen scavenger to adjust the dissolved oxygen concentration to 1 mg / L or less.
• the temperature of the steam condensate was kept at about 40 ° C.
• Softened water was obtained by treating tap water from Nogi Town in Tochigi Prefecture, Japan, and the average acid consumption (pH 4.8) was 40 mg-CaCO / L.
• the amount of the preparation added was 100 mg / L—water supply (the amount of amine added was 30 mg / L water-soluble amine and 0.7 mg / U octadecinoleamine).

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• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)

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• 2006
  • 2006-10-03 JP JP2006271974A patent/JP5092334B2/ja active Active
• 2007
  • 2007-09-26 WO PCT/JP2007/068619 patent/WO2008041569A1/ja active Application Filing
  • 2007-09-26 CN CN2007800372657A patent/CN101528982B/zh not_active Expired - Fee Related
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