WO2014104262A1 - Method for preventing corrosion of steam/condensate system, and corrosion inhibitor for use in said method - Google Patents

Method for preventing corrosion of steam/condensate system, and corrosion inhibitor for use in said method Download PDF

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Publication number
WO2014104262A1
WO2014104262A1 PCT/JP2013/085012 JP2013085012W WO2014104262A1 WO 2014104262 A1 WO2014104262 A1 WO 2014104262A1 JP 2013085012 W JP2013085012 W JP 2013085012W WO 2014104262 A1 WO2014104262 A1 WO 2014104262A1
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oil
steam
palm
acid
condensate
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PCT/JP2013/085012
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French (fr)
Japanese (ja)
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周子 進邦
幸祐 志村
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栗田工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C23F11/126—Aliphatic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • 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

Definitions

  • the present invention relates to an anticorrosion method for a steam condensate system in a boiler and / or other steam generating plant, and an anticorrosive agent used in the method.
  • Patent Documents 1 and 2 propose a method of operating a steam boiler apparatus in which fatty acid salts such as ammonium oleate and ammonium stearate are added. Although these fatty acid salts exhibit a certain degree of anticorrosion effect on steam condensate steel, there is a problem that the corrosiveness increases on copper. Moreover, when these ammonium salts are added, ammonia is transferred to the condensate from the condensate, and the ammonia is transferred to the steam condensate system, which is condensed while circulating in the system, so that a pressure gauge, a differential pressure transmitter, etc.
  • fatty acid salts such as ammonium oleate and ammonium stearate are added.
  • An object of the present invention is to provide a steam condensate anticorrosion method that exhibits an excellent anticorrosion effect on both steel and copper, and an anticorrosive used in the anticorrosion method.
  • a steam condensate anticorrosion method in which an emulsion emulsified with vegetable oil is added to steam or condensate in a boiler and / or other steam generating plant, wherein the vegetable oil is safflower oil, olive oil Steam condensate anticorrosion method comprising one or more selected from sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, palm oil, rice bran oil, linseed oil, and peanut oil .
  • the steam condensate anticorrosion method according to [1] wherein the plant oil is emulsified using a plant-derived ester emulsifier.
  • the vegetable oil or fat is selected from (i) safflower oil, (ii) olive oil, or (iii) safflower oil, olive oil, and rapeseed oil, sunflower oil, cottonseed oil, palm oil, palm kernel oil,
  • the steam condensate anticorrosion method according to any one of [1] to [3] above, which is a mixed oil containing a combination of at least one selected from coconut oil, rice bran oil, linseed oil, and peanut oil.
  • a steam condensate anticorrosion method in which an emulsion emulsified with vegetable oil is added to steam or condensate in a boiler and / or other steam generating plant, the vegetable oil Is characterized by containing one or more selected from safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, palm oil, rice bran oil, linseed oil, and peanut oil
  • An anti-corrosion method for steam condensate, and (2) an anti-corrosion agent used in the anti-corrosion method can be provided.
  • the steam condensate anticorrosion method of the present invention (hereinafter also simply referred to as “corrosion preventive method”) is an emulsion obtained by emulsifying plant oils and fats in a boiler and / or other steam generating plant (hereinafter also referred to as “boilers”).
  • a steam condensate-type anticorrosion method for adding water to steam or condensate wherein the vegetable oil is safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, coconut oil, rice bran oil , Linseed oil, and peanut oil, one or more selected from peanut oil.
  • the anticorrosive agent of the present invention is a steam condensate anticorrosive agent in boilers and / or other evaporation generating plants, and includes safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, and palm. It is an emulsion formed by emulsifying one or more kinds of vegetable oils and fats selected from oil, rice bran oil, linseed oil, and peanut oil.
  • the anticorrosion method and anticorrosive agent of this invention are demonstrated sequentially.
  • Such steam boilers mainly use steel pipes for steam piping for supplying generated steam to a load device, etc., and for condensate piping for collecting condensate and mixing it with feed water. Since copper also uses copper material, corrosion may occur in the piping with the long-term operation of the steam boiler device. Such corrosion is a cause of hindering the continuous and stable operation of the steam boiler apparatus. Therefore, in the steam boiler apparatus, as a chemical for suppressing corrosion, a method of adding a neutralizing amine, a film-forming amine, a fatty acid salt such as ammonium oleate or ammonium stearate, etc. is known, There is the above-mentioned problem. On the other hand, in the anticorrosion method of the present invention, by adding an emulsified emulsion of a vegetable oil to steam or condensate in the boiler, it is possible to prevent corrosion very effectively in the steam system of the boiler. it can.
  • the vegetable oils and fats that are raw materials of the emulsion used in the anticorrosion method of the present invention mean fatty acid triglycerides, diglycerides, monoglycerides, and mixtures thereof.
  • the fats and oils which have the triglyceride of a fatty acid as a main component are preferable, and may contain diglyceride, monoglyceride, and free fatty acid.
  • plant oils and fats those mainly composed of triglycerides of saturated or unsaturated higher fatty acids having 8 or more carbon atoms are preferred, so safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, One or more selected from palm oil, rice bran oil, linseed oil, and peanut oil are selected.
  • safflower oil (i) olive oil, (iii) safflower oil, olive oil, and rapeseed oil, sunflower oil, cottonseed oil, palm oil, palm kernel oil, palm oil, rice bran
  • a mixed oil containing a combination with one or more selected from the above is preferred.
  • (Iii) As mixed oil (a) mixed oil containing olive oil and coconut oil, (b) mixed oil containing rapeseed oil, sunflower oil and coconut oil, (c) mixed oil containing palm kernel oil and rapeseed oil Etc. are preferable.
  • the mass ratio of the mixed oil containing olive oil and palm oil (olive oil / coconut oil) is not particularly limited, but is preferably 20/80 to 95/5, more preferably 40/60 to 90/10. More preferably, it is 60/40 to 80/20.
  • (B) The mass ratio of the rapeseed oil and the mixed oil containing sunflower oil and palm oil [rapeseed oil / (sunflower oil + coconut oil)] is not particularly limited, but is preferably 20/80 to 95/5.
  • the mass ratio of the mixed oil containing palm kernel oil and rapeseed oil is not particularly limited, but is preferably 20/80 to 95/5, more preferably 40/60 to 90/10. More preferably, it is 50/50 to 85/15, and still more preferably 60/40 to 80/20.
  • the fatty acid component of the above-mentioned vegetable oil contains the following various higher fatty acids (mass%).
  • the ratios of higher fatty acids shown below are based on the composition of general vegetable oils and fats, and when using vegetable oils based on improved varieties (such as high oleic and hylinol species), the following ratio ranges May be used, but they may be used.
  • Fatty acid composition of safflower oil 4-8% palmitic acid, 0-1% palmitoleic acid, 1-4% stearic acid, 8-25% oleic acid, 60-80% linoleic acid, 0-1% linolenic acid
  • Fatty acid composition of olive oil [from Italy] palmitic acid 9.2%, stearic acid 2.0%, oleic acid 83.1%, linoleic acid 3.9%
  • Fatty acid composition of sunflower oil [palmitic acid, stearic acid, arachidic acid] 8.7 to 14.2%, oleic acid 14.1 to 43.1%, linoleic acid 44.2 to 75.4%, unsken 1.5% or less of chemicals ⁇
  • Fatty acid components of rapeseed oil palmitic acid 1-3%, stearic acid 0.2-3%, oleic acid 12-18%, eicosenoic acid 3-6%, erucic acid 45-55%, linole Acid 12-16%, Linolenic
  • ⁇ Fatty acid composition of palm oil 1 to 3% mistylic acid, 35 to 48% palmitic acid, 3 to 7% stearic acid, 37 to 50% oleic acid, 7 to 11% linoleic acid
  • Fatty acid composition of palm kernel oil lauric acid 44-55%, myristic acid 10-17%, palmitic acid 6-10%, stearic acid 1-7%, oleic acid 1-17%, linoleic acid 0-2%
  • -Fatty acid composition of palm oil 45-52% lauric acid, 15-22% myristylic acid, 4-10% palmitic acid, 1-5% stearic acid, 2-10% oleic acid, 1-3% linoleic acid -Fatty acid composition of koji oil: mistylic acid 0-1%, palmitic acid 11-21%, palmitoleic acid 0-1%, stearic acid 1-3%, oleic acid 35-50%, linoleic acid 25-40%, linole
  • ⁇ Emulsified emulsion of vegetable oil> Although there is no restriction
  • the vegetable oil concentration and emulsifier concentration in the emulsion are not particularly limited as long as the emulsion is stable.
  • the emulsifier plant-derived ester emulsifiers, ether-based emulsifiers and the like are preferable, and plant-derived ester-based emulsifiers are more preferable. This plant-derived emulsifier is also preferable from the viewpoint of safety when touching the human body.
  • Plant-derived ester emulsifier examples include glycerin fatty acid ester obtained by heating reaction of vegetable oil and glycerin, sucrose fatty acid ester obtained by transesterification of sucrose and fatty acid methyl ester, various fatty acids and sorbitol. And sorbitan fatty acid ester obtained by esterification using an alkali as a catalyst, propylene glycol fatty acid ester obtained by esterifying propylene glycol and fatty acid, soybean phospholipid obtained from soybean, polyoxyethylene fatty acid ester and the like.
  • one or more glycerin fatty acid esters selected from fatty acid monoglycerides and fatty acid diglycerides are more preferable, and fatty acid monoglycerides are more preferable.
  • the average number of glycerin units of the fatty acid monoglyceride is preferably 2 to 14, more preferably 6 to 12, and still more preferably 8 to 12.
  • the number of carbon atoms of the fatty acid of the fatty acid monoglyceride is preferably 2 to 30. Most preferred is decaglyceryl monostearate.
  • Examples of a method for preparing an emulsion by emulsifying vegetable oils and fats include a method in which vegetable oils and fats are homogenized in an aqueous medium using a homogenizer in the presence of a plant-derived ester emulsifier.
  • Examples of the homogenizer include a colloid mill, a vibration stirrer, a two-stage high-pressure pump, a high-pressure jet from a nozzle and an orifice, and ultrasonic stirring.
  • the adjustment of the particle size of the oil droplets in the emulsion is influenced by the control of the shearing force during the homogenization process, the amount of the emulsifier, etc., and these can be selected by simple preliminary experiments.
  • the size of the oil droplet diameter is a value measured by a dynamic light scattering method, preferably about 0.8 nm to 50 ⁇ m, more preferably 10 nm to 10 ⁇ m, more preferably 20 nm to 2 ⁇ m, and still more preferably 40 nm to 1 ⁇ m. .
  • the concentration of the vegetable oil / fat in the condensed oil obtained by condensing the vapor of the vegetable oil / fat thus obtained is preferably 0.05 to 50 mg / L, more preferably.
  • the range is 0.1 to 25 mg / L, more preferably 0.5 to 25 mg / L, still more preferably 1 to 25 mg / L, still more preferably 5 to 25 mg / L, and still more preferably 8 to 25 mg / L.
  • the addition site may be either a steam line or a condensate line, but it is preferable to add to the steam line because the vegetable oil is uniformly dispersed in the steam and condensed water.
  • a dead end pipe such as a pressure gauge or a differential pressure transmitter is used.
  • Condensed water such as steam condensate piping and heat exchangers can be added with low concentration even if carbon dioxide or oxygen is present in the steam without causing clogging trouble or alkali corrosion in the decompression section. It is possible to satisfactorily prevent corrosion of the surface in contact with both steel and copper.
  • the effects of the present invention can be sufficiently exerted by adding an emulsified emulsion of vegetable oils to the condensate line or steam line, but the object of the present invention is not impaired.
  • various additive components such as alkali agents, pH adjusters, anticorrosives, scale inhibitors and the like can be added in effective amounts to the condensate and boiler water. These additive components can be used alone or in combination of two or more.
  • alkaline agent examples include potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate.
  • pH adjuster examples include trisodium phosphate, disodium phosphate, and a mixture of trisodium phosphate and disodium phosphate in a predetermined ratio.
  • oxygen absorber examples include erythorbic acid (salt), ascorbic acid (salt), sulfurous acid (salt), tannin, tannic acid (salt), and the like.
  • anticorrosive agent for example, neutralizing amine, film-forming amine, various acids and / or salts thereof, water-soluble polymer and / or copolymer having a carboxyl group, scale inhibitor, scale remover and the like can be used.
  • Neutralizing amine examples include monoethanolamine (MEA), cyclohexylamine (CHA), morpholine (MOR), diethylethanolamine (DEEA), monoisopropanolamine (MIPA), 3- Examples include methoxypropylamine (MOPA), 2-amino-2-methyl-1-propanol (AMP), and the like.
  • Film-forming amine examples include long-chain alkylamines such as octadecylamine.
  • Various acids and / or salts thereof examples of various acids and / or salts thereof include citric acid and / or salts thereof, potassium succinate and the like.
  • Citrate is a salt obtained by substituting the hydrogen atom of the carboxyl group of citric acid with an alkali metal such as sodium or potassium.
  • Specific examples of the citrate include salts such as sodium citrate, sodium hydrogen citrate, potassium citrate, potassium hydrogen citrate, and hydrates thereof.
  • (Iv) Water-soluble polymer As the water-soluble polymer, a water-soluble homopolymer and / or copolymer having a carboxyl group is used. Specific examples thereof include homopolymers obtained using monomers selected from acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, and salts thereof. , Polymers selected from copolymers and copolymers with isobutylene, and the like.
  • Scale inhibitors, scale removers Specific examples of scale inhibitors and scale removers include various phosphates, water-soluble polymer compounds such as polyacrylic acid, polymaleic acid, and sodium salts thereof, and phosphones. Examples thereof include acid salts and chelating agents.
  • the anticorrosive agent of the present invention is a steam condensate anticorrosive agent in boilers and / or other evaporation generating plants, including safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, coconut oil, It is an emulsion obtained by emulsifying vegetable oil containing one or more selected from rice oil, linseed oil, and peanut oil. In addition, it is preferable to prepare an emulsion by emulsifying the vegetable oil using a plant-derived ester emulsifier.
  • the anticorrosive of this invention can contain the said various arbitrary addition components suitably as needed with the emulsion emulsion of the said vegetable oil and fat as needed.
  • the acidic sodium carbonate of Nogimachi water was 52 mg / L.
  • potassium succinate (anticorrosive) 20mg / L, sodium polyacrylate (scale inhibitor) 3mg / L, potassium hydroxide (alkali agent) 5mg / L as treatment agents in boiler cans did.
  • Preparation Example 1 (Preparation of safflower oil emulsion)
  • a polyglycerin fatty acid ester plant-derived ester emulsifier [manufactured by Nikko Chemicals Co., Ltd., trade name: NIKKOL Decaglyn 1-SV]
  • a homogenizer manufactured by IKA, model By emulsifying 30 parts by weight of safflower oil using a name: ULTRA-TURRAX T50 basic]
  • an emulsified safflower oil emulsion having an oil droplet average diameter of about 100 nm was prepared.
  • Preparation Example 2 (Preparation of olive oil emulsion) An olive oil emulsified emulsion with an average of about 100 nm of oil droplets was prepared in the same manner as in Preparation Example 1 except that olive oil was used instead of safflower oil in Preparation Example 1.
  • Preparation Example 3 (Preparation of olive oil / coconut oil mixed emulsion)
  • olive oil having an average droplet diameter of about 200 nm was used in the same manner as in Preparation Example 1 except that a mixed oil having a mass ratio of (olive oil / coconut oil) of 70:30 was used instead of safflower oil.
  • a coconut oil mixed emulsion was prepared.
  • Preparation Example 4 (Preparation of rapeseed oil / sunflower oil / coconut oil mixed emulsion)
  • a mixed oil of (rapeseed oil / sunflower oil / coconut oil) in a mass ratio of 60:20:20 was used.
  • a rapeseed oil / sunflower oil / coconut oil mixed emulsion having a diameter of about 200 nm was prepared.
  • Preparation Example 5 (Preparation of palm kernel oil / rapeseed oil mixed emulsion)
  • palm oil having an average droplet diameter of about 200 nm was prepared in the same manner as Preparation Example 1 except that a mixed oil having a mass ratio of 60:40 (palm kernel oil / rapeseed oil) was used instead of safflower oil.
  • a nuclear oil / rapeseed oil mixed emulsion was prepared.
  • Comparative Example 1 While operating the boiler under the above experimental conditions, 200 mL / min is continuously collected from the steam condensate, and a steel and copper test piece (50 ⁇ 15 ⁇ 1 mm, # 400 polished, degreased and weighed) The test piece was removed after 72 hours, derusted and weighed, and the corrosion rate was determined from the corrosion weight loss. The results are shown in Table 1. Comparative Example 2 During the test period, the test was carried out in the same manner as in Comparative Example 1 except that 50 mg / L of the neutralizing amine morpholine as a steam condensate anticorrosive was added to the steam in terms of condensed water. The corrosion rate of the material was determined. The results are shown in Table 1.
  • Comparative Example 3 In Comparative Example 2, the test was performed in the same manner as in Comparative Example 2 except that 25 mg / L of morpholine was added to the steam in terms of condensed water, and the corrosion rates of the steel material and the copper material were obtained. The results are shown in Table 1.
  • Comparative Example 4 During the test period, the test was conducted in the same manner as in Comparative Example 1 except that octadecylamine, a film-forming amine, was added as a steam condensate anticorrosive to the steam in terms of condensed water. The corrosion rate of the material was determined. The results are shown in Table 1. Comparative Example 5 In Comparative Example 4, a test was conducted in the same manner as in Comparative Example 4 except that 0.5 mg / L of octadecylamine was added to steam in terms of condensed water, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
  • Comparative Example 6 During the test period, the test was carried out in the same manner as in Comparative Example 1 except that sodium oleate, which is a fatty acid salt, was added as a steam condensate anticorrosive to the steam in an amount of 10 mg / L in terms of condensed water. The corrosion rate of the copper material was determined. The results are shown in Table 1.
  • Example 1 During the test period, the safflower oil emulsion obtained in Preparation Example 1 was tested in the same manner as in Comparative Example 1 except that 10 mg / L of safflower oil was added to the steam as safflower oil in terms of condensed water. The corrosion rate of the material was determined. The results are shown in Table 1.
  • Example 2 In Example 1, a test was performed in the same manner as in Example 1 except that 1 mg / L of safflower oil emulsified emulsion was added as safflower oil, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
  • Example 3 During the test period, the olive oil emulsion obtained in Preparation Example 2 was tested in the same manner as in Comparative Example 1 except that 10 mg / L of olive oil was added to the steam as olive oil in terms of condensed water. The corrosion rate was determined. The results are shown in Table 1.
  • Example 4 In Example 3, the test was conducted in the same manner as in Example 3 except that 1 mg / L of the olive oil emulsion was added as olive oil, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
  • Example 5 Comparison was made except that during the test period, the olive oil / coconut oil mixed emulsion obtained in Preparation Example 3 was added to the steam so that the total amount of olive oil / coconut oil mixed oil was 10 mg / L in terms of condensed water. The test was carried out in the same manner as in Example 1, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
  • Example 6 In Example 5, an olive oil / coconut oil mixed emulsion was added in the same manner as in Example 5 except that the total amount of olive oil / coconut oil mixed oil in terms of condensed water was 1 mg / L in terms of condensed water. The test was carried out to determine the corrosion rates of the steel and copper materials. The results are shown in Table 1.
  • Example 7 During the test period, the rapeseed oil / sunflower oil / coconut oil mixed emulsion obtained in Preparation Example 4 is 25 mg / L in total as rapeseed oil / sunflower oil / coconut oil mixed oil in terms of condensed water with respect to steam. The test was carried out in the same manner as in Comparative Example 1 except that the corrosion rate of the steel material and the copper material was determined. The results are shown in Table 1.
  • Example 8 In Example 7, except that the rapeseed oil / sunflower oil / coconut oil mixed emulsion was added to the steam so that the total amount of rapeseed oil / sunflower oil / coconut oil mixed oil was 10 mg / L in terms of condensed water, The test was carried out in the same manner as in Example 7, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
  • Example 9 In Example 7, except that the rapeseed oil / sunflower oil / coconut oil mixed emulsion was added to the steam so that the total amount of rapeseed oil / sunflower oil / coconut oil mixed oil was 1 mg / L in terms of condensed water, The test was carried out in the same manner as in Example 7, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
  • Example 10 Comparison was made except that during the test period, the palm kernel oil / rapeseed oil mixed emulsion obtained in Preparation Example 5 was added to the steam to give a total of 10 mg / L as a palm kernel oil / rapeseed oil mixed oil in terms of condensed water. The test was carried out in the same manner as in Example 1, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
  • Example 11 Comparison was made except that during the test period, the palm kernel oil / rapeseed oil mixed emulsion obtained in Preparation Example 5 was added to the steam so that the total amount of palm kernel oil / rapeseed oil mixed oil was 1 mg / L in terms of condensed water. The test was carried out in the same manner as in Example 1, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
  • an anticorrosive agent one selected from safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, palm oil, rice bran oil, linseed oil, and peanut oil
  • an emulsified emulsion of vegetable oils and fats comprising two or more, in particular, one selected from (i) safflower oil, (ii) olive oil, or (iii) safflower oil, olive oil, and rapeseed oil, and sunflower oil, cottonseed oil, palm oil , Mixed oil containing a combination of one or more selected from palm kernel oil, palm oil, rice bran oil, linseed oil, and peanut oil, in particular, one selected from olive oil and rapeseed oil, sunflower oil, palm oil, When emulsified emulsion of mixed oil containing a combination of one or more selected from palm kernel oil and palm oil, it exhibits excellent anticorrosive effect for both steam condensate

Abstract

A method for preventing the corrosion of a steam/condensate system, etc. are provided with which the corrosion of both the steel material and the copper material in the steam/condensate system is highly effectively prevented with a low concentration of a chemical without arousing a clogging trouble in dead-end piping and even when carbon dioxide or oxygen is present in the steam. (1) The method for preventing the corrosion of a steam/condensate system comprises adding an emulsion of one or more vegetable fats or oils to the steam or condensate in a boiler and/or another steam generation plant, the vegetable fats or oils comprising one or more oils selected from safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, coconut oil, rice oil, linseed oil, and peanut oil.

Description

蒸気復水系の防食方法、及びその方法に用いる防食剤Steam condensate anticorrosion method and anticorrosive used in the method
　本発明は、ボイラ及び／又は他の蒸気発生プラントにおける蒸気復水系の防食方法、及びその方法に用いる防食剤に関する。 The present invention relates to an anticorrosion method for a steam condensate system in a boiler and / or other steam generating plant, and an anticorrosive agent used in the method.
　蒸気復水系の防食方法としては、モノエタノールアミン、シクロヘキシルアミン、モルホリン等のいわゆる中和性アミンを蒸気発生プラントの給水や蒸気に添加して、凝縮水のｐＨを上昇させることにより防食する方法が広く行われてきた。
　しかしながら、蒸気発生プラントの補給水として、軟化水を使用する場合は、水中の重炭酸塩や炭酸塩が熱分解することによって発生する二酸化炭素が蒸気とともに蒸気復水系に移行して、生成した凝縮水に溶解して炭酸となりｐＨを大きく低下させる。このため、前記の中和性アミンを添加して発生する炭酸を中和し、ｐＨを上昇させ腐食を抑制するためには多くの添加量が必要になり、不経済性が問題となる。また、前記の中和性アミンが蒸気や凝縮水に多量に混入すると蒸気使用プロセスや排水への悪影響が問題となる。 As a method for preventing corrosion of steam condensate, there is a method in which so-called neutralizing amines such as monoethanolamine, cyclohexylamine, and morpholine are added to the feed water and steam of the steam generation plant to prevent corrosion by increasing the pH of the condensed water. It has been done widely.
However, when softening water is used as make-up water for the steam generation plant, the carbon dioxide generated by the thermal decomposition of bicarbonate or carbonate in the water is transferred to the steam condensate system along with the steam, resulting in the generated condensation. Dissolves in water to form carbonic acid, greatly reducing pH. For this reason, in order to neutralize the carbonic acid which generate | occur | produces by adding the said neutralizing amine, raise pH and suppress corrosion, many addition amounts are needed, and uneconomical becomes a problem. Moreover, when the neutralizing amine is mixed in a large amount in steam or condensed water, adverse effects on the steam use process and waste water become a problem.
　これに対して、少ない添加量で防食する方法として、皮膜性アミンと呼ばれるオクタデシルアミン等の長鎖アルキルアミンを添加して、蒸気復水系配管内の金属表面に撥水性皮膜を形成することで防食する方法が用いられてきた。しかしながら、給水に溶存している酸素が持ち込まれて脱酸素剤等で十分に除去されずに蒸気復水系に該酸素が移行すると、皮膜性アミンだけでは十分な防食効果が得られなくなるという問題点がある。また、皮膜性アミンを添加しすぎて高濃度にすると、スチームトラップやオリフィス等を閉塞させるトラブルが発生するおそれがあるため、該トラブル防止のため、給水ないし蒸気（凝縮水）に対して１ｍｇ／Ｌ程度までしか添加できないことから、添加量を上げることで防食効果を高めることができない。 On the other hand, as a method to prevent corrosion with a small addition amount, corrosion resistance is achieved by adding a long-chain alkylamine such as octadecylamine called a film-forming amine to form a water-repellent film on the metal surface in the steam condensate piping. A method has been used. However, when oxygen dissolved in the feed water is brought into the steam condensate system without being sufficiently removed by an oxygen scavenger or the like, the film-forming amine alone cannot provide a sufficient anticorrosive effect. There is. In addition, if a film-forming amine is added too much to increase the concentration, troubles that block the steam trap or the orifice may occur. Therefore, to prevent the trouble, 1 mg / mg of feed water or steam (condensed water) is required. Since it can only be added up to about L, the anticorrosion effect cannot be increased by increasing the amount added.
　一方、特許文献１及び２には、オレイン酸アンモニウム塩やステアリン酸アンモニウム塩等の脂肪酸塩を添加する蒸気ボイラ装置の運転方法が提案されている。
　これらの脂肪酸塩は蒸気復水系の鋼材に対してはある程度の防食効果を示すものの、銅材に対してはかえって腐食性が増すという問題点がある。また、これらのアンモニウム塩を添加すると、復水から再び給水に持ち込まれることでアンモニアが蒸気復水系に移行し、これが系内を循環しながら濃縮することで、圧力計や差圧発信機等の行き止まり配管で炭酸アンモニウムとして析出し、閉塞させて機器を誤作動させるというトラブルにいたる懸念がある。さらに、アルカリ金属塩を使用すると、蒸気に添加した場合に、減圧部等でアルカリ金属塩が濃縮・析出してアルカリ腐食を引き起こしたり、水溶液の薬液を調整すると泡立ちが著しくハンドリングが悪い等の問題点がある。 On the other hand, Patent Documents 1 and 2 propose a method of operating a steam boiler apparatus in which fatty acid salts such as ammonium oleate and ammonium stearate are added.
Although these fatty acid salts exhibit a certain degree of anticorrosion effect on steam condensate steel, there is a problem that the corrosiveness increases on copper. Moreover, when these ammonium salts are added, ammonia is transferred to the condensate from the condensate, and the ammonia is transferred to the steam condensate system, which is condensed while circulating in the system, so that a pressure gauge, a differential pressure transmitter, etc. There is concern that it will precipitate as ammonium carbonate in the dead-end piping and cause troubles that cause the device to malfunction due to clogging. In addition, when using alkali metal salts, when added to steam, the alkali metal salt concentrates and precipitates at the decompression section, etc., causing alkali corrosion, and adjusting the chemical solution of the aqueous solution causes problems such as foaming and poor handling. There is a point.
特開２００４－８５１１６号公報JP 2004-85116 A 特開２０１０－１５９９６５号公報JP 2010-159965 A
　本発明は、このような状況下になされたものであり、行き止まり配管等の閉塞トラブルを生じることなく、また、蒸気中に二酸化炭素や酸素が存在しても、低濃度の薬剤で蒸気復水系の鋼材及び銅材の両方に対して優れた防食効果を発揮する蒸気復水系の防食方法、及び該防食方法に用いる防食剤を提供することを目的とする。 The present invention has been made under such circumstances, and does not cause troubles such as dead-end piping and the like, and even if carbon dioxide or oxygen is present in the steam, the steam condensate system with a low concentration of chemicals. An object of the present invention is to provide a steam condensate anticorrosion method that exhibits an excellent anticorrosion effect on both steel and copper, and an anticorrosive used in the anticorrosion method.
　本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、植物系油脂を乳化したエマルションを蒸気若しくは復水に添加することで蒸気復水系の防食を図ることができることを見出した。本発明は、かかる知見に基づいて完成したものである。
　すなわち、本発明は、次の［１］～［６］を提供するものである。
［１］ボイラ及び／又は他の蒸気発生プラントにおいて、植物系油脂を乳化したエマルションを、蒸気若しくは復水に添加する蒸気復水系の防食方法であって、前記植物系油脂が、紅花油、オリーブ油、ひまわり油、菜種油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種又は２種以上を含むことを特徴とする蒸気復水系の防食方法。
［２］植物系油脂の乳化を、植物由来のエステル系乳化剤を用いて行う、上記［１］の蒸気復水系の防食方法。
［３］植物系油脂を乳化してなるエマルションを、凝縮水中における植物系油脂類の濃度が０．０５～５０ｍｇ／Ｌの範囲になるように添加する、上記［１］又は［２］の蒸気復水系の防食方法。
［４］植物系油脂が、（i）紅花油、（ii）オリーブ油、又は（iii）紅花油、オリーブ油、及び菜種油から選ばれる１種と、ひまわり油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種以上との組合せを含む混合油である、上記［１］～［３］のいずれかの蒸気復水系の防食方法。
［５］ボイラ及び／又は他の蒸発発生プラントにおける蒸気復水系の防食剤であって、紅花油、オリーブ油、ひまわり油、菜種油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種又は２種以上を含む植物系油脂を乳化してなるエマルションであることを特徴とする防食剤。
［６］植物系油脂が、植物由来のエステル系乳化剤で乳化されてなる、上記［５］の防食剤。 As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that an anti-corrosion of a steam condensate system can be achieved by adding an emulsion emulsified with vegetable oil to steam or condensate. . The present invention has been completed based on such findings.
That is, the present invention provides the following [1] to [6].
[1] A steam condensate anticorrosion method in which an emulsion emulsified with vegetable oil is added to steam or condensate in a boiler and / or other steam generating plant, wherein the vegetable oil is safflower oil, olive oil Steam condensate anticorrosion method comprising one or more selected from sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, palm oil, rice bran oil, linseed oil, and peanut oil .
[2] The steam condensate anticorrosion method according to [1], wherein the plant oil is emulsified using a plant-derived ester emulsifier.
[3] Steam according to [1] or [2] above, wherein an emulsion obtained by emulsifying vegetable oil is added so that the concentration of vegetable oil in the condensed water is in the range of 0.05 to 50 mg / L. Condensation protection method.
[4] The vegetable oil or fat is selected from (i) safflower oil, (ii) olive oil, or (iii) safflower oil, olive oil, and rapeseed oil, sunflower oil, cottonseed oil, palm oil, palm kernel oil, The steam condensate anticorrosion method according to any one of [1] to [3] above, which is a mixed oil containing a combination of at least one selected from coconut oil, rice bran oil, linseed oil, and peanut oil.
[5] Steam condensate anticorrosives in boilers and / or other evaporation generating plants, including safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, palm oil, rice bran oil, flaxseed An anticorrosive agent characterized by being an emulsion obtained by emulsifying vegetable oils and fats containing one or more selected from oil and peanut oil.
[6] The anticorrosive agent according to the above [5], wherein the plant oil is emulsified with a plant-derived ester emulsifier.
　本発明によれば、（１）ボイラ及び／又は他の蒸気発生プラントにおいて、植物系油脂を乳化したエマルションを、蒸気若しくは復水に添加する蒸気復水系の防食方法であって、前記植物系油脂が、紅花油、オリーブ油、ひまわり油、菜種油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種又は２種以上を含むことを特徴とする蒸気復水系の防食方法、及び（２）該防食方法に使用される防食剤を提供することができる。 According to the present invention, (1) a steam condensate anticorrosion method in which an emulsion emulsified with vegetable oil is added to steam or condensate in a boiler and / or other steam generating plant, the vegetable oil Is characterized by containing one or more selected from safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, palm oil, rice bran oil, linseed oil, and peanut oil An anti-corrosion method for steam condensate, and (2) an anti-corrosion agent used in the anti-corrosion method can be provided.
　本発明の蒸気復水系の防食方法（以下、単に「防食方法」ともいう）は、ボイラ及び／又は他の蒸気発生プラント（以下、「ボイラ類」ともいう）において、植物系油脂を乳化したエマルションを、蒸気若しくは復水に添加する蒸気復水系の防食方法であって、前記植物系油脂が、紅花油、オリーブ油、ひまわり油、菜種油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種又は２種以上であることを特徴とする。
　また、本発明の防食剤は、ボイラ及び／又は他の蒸発発生プラントにおける蒸気復水系の防食剤であって、紅花油、オリーブ油、ひまわり油、菜種油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種又は２種以上の植物系油脂を乳化してなるエマルションであることを特徴とする。
　以下、本発明の防食方法、及び防食剤について順次説明する。 The steam condensate anticorrosion method of the present invention (hereinafter also simply referred to as “corrosion preventive method”) is an emulsion obtained by emulsifying plant oils and fats in a boiler and / or other steam generating plant (hereinafter also referred to as “boilers”). A steam condensate-type anticorrosion method for adding water to steam or condensate, wherein the vegetable oil is safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, coconut oil, rice bran oil , Linseed oil, and peanut oil, one or more selected from peanut oil.
The anticorrosive agent of the present invention is a steam condensate anticorrosive agent in boilers and / or other evaporation generating plants, and includes safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, and palm. It is an emulsion formed by emulsifying one or more kinds of vegetable oils and fats selected from oil, rice bran oil, linseed oil, and peanut oil.
Hereinafter, the anticorrosion method and anticorrosive agent of this invention are demonstrated sequentially.
［蒸気復水系の防食方法］
＜ボイラ類＞
　本発明の防食方法においては、ボイラ類として、蒸気ボイラに給水を供給して加熱し、それにより発生する蒸気を負荷装置等において利用すると共に、該蒸気が凝縮して得られる復水を蒸気ボイラに供給する給水に混合して再利用する蒸気ボイラ装置が好適に用いられる。このような蒸気ボイラ装置では、復水を給水の一部として再利用しているため、給水の絶対量を減少させることができ、蒸気ボイラの経済的な運転が可能になる。 [Anti-corrosion method for steam condensate]
<Boilers>
In the anticorrosion method of the present invention, as boilers, water is supplied to a steam boiler and heated, and steam generated thereby is used in a load device or the like, and condensate obtained by condensing the steam is used as a steam boiler. A steam boiler apparatus that is reused by being mixed with the feed water supplied to the tank is preferably used. In such a steam boiler apparatus, since the condensate is reused as a part of the water supply, the absolute amount of water supply can be reduced, and the steam boiler can be operated economically.
　このような蒸気ボイラ類は、発生した蒸気を負荷装置等に供給するための蒸気配管や、復水を回収して給水に混合するための復水配管等に、主として鋼管を使用し熱交換器は銅材も使用しているため、蒸気ボイラ装置の長期運転に伴って、該配管内に腐食が生じる場合がある。このような腐食は、蒸気ボイラ装置の継続的かつ安定な運転を妨げる原因となる。そこで、蒸気ボイラ装置では、腐食を抑制するための薬剤として、中和性アミン、皮膜性アミン、オレイン酸アンモニウム塩やステアリン酸アンモニウム塩等の脂肪酸塩等を添加する方法が知られているが、前記の問題点がある。
　これに対し、本発明の防食方法においては、植物系油脂の乳化エマルションを、該ボイラ類における蒸気若しくは復水に添加することにより、該ボイラ類の蒸気系において、極めて効果的に防食することができる。 Such steam boilers mainly use steel pipes for steam piping for supplying generated steam to a load device, etc., and for condensate piping for collecting condensate and mixing it with feed water. Since copper also uses copper material, corrosion may occur in the piping with the long-term operation of the steam boiler device. Such corrosion is a cause of hindering the continuous and stable operation of the steam boiler apparatus. Therefore, in the steam boiler apparatus, as a chemical for suppressing corrosion, a method of adding a neutralizing amine, a film-forming amine, a fatty acid salt such as ammonium oleate or ammonium stearate, etc. is known, There is the above-mentioned problem.
On the other hand, in the anticorrosion method of the present invention, by adding an emulsified emulsion of a vegetable oil to steam or condensate in the boiler, it is possible to prevent corrosion very effectively in the steam system of the boiler. it can.
＜植物系油脂＞
　本発明の防食方法において用いるエマルションの原料である植物系油脂とは、脂肪酸のトリグリセリド、ジグリセリド、モノグリセリド及びこれらの混合物を意味する。これらの中では、脂肪酸のトリグリセリドを主成分とする油脂が好ましく、ジグリセリド、モノグリセリド及び遊離脂肪酸を含有していてもよい。 <Vegetable fats and oils>
The vegetable oils and fats that are raw materials of the emulsion used in the anticorrosion method of the present invention mean fatty acid triglycerides, diglycerides, monoglycerides, and mixtures thereof. In these, the fats and oils which have the triglyceride of a fatty acid as a main component are preferable, and may contain diglyceride, monoglyceride, and free fatty acid.
　植物系油脂としては、炭素数８以上の飽和又は不飽和の高級脂肪酸のトリグリセリドを主成分とするものが好ましいことから、紅花油、オリーブ油、ひまわり油、菜種油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種又は２種以上が選択される。
　これらの中では、（i）紅花油、（ii）オリーブ油、（iii）紅花油、オリーブ油、及び菜種油から選ばれる１種と、ひまわり油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種以上との組合せを含む混合油、特に、オリーブ油及び菜種油から選ばれる１種と、ひまわり油、パーム油、パーム核油、及びやし油から選ばれる１種以上との組合せを含む混合油が好ましい。 As plant oils and fats, those mainly composed of triglycerides of saturated or unsaturated higher fatty acids having 8 or more carbon atoms are preferred, so safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, One or more selected from palm oil, rice bran oil, linseed oil, and peanut oil are selected.
Among these, (i) safflower oil, (ii) olive oil, (iii) safflower oil, olive oil, and rapeseed oil, sunflower oil, cottonseed oil, palm oil, palm kernel oil, palm oil, rice bran A mixed oil containing a combination of one or more selected from oil, linseed oil, and peanut oil, in particular, one selected from olive oil and rapeseed oil, and selected from sunflower oil, palm oil, palm kernel oil, and palm oil A mixed oil containing a combination with one or more selected from the above is preferred.
　（iii）混合油としては、（ａ）オリーブ油とやし油を含む混合油、（ｂ）菜種油と、ひまわり油及びやし油を含む混合油、（ｃ）パーム核油と菜種油を含む混合油等が好ましく挙げられる。
（ａ）オリーブ油とやし油を含む混合油の質量比（オリーブ油／やし油）は、特に限定はないが、好ましくは２０／８０～９５／５、より好ましくは４０／６０～９０／１０、更に好ましくは６０／４０～８０／２０である。
（ｂ）菜種油と、ひまわり油及びやし油を含む混合油の質量比〔菜種油／（ひまわり油＋やし油）〕は、特に限定はないが、好ましくは２０／８０～９５／５、より好ましくは４０／６０～９０／１０、より好ましくは５０／５０～８５／１５、更に好ましくは６０／４０～８０／２０であり、（ひまわり油／やし油）が、好ましくは３０／７０～７０／３０、より好ましくは４０／６０～６０／４０である。
（ｃ）パーム核油と菜種油を含む混合油の質量比（パーム核油／菜種油）は、特に限定はないが、好ましくは２０／８０～９５／５、より好ましくは４０／６０～９０／１０、より好ましくは５０／５０～８５／１５、更に好ましくは６０／４０～８０／２０である。 (Iii) As mixed oil, (a) mixed oil containing olive oil and coconut oil, (b) mixed oil containing rapeseed oil, sunflower oil and coconut oil, (c) mixed oil containing palm kernel oil and rapeseed oil Etc. are preferable.
(A) The mass ratio of the mixed oil containing olive oil and palm oil (olive oil / coconut oil) is not particularly limited, but is preferably 20/80 to 95/5, more preferably 40/60 to 90/10. More preferably, it is 60/40 to 80/20.
(B) The mass ratio of the rapeseed oil and the mixed oil containing sunflower oil and palm oil [rapeseed oil / (sunflower oil + coconut oil)] is not particularly limited, but is preferably 20/80 to 95/5. Preferably 40/60 to 90/10, more preferably 50/50 to 85/15, still more preferably 60/40 to 80/20, and (sunflower oil / coconut oil) is preferably 30/70 to 70/30, more preferably 40/60 to 60/40.
(C) The mass ratio of the mixed oil containing palm kernel oil and rapeseed oil (palm kernel oil / rapeseed oil) is not particularly limited, but is preferably 20/80 to 95/5, more preferably 40/60 to 90/10. More preferably, it is 50/50 to 85/15, and still more preferably 60/40 to 80/20.
　上記の植物系油脂の脂肪酸成分は以下の各種の高級脂肪酸（質量％）を含む。なお、以下に示す高級脂肪酸の比率は一般的な植物系油脂の組成に基づいており、品種改良品（ハイオレイックやハイリノール種等）を元にした植物油を使用する場合は、以下の比率の範囲を超えることもあり得るが、それらを使用してもよい。 The fatty acid component of the above-mentioned vegetable oil contains the following various higher fatty acids (mass%). The ratios of higher fatty acids shown below are based on the composition of general vegetable oils and fats, and when using vegetable oils based on improved varieties (such as high oleic and hylinol species), the following ratio ranges May be used, but they may be used.
・紅花油の脂肪酸組成：パルミチン酸４～８％、パルミトレイン酸０～１％、ステアリン酸１～４％、オレイン酸８～２５％、リノール酸６０～８０％、リノレン酸０～１％
・オリーブ油［イタリア産］の脂肪酸組成：パルミチン酸９．２％、ステアリン酸２．０％、オレイン酸８３．１％、リノール酸３．９％
・ひまわり油の脂肪酸組成：［パルミチン酸、ステアリン酸、アラキン酸］８．７～１４．２％、オレイン酸１４．１～４３．１％、リノール酸４４．２～７５．４％、不ケン化物１．５％以下
・菜種油の脂肪酸成分：パルミチン酸１～３％、ステアリン酸０．２～３％、オレイン酸１２～１８％、エイコセン酸３～６％、エルカ酸４５～５５％、リノール酸１２～１６％、リノレン酸７～９％、不ケン化物０．６～１．２％
・綿実油の脂肪酸組成：ミスチリン酸０～３％、パルミチン酸２０～３０％、パルミトレイン酸０～２％、ステアリン酸１～５％、オレイン酸１５～３０％、リノール酸４０～５２％ Fatty acid composition of safflower oil: 4-8% palmitic acid, 0-1% palmitoleic acid, 1-4% stearic acid, 8-25% oleic acid, 60-80% linoleic acid, 0-1% linolenic acid
Fatty acid composition of olive oil [from Italy]: palmitic acid 9.2%, stearic acid 2.0%, oleic acid 83.1%, linoleic acid 3.9%
Fatty acid composition of sunflower oil: [palmitic acid, stearic acid, arachidic acid] 8.7 to 14.2%, oleic acid 14.1 to 43.1%, linoleic acid 44.2 to 75.4%, unsken 1.5% or less of chemicals ・ Fatty acid components of rapeseed oil: palmitic acid 1-3%, stearic acid 0.2-3%, oleic acid 12-18%, eicosenoic acid 3-6%, erucic acid 45-55%, linole Acid 12-16%, Linolenic acid 7-9%, Unsaponified product 0.6-1.2%
・ Fatty acid composition of cottonseed oil: 0-3% mytilic acid, 20-30% palmitic acid, 0-2% palmitoleic acid, 1-5% stearic acid, 15-30% oleic acid, 40-52% linoleic acid
・パーム油の脂肪酸組成：ミスチリン酸１～３％、パルミチン酸３５～４８％、ステアリン酸３～７％、オレイン酸３７～５０％、リノール酸７～１１％
・パーム核油の脂肪酸組成：ラウリン酸４４～５５％、ミスチリン酸１０～１７％、パルミチン酸６～１０％、ステアリン酸１～７％、オレイン酸１～１７％、リノール酸０～２％
・やし油の脂肪酸組成：ラウリン酸４５～５２％、ミスチリン酸１５～２２％、パルミチン酸４～１０％、ステアリン酸１～５％、オレイン酸２～１０％、リノール酸１～３％
・こめ油の脂肪酸組成：ミスチリン酸０～１％、パルミチン酸１１～２１％、パルミトレイン酸０～１％、ステアリン酸１～３％、オレイン酸３５～５０％、リノール酸２５～４０％、リノレン酸０～１％
・アマニ油の脂肪酸組成：パルミチン酸４～９％、パルミトレイン酸０～１％、ステアリン酸２～５％、オレイン酸２０～３５％、リノール酸５～２０％、リノレン酸３０～５８％、アラキジン酸０～１％、エコイセン酸０～１％
・落花生油の脂肪酸組成：ラウリン酸０～２％、パルミチン酸６～１３％、ステアリン酸２～７％、オレイン酸３５～７０％、リノール酸２０～４０％、リノレン酸０～１％、アラキジン酸１～５％、エコイセン酸０～２％、ベヘン酸１～３％、エルシン酸０～１％、リグノセリン酸１～３％
　上記の油脂類は、一種単独で又は二種以上を組み合わせて用いることができる。 ・ Fatty acid composition of palm oil: 1 to 3% mistylic acid, 35 to 48% palmitic acid, 3 to 7% stearic acid, 37 to 50% oleic acid, 7 to 11% linoleic acid
Fatty acid composition of palm kernel oil: lauric acid 44-55%, myristic acid 10-17%, palmitic acid 6-10%, stearic acid 1-7%, oleic acid 1-17%, linoleic acid 0-2%
-Fatty acid composition of palm oil: 45-52% lauric acid, 15-22% myristylic acid, 4-10% palmitic acid, 1-5% stearic acid, 2-10% oleic acid, 1-3% linoleic acid
-Fatty acid composition of koji oil: mistylic acid 0-1%, palmitic acid 11-21%, palmitoleic acid 0-1%, stearic acid 1-3%, oleic acid 35-50%, linoleic acid 25-40%, linolenic Acid 0-1%
Fatty acid composition of linseed oil: 4-9% palmitic acid, 0-1% palmitoleic acid, 2-5% stearic acid, 20-35% oleic acid, 5-20% linoleic acid, 30-58% linolenic acid, arachidin Acid 0-1%, Ecoisenoic acid 0-1%
・ Fatty acid composition of peanut oil: 0-2% lauric acid, 6-13% palmitic acid, 2-7% stearic acid, 35-70% oleic acid, 20-40% linoleic acid, 0-1% linolenic acid, arachidin Acid 1-5%, ecoisenoic acid 0-2%, behenic acid 1-3%, erucic acid 0-1%, lignoceric acid 1-3%
Said fats and oils can be used individually by 1 type or in combination of 2 or more types.
＜植物系油脂の乳化エマルション＞
　植物系油脂を乳化処理してエマルションを調製する方法に特に制限はないが、植物系油脂を乳化できる乳化剤を添加し、水を加えて混練してエマルション化する方法が挙げられる。エマルション中の植物系油脂濃度、乳化剤濃度は特には限定されず、エマルションが安定であればよい。
　乳化剤としては、植物由来のエステル系乳化剤、エーテル系乳化剤等が好ましく、植物由来のエステル系乳化剤がより好ましい。この植物由来の乳化剤は、人体に触れた際の安全性の観点からも好ましい。 <Emulsified emulsion of vegetable oil>
Although there is no restriction | limiting in particular in the method of emulsifying vegetable oil and fat, and preparing an emulsion, The method of adding the emulsifier which can emulsify vegetable oil and fat, knead | mixing and emulsifying is mentioned. The vegetable oil concentration and emulsifier concentration in the emulsion are not particularly limited as long as the emulsion is stable.
As the emulsifier, plant-derived ester emulsifiers, ether-based emulsifiers and the like are preferable, and plant-derived ester-based emulsifiers are more preferable. This plant-derived emulsifier is also preferable from the viewpoint of safety when touching the human body.
（植物由来のエステル系乳化剤）
　植物由来のエステル系乳化剤としては、植物系油脂とグリセリンとの加熱反応で得られるグリセリン脂肪酸エステル、ショ糖と脂肪酸メチルエステルをエステル交換反応させて得られるショ糖脂肪酸エステル、各種の脂肪酸とソルビトールを、アルカリを触媒としてエステル化することにより得られるソルビタン脂肪酸エステル、プロピレングリコールと脂肪酸をエステル化させて得られるプロピレングリコール脂肪酸エステル、大豆から得られる大豆リン脂質、ポリオキシエチレン脂肪酸エステル等が挙げられる。これらの中では、脂肪酸モノグリセライド、脂肪酸ジグリセライドから選ばれる一種又は二種以上のグリセリン脂肪酸エステルがより好ましく、脂肪酸モノグリセライドがより好ましい。また、脂肪酸モノグリセライドのグリセリン単位の平均数は、好ましくは２～１４、より好ましくは６～１２、更に好ましくは８～１２であり、脂肪酸モノグリセライドの脂肪酸の炭素数は、好ましくは２～３０であり、モノステアリン酸デカグリセリルが最も好ましい。
　これらの植物由来のエステル系乳化剤は、一種単独で又は二種以上を組み合わせて用いることができる。 (Plant-derived ester emulsifier)
Examples of plant-derived ester emulsifiers include glycerin fatty acid ester obtained by heating reaction of vegetable oil and glycerin, sucrose fatty acid ester obtained by transesterification of sucrose and fatty acid methyl ester, various fatty acids and sorbitol. And sorbitan fatty acid ester obtained by esterification using an alkali as a catalyst, propylene glycol fatty acid ester obtained by esterifying propylene glycol and fatty acid, soybean phospholipid obtained from soybean, polyoxyethylene fatty acid ester and the like. Among these, one or more glycerin fatty acid esters selected from fatty acid monoglycerides and fatty acid diglycerides are more preferable, and fatty acid monoglycerides are more preferable. The average number of glycerin units of the fatty acid monoglyceride is preferably 2 to 14, more preferably 6 to 12, and still more preferably 8 to 12. The number of carbon atoms of the fatty acid of the fatty acid monoglyceride is preferably 2 to 30. Most preferred is decaglyceryl monostearate.
These plant-derived ester emulsifiers can be used singly or in combination of two or more.
（乳化エマルションの調製方法）
　植物系油脂を乳化処理してエマルションを調製する方法としては、植物系油脂を、水性媒体中において、植物由来のエステル系乳化剤の存在下、ホモジナイザーを用いて均質化処理する方法が挙げられる。該ホモジナイザーとしては、例えばコロイドミル、振動撹拌機、二段式高圧ポンプ、ノズルやオリフィスからの高圧噴出、超音波撹拌等が挙げられる。さらに、エマルションにおける油滴の粒径の調節は、均質化処理時の剪断力の制御、乳化剤の量等により影響されるが、これらは簡単な予備実験により、適当な条件を選択することができる。
　該油滴径の大きさは、動的光散乱法による測定値で、好ましくは０．８ｎｍ～５０μｍ程度、より好ましくは１０ｎｍ～１０μｍ、より好ましくは２０ｎｍ～２μｍ、更に好ましくは４０ｎｍ～１μｍである。 (Method for preparing emulsified emulsion)
Examples of a method for preparing an emulsion by emulsifying vegetable oils and fats include a method in which vegetable oils and fats are homogenized in an aqueous medium using a homogenizer in the presence of a plant-derived ester emulsifier. Examples of the homogenizer include a colloid mill, a vibration stirrer, a two-stage high-pressure pump, a high-pressure jet from a nozzle and an orifice, and ultrasonic stirring. Furthermore, the adjustment of the particle size of the oil droplets in the emulsion is influenced by the control of the shearing force during the homogenization process, the amount of the emulsifier, etc., and these can be selected by simple preliminary experiments. .
The size of the oil droplet diameter is a value measured by a dynamic light scattering method, preferably about 0.8 nm to 50 μm, more preferably 10 nm to 10 μm, more preferably 20 nm to 2 μm, and still more preferably 40 nm to 1 μm. .
（蒸気復水系の防食方法）
　本発明の防食方法においては、このようにして得られた植物系油脂の乳化エマルションを、蒸気が凝縮した凝縮水中における植物系油脂の濃度が、好ましくは０．０５～５０ｍｇ／Ｌ、より好ましくは０．１～２５ｍｇ／Ｌ、更に好ましくは０．５～２５ｍｇ／Ｌ、より更に好ましくは１～２５ｍｇ／Ｌ、より更に好ましくは５～２５ｍｇ／Ｌ、より更に好ましくは８～２５ｍｇ／Ｌの範囲となるように、ケミカルポンプ等を用いて蒸気中に添加する。添加場所は、蒸気ライン及び復水ラインのいずれでもよいが、蒸気ラインに添加する方が、植物系油脂が蒸気や凝縮水中に均一に分散されるため好ましい。
　本発明の防食方法においては、植物系油脂の乳化エマルションをボイラ類の復水ラインや蒸気ラインに添加することにより、該ボイラ類の蒸気系において、圧力計や差圧発信機等の行き止まり配管で閉塞トラブルを生じたり、減圧部でアルカリ腐食を引き起こしたりすることなく、また、蒸気中に二酸化炭素や酸素が存在しても、低濃度の添加で蒸気復水系の配管・熱交換機等の凝縮水が接触する面の腐食を鋼材・銅材ともに良好に防止することができる。 (Anti-corrosion method for steam condensate)
In the anticorrosion method of the present invention, the concentration of the vegetable oil / fat in the condensed oil obtained by condensing the vapor of the vegetable oil / fat thus obtained is preferably 0.05 to 50 mg / L, more preferably. The range is 0.1 to 25 mg / L, more preferably 0.5 to 25 mg / L, still more preferably 1 to 25 mg / L, still more preferably 5 to 25 mg / L, and still more preferably 8 to 25 mg / L. Add to the steam using a chemical pump or the like. The addition site may be either a steam line or a condensate line, but it is preferable to add to the steam line because the vegetable oil is uniformly dispersed in the steam and condensed water.
In the anticorrosion method of the present invention, by adding an emulsified emulsion of vegetable oil to a condensate line or a steam line of a boiler, in the steam system of the boiler, a dead end pipe such as a pressure gauge or a differential pressure transmitter is used. Condensed water such as steam condensate piping and heat exchangers can be added with low concentration even if carbon dioxide or oxygen is present in the steam without causing clogging trouble or alkali corrosion in the decompression section. It is possible to satisfactorily prevent corrosion of the surface in contact with both steel and copper.
＜任意添加成分＞
　本発明の防食方法においては、植物系油脂類の乳化エマルションを復水ラインや蒸気ラインに添加することにより、本発明の効果を充分に発揮することができるが、本発明の目的が損なわれない範囲で、必要に応じて、各種の添加成分、例えばアルカリ剤、ｐＨ調整剤、防食剤、スケール防止剤等を復水やボイラ水に対して有効量添加することできる。
　これらの添加成分は一種単独で又は二種以上を組み合わせて用いることができる。 <Optional components>
In the anticorrosion method of the present invention, the effects of the present invention can be sufficiently exerted by adding an emulsified emulsion of vegetable oils to the condensate line or steam line, but the object of the present invention is not impaired. If necessary, various additive components such as alkali agents, pH adjusters, anticorrosives, scale inhibitors and the like can be added in effective amounts to the condensate and boiler water.
These additive components can be used alone or in combination of two or more.
（アルカリ剤、ｐＨ調整剤）
　アルカリ剤としては、例えば水酸化カリウム、水酸化ナトリウム、炭酸カリウム及び炭酸ナトリウム等が挙げられる。
　ｐＨ調整剤としては、リン酸３ナトリウム、リン酸２ナトリウム、リン酸３ナトリウムとリン酸２ナトリウムを所定の比率で混合したもの等が挙げられる。
（脱酸素剤）
　脱酸素剤としては、エリソルビン酸（塩）、アスコルビン酸(塩)、亜硫酸(塩)、タンニン、タンニン酸(塩)等が挙げられる。
（防食剤）
　防食剤としては、例えば中和性アミン、皮膜性アミン、各種の酸及び／又はその塩、カルボキシル基を有する水溶性ポリマー及び／又はコポリマー、スケール防止剤、スケール除去剤等を用いることができる。 (Alkaline agent, pH adjuster)
Examples of the alkaline agent include potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate.
Examples of the pH adjuster include trisodium phosphate, disodium phosphate, and a mixture of trisodium phosphate and disodium phosphate in a predetermined ratio.
(Oxygen absorber)
Examples of the oxygen scavenger include erythorbic acid (salt), ascorbic acid (salt), sulfurous acid (salt), tannin, tannic acid (salt), and the like.
(Anticorrosive)
As the anticorrosive agent, for example, neutralizing amine, film-forming amine, various acids and / or salts thereof, water-soluble polymer and / or copolymer having a carboxyl group, scale inhibitor, scale remover and the like can be used.
（i）中和性アミン
　中和性アミンとしては、例えばモノエタノールアミン（ＭＥＡ）、シクロへキシルアミン（ＣＨＡ）、モルホリン（ＭＯＲ）、ジエチルエタノールアミン（ＤＥＥＡ）、モノイソプロパノールアミン（ＭＩＰＡ）、３－メトキシプロピルアミン（ＭＯＰＡ）、２－アミノ－２－メチル－１－プロパノール（ＡＭＰ）等が挙げられる。
（ii）皮膜性アミン
　皮膜性アミンとしては、例えばオクタデシルアミン等の長鎖アルキルアミン等が挙げられる。
（iii）各種の酸及び／又はその塩
　各種の酸及び／又はその塩としては、例えばクエン酸及び／又はその塩、コハク酸カリウム塩等が挙げられる。
　クエン酸塩は、クエン酸のカルボキシル基の水素原子を、例えば、ナトリウム、カリウム等のアルカリ金属で置換して得られる塩である。クエン酸塩の具体例としては、クエン酸ナトリウム、クエン酸水素ナトリウム、クエン酸カリウム、クエン酸水素カリウム等の塩及びそれらの水和物等が挙げられる。 (I) Neutralizing amine Examples of the neutralizing amine include monoethanolamine (MEA), cyclohexylamine (CHA), morpholine (MOR), diethylethanolamine (DEEA), monoisopropanolamine (MIPA), 3- Examples include methoxypropylamine (MOPA), 2-amino-2-methyl-1-propanol (AMP), and the like.
(Ii) Film-forming amine Examples of film-forming amines include long-chain alkylamines such as octadecylamine.
(Iii) Various acids and / or salts thereof Examples of various acids and / or salts thereof include citric acid and / or salts thereof, potassium succinate and the like.
Citrate is a salt obtained by substituting the hydrogen atom of the carboxyl group of citric acid with an alkali metal such as sodium or potassium. Specific examples of the citrate include salts such as sodium citrate, sodium hydrogen citrate, potassium citrate, potassium hydrogen citrate, and hydrates thereof.
（iv）水溶性ポリマー
　水溶性ポリマーとしては、カルボキシル基を有する水溶性ホモポリマー及び／又はコポリマーが用いられる。その具体例としては、アクリル酸、マレイン酸、２－アクリルアミド－２－メチルプロパンスルホン酸、３－アリロキシ－２－ヒドロキシプロパンスルホン酸及びそれらの塩等から選ばれるモノマーを用いて得られたホモポリマー、コポリマー及びイソブチレンとのコポリマーの中から選ばれるポリマー等が挙げられる。
（v）スケール防止剤、スケール除去剤
　スケール防止剤、スケール除去剤の具体例としては、各種リン酸塩や、ポリアクリル酸、ポリマレイン酸、及びそれらのナトリウム塩等の水溶性高分子化合物、ホスホン酸塩、キレート剤等が挙げられる。 (Iv) Water-soluble polymer As the water-soluble polymer, a water-soluble homopolymer and / or copolymer having a carboxyl group is used. Specific examples thereof include homopolymers obtained using monomers selected from acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, and salts thereof. , Polymers selected from copolymers and copolymers with isobutylene, and the like.
(V) Scale inhibitors, scale removers Specific examples of scale inhibitors and scale removers include various phosphates, water-soluble polymer compounds such as polyacrylic acid, polymaleic acid, and sodium salts thereof, and phosphones. Examples thereof include acid salts and chelating agents.
［防食剤］
　本発明の防食剤は、ボイラ及び／又は他の蒸発発生プラントにおける蒸気復水系の防食剤であって、紅花油、オリーブ油、ひまわり油、菜種油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種又は２種以上を含む植物系油脂を乳化してなるエマルションである。
　また、植物由来のエステル系乳化剤を用いて、該植物系油脂を乳化処理し、エマルションを調製することが好ましい。
　本発明の防食剤は、前記植物系油脂の乳化エマルションと共に、必要に応じて、前記の各種の任意添加成分を適宜量含有することができる。 [Anticorrosive]
The anticorrosive agent of the present invention is a steam condensate anticorrosive agent in boilers and / or other evaporation generating plants, including safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, coconut oil, It is an emulsion obtained by emulsifying vegetable oil containing one or more selected from rice oil, linseed oil, and peanut oil.
In addition, it is preferable to prepare an emulsion by emulsifying the vegetable oil using a plant-derived ester emulsifier.
The anticorrosive of this invention can contain the said various arbitrary addition components suitably as needed with the emulsion emulsion of the said vegetable oil and fat as needed.
　次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
＜実験条件＞
　栃木県下都賀郡野木町水の軟化水を補給水として換算蒸発量６００Ｌ／ｈの小型貫流ボイラを圧力０．６ＭＰａ、給水量４４０Ｌ／ｈ、ブロー量４０Ｌ／ｈで運転した。発生した蒸気は鋼材製熱交換器にて冷却し、生成した７０℃の凝縮水のうちの半分の２００Ｌ／ｈを復水として給水タンクに回収し、給水として再利用した。
　運転中の給水温度は約４５℃、給水中の溶存酸素濃度は約６．０ｍｇ／Ｌで推移した。また、前記野木町水の酸性炭酸ナトリウムは５２ｍｇ／Ｌであった。給水にはボイラ缶内の処理剤として、コハク酸カリウム塩（防食剤）を２０ｍｇ／Ｌ、ポリアクリル酸ナトリウム（スケール防止剤）を３ｍｇ／Ｌ、水酸化カリウム（アルカリ剤）を５ｍｇ／Ｌ添加した。 <Experimental conditions>
A small once-through boiler with a converted evaporation amount of 600 L / h was operated at a pressure of 0.6 MPa, a water supply amount of 440 L / h, and a blow rate of 40 L / h using softened water of Nogi-cho, Shimotsuga-gun, Tochigi Prefecture as makeup water. The generated steam was cooled in a steel heat exchanger, and 200 L / h, half of the generated 70 ° C. condensed water, was collected in the water supply tank as condensate and reused as water supply.
During operation, the feed water temperature was about 45 ° C., and the dissolved oxygen concentration in the feed water was about 6.0 mg / L. Moreover, the acidic sodium carbonate of Nogimachi water was 52 mg / L. For water supply, potassium succinate (anticorrosive) 20mg / L, sodium polyacrylate (scale inhibitor) 3mg / L, potassium hydroxide (alkali agent) 5mg / L as treatment agents in boiler cans did.
調製例１（紅花油乳化エマルションの調製）
　水性媒体１００質量部中において、ポリグリセリン脂肪酸エステル（植物由来のエステル系乳化剤）［日光ケミカルズ株式会社製、商品名：NIKKOL Decaglyn 1-SV］５質量部の存在下、ホモジナイザー［ＩＫＡ社製、機種名：ＵＬＴＲＡ－ＴＵＲＲＡＸ　Ｔ５０　ｂａｓｉｃ］を用いて紅花油３０質量部を乳化処理することにより、油滴の平均径１００ｎｍ程度の紅花油乳化エマルションを調製した。 Preparation Example 1 (Preparation of safflower oil emulsion)
In 100 parts by mass of an aqueous medium, a polyglycerin fatty acid ester (plant-derived ester emulsifier) [manufactured by Nikko Chemicals Co., Ltd., trade name: NIKKOL Decaglyn 1-SV] in the presence of 5 parts by mass, a homogenizer [manufactured by IKA, model By emulsifying 30 parts by weight of safflower oil using a name: ULTRA-TURRAX T50 basic], an emulsified safflower oil emulsion having an oil droplet average diameter of about 100 nm was prepared.
調製例２（オリーブ油乳化エマルションの調製）
　調製例１において、紅花油の代わりにオリーブ油を用いた以外は、調製例１と同様にした、油滴の平均１００ｎｍ程度のオリーブ油乳化エマルションを調製した。 Preparation Example 2 (Preparation of olive oil emulsion)
An olive oil emulsified emulsion with an average of about 100 nm of oil droplets was prepared in the same manner as in Preparation Example 1 except that olive oil was used instead of safflower oil in Preparation Example 1.
調製例３（オリーブ油／やし油混合乳化エマルションの調製）
　調製例１において、紅花油の代わりに、（オリーブ油／やし油）の質量比７０：３０の混合油を用いた以外は、調製例１と同様にして、油滴の平均径２００ｎｍ程度のオリーブ油／やし油混合乳化エマルションを調製した。 Preparation Example 3 (Preparation of olive oil / coconut oil mixed emulsion)
In Preparation Example 1, olive oil having an average droplet diameter of about 200 nm was used in the same manner as in Preparation Example 1 except that a mixed oil having a mass ratio of (olive oil / coconut oil) of 70:30 was used instead of safflower oil. A coconut oil mixed emulsion was prepared.
調製例４（菜種油／ひまわり油／やし油混合乳化エマルションの調製）
　調製例１において、紅花油の代わりに、（菜種油／ひまわり油／やし油）の質量比６０：２０：２０の混合油を用いた以外は、調製例１と同様にして、油滴の平均径２００ｎｍ程度の菜種油／ひまわり油／やし油混合乳化エマルションを調製した。 Preparation Example 4 (Preparation of rapeseed oil / sunflower oil / coconut oil mixed emulsion)
In Preparation Example 1, instead of safflower oil, an average of oil droplets was obtained in the same manner as in Preparation Example 1, except that a mixed oil of (rapeseed oil / sunflower oil / coconut oil) in a mass ratio of 60:20:20 was used. A rapeseed oil / sunflower oil / coconut oil mixed emulsion having a diameter of about 200 nm was prepared.
調製例５（パーム核油/菜種油混合乳化エマルションの調製）
　調製例１において、紅花油の代わりに、（パーム核油/菜種油）の質量比６０：４０の混合油を用いた以外は、調製例１と同様にして、油滴の平均径２００ｎｍ程度のパーム核油/菜種油混合乳化エマルションを調製した。 Preparation Example 5 (Preparation of palm kernel oil / rapeseed oil mixed emulsion)
In Preparation Example 1, palm oil having an average droplet diameter of about 200 nm was prepared in the same manner as Preparation Example 1 except that a mixed oil having a mass ratio of 60:40 (palm kernel oil / rapeseed oil) was used instead of safflower oil. A nuclear oil / rapeseed oil mixed emulsion was prepared.
比較例１
　上記実験条件にてボイラを運転しながら、蒸気凝縮水より２００ｍＬ／分を連続的に採取し、鋼材及び銅材製のテストピース（５０×１５×１ｍｍ、＃４００番研磨処理し、脱脂・秤量したもの）を設置したカラムに通水し、７２時間経過後にテストピースを取り外して、脱錆・秤量し、腐食減量より腐食速度を求めた。結果を第１表に示す。
比較例２
　試験期間中、蒸気復水系防食剤として、中和性アミンのモルホリンを、蒸気に対し、凝縮水換算で５０ｍｇ／Ｌ添加した以外は、比較例１と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。
比較例３
　比較例２において、モルホリンを蒸気に対し、凝縮水換算で２５ｍｇ／Ｌ添加した以外は、比較例２と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。 Comparative Example 1
While operating the boiler under the above experimental conditions, 200 mL / min is continuously collected from the steam condensate, and a steel and copper test piece (50 × 15 × 1 mm, # 400 polished, degreased and weighed) The test piece was removed after 72 hours, derusted and weighed, and the corrosion rate was determined from the corrosion weight loss. The results are shown in Table 1.
Comparative Example 2
During the test period, the test was carried out in the same manner as in Comparative Example 1 except that 50 mg / L of the neutralizing amine morpholine as a steam condensate anticorrosive was added to the steam in terms of condensed water. The corrosion rate of the material was determined. The results are shown in Table 1.
Comparative Example 3
In Comparative Example 2, the test was performed in the same manner as in Comparative Example 2 except that 25 mg / L of morpholine was added to the steam in terms of condensed water, and the corrosion rates of the steel material and the copper material were obtained. The results are shown in Table 1.
比較例４
　試験期間中、蒸気復水系防食剤として、皮膜性アミンのオクタデシルアミンを、蒸気に対し、凝縮水換算で１ｍｇ／Ｌ添加した以外は、比較例１と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。
比較例５
　比較例４において、オクタデシルアミンを蒸気に対し、凝縮水換算で０．５ｍｇ／Ｌ添加した以外は、比較例４と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。
比較例６
　試験期間中、蒸気復水系防食剤として、脂肪酸塩であるオレイン酸ナトリウムを、蒸気に対し、凝縮水換算で１０ｍｇ／Ｌ添加した以外は、比較例１と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。 Comparative Example 4
During the test period, the test was conducted in the same manner as in Comparative Example 1 except that octadecylamine, a film-forming amine, was added as a steam condensate anticorrosive to the steam in terms of condensed water. The corrosion rate of the material was determined. The results are shown in Table 1.
Comparative Example 5
In Comparative Example 4, a test was conducted in the same manner as in Comparative Example 4 except that 0.5 mg / L of octadecylamine was added to steam in terms of condensed water, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
Comparative Example 6
During the test period, the test was carried out in the same manner as in Comparative Example 1 except that sodium oleate, which is a fatty acid salt, was added as a steam condensate anticorrosive to the steam in an amount of 10 mg / L in terms of condensed water. The corrosion rate of the copper material was determined. The results are shown in Table 1.
実施例１
　試験期間中、調製例１で得た紅花油乳化エマルションを、蒸気に対し、凝縮水換算で紅花油として１０ｍｇ／Ｌ添加した以外は、比較例１と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。
実施例２
　実施例１において、紅花油乳化エマルションを紅花油として１ｍｇ／Ｌ添加した以外は、実施例１と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。 Example 1
During the test period, the safflower oil emulsion obtained in Preparation Example 1 was tested in the same manner as in Comparative Example 1 except that 10 mg / L of safflower oil was added to the steam as safflower oil in terms of condensed water. The corrosion rate of the material was determined. The results are shown in Table 1.
Example 2
In Example 1, a test was performed in the same manner as in Example 1 except that 1 mg / L of safflower oil emulsified emulsion was added as safflower oil, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
実施例３
　試験期間中、調製例２で得たオリーブ油乳化エマルションを、蒸気に対し、凝縮水換算でオリーブ油として１０ｍｇ／Ｌ添加した以外は、比較例１と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。
実施例４
　実施例３において、オリーブ油乳化エマルションをオリーブ油として１ｍｇ／Ｌ添加した以外は、実施例３と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。 Example 3
During the test period, the olive oil emulsion obtained in Preparation Example 2 was tested in the same manner as in Comparative Example 1 except that 10 mg / L of olive oil was added to the steam as olive oil in terms of condensed water. The corrosion rate was determined. The results are shown in Table 1.
Example 4
In Example 3, the test was conducted in the same manner as in Example 3 except that 1 mg / L of the olive oil emulsion was added as olive oil, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
実施例５
　試験期間中、調製例３で得たオリーブ油／やし油混合乳化エマルションを、蒸気に対し、凝縮水換算でオリーブ油／やし油混合油として合計１０ｍｇ／Ｌになるように添加した以外は、比較例１と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。
実施例６
　実施例５において、オリーブ油／やし油混合乳化エマルションを、蒸気に対し、凝縮水換算でオリーブ油／やし油混合油として合計１ｍｇ／Ｌになるように添加した以外は、実施例５と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。 Example 5
Comparison was made except that during the test period, the olive oil / coconut oil mixed emulsion obtained in Preparation Example 3 was added to the steam so that the total amount of olive oil / coconut oil mixed oil was 10 mg / L in terms of condensed water. The test was carried out in the same manner as in Example 1, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
Example 6
In Example 5, an olive oil / coconut oil mixed emulsion was added in the same manner as in Example 5 except that the total amount of olive oil / coconut oil mixed oil in terms of condensed water was 1 mg / L in terms of condensed water. The test was carried out to determine the corrosion rates of the steel and copper materials. The results are shown in Table 1.
実施例７
　試験期間中、調製例４で得た菜種油／ひまわり油／やし油混合乳化エマルションを、蒸気に対し、凝縮水換算で菜種油／ひまわり油／やし油混合油として合計２５ｍｇ／Ｌになるように添加した以外は、比較例１と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。
実施例８
　実施例７において、菜種油／ひまわり油／やし油混合乳化エマルションを、蒸気に対し、凝縮水換算で菜種油／ひまわり油／やし油混合油として合計１０ｍｇ／Ｌになるように添加した以外は、実施例７と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。
実施例９
　実施例７において、菜種油／ひまわり油／やし油混合乳化エマルションを、蒸気に対し、凝縮水換算で菜種油／ひまわり油／やし油混合油として合計１ｍｇ／Ｌになるように添加した以外は、実施例７と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。 Example 7
During the test period, the rapeseed oil / sunflower oil / coconut oil mixed emulsion obtained in Preparation Example 4 is 25 mg / L in total as rapeseed oil / sunflower oil / coconut oil mixed oil in terms of condensed water with respect to steam. The test was carried out in the same manner as in Comparative Example 1 except that the corrosion rate of the steel material and the copper material was determined. The results are shown in Table 1.
Example 8
In Example 7, except that the rapeseed oil / sunflower oil / coconut oil mixed emulsion was added to the steam so that the total amount of rapeseed oil / sunflower oil / coconut oil mixed oil was 10 mg / L in terms of condensed water, The test was carried out in the same manner as in Example 7, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
Example 9
In Example 7, except that the rapeseed oil / sunflower oil / coconut oil mixed emulsion was added to the steam so that the total amount of rapeseed oil / sunflower oil / coconut oil mixed oil was 1 mg / L in terms of condensed water, The test was carried out in the same manner as in Example 7, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
実施例１０
　試験期間中、調製例５で得たパーム核油／菜種油混合乳化エマルションを、蒸気に対し、凝縮水換算でパーム核油／菜種油混合油として合計１０ｍｇ／Ｌになるように添加した以外は、比較例１と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。
実施例１１
　試験期間中、調製例５で得たパーム核油／菜種油混合乳化エマルションを、蒸気に対し、凝縮水換算でパーム核油／菜種油混合油として合計１ｍｇ／Ｌになるように添加した以外は、比較例１と同様にして試験を実施し、鋼材及び銅材の腐食速度を求めた。結果を第１表に示す。 Example 10
Comparison was made except that during the test period, the palm kernel oil / rapeseed oil mixed emulsion obtained in Preparation Example 5 was added to the steam to give a total of 10 mg / L as a palm kernel oil / rapeseed oil mixed oil in terms of condensed water. The test was carried out in the same manner as in Example 1, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
Example 11
Comparison was made except that during the test period, the palm kernel oil / rapeseed oil mixed emulsion obtained in Preparation Example 5 was added to the steam so that the total amount of palm kernel oil / rapeseed oil mixed oil was 1 mg / L in terms of condensed water. The test was carried out in the same manner as in Example 1, and the corrosion rates of the steel material and the copper material were determined. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　第１表から明らかなように、防食剤として、紅花油、オリーブ油、ひまわり油、菜種油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種又は２種以上を含む植物系油脂の乳化エマルション、特に（i）紅花油、（ii）オリーブ油、又は（iii）紅花油、オリーブ油、及び菜種油から選ばれる１種と、ひまわり油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種以上との組合せを含む混合油、特に、オリーブ油及び菜種油から選ばれる１種と、ひまわり油、パーム油、パーム核油、及びやし油から選ばれる１種以上との組合せを含む混合油の乳化エマルションを用いると、低濃度で蒸気復水系の鋼材及び銅材の両方に対して優れた防食効果を発揮することができる。 As is apparent from Table 1, as an anticorrosive agent, one selected from safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, palm oil, rice bran oil, linseed oil, and peanut oil Or an emulsified emulsion of vegetable oils and fats comprising two or more, in particular, one selected from (i) safflower oil, (ii) olive oil, or (iii) safflower oil, olive oil, and rapeseed oil, and sunflower oil, cottonseed oil, palm oil , Mixed oil containing a combination of one or more selected from palm kernel oil, palm oil, rice bran oil, linseed oil, and peanut oil, in particular, one selected from olive oil and rapeseed oil, sunflower oil, palm oil, When emulsified emulsion of mixed oil containing a combination of one or more selected from palm kernel oil and palm oil, it exhibits excellent anticorrosive effect for both steam condensate steel and copper at low concentrations To do Can.

Claims (6)

  1. 　ボイラ及び／又は他の蒸気発生プラントにおいて、植物系油脂を乳化したエマルションを、蒸気若しくは復水に添加する蒸気復水系の防食方法であって、前記植物系油脂が、紅花油、オリーブ油、ひまわり油、菜種油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種又は２種以上を含むことを特徴とする蒸気復水系の防食方法。 In a boiler and / or other steam generating plant, a steam condensate anticorrosion method in which an emulsion emulsified with vegetable oil is added to steam or condensate, the vegetable oil being safflower oil, olive oil, sunflower oil A steam condensate anticorrosion method comprising one or more selected from rapeseed oil, cottonseed oil, palm oil, palm kernel oil, palm oil, rice bran oil, linseed oil, and peanut oil.
  2. 　植物系油脂の乳化を、植物由来のエステル系乳化剤を用いて行う、請求項１に記載の蒸気復水系の防食方法。 The steam condensate anticorrosion method according to claim 1, wherein the emulsification of the plant oil is performed using an ester emulsifier derived from a plant.
  3. 　植物系油脂を乳化したエマルションを、凝縮水中における植物系油脂類の濃度が０．０５～５０ｍｇ／Ｌの範囲になるように添加する、請求項１又は２に記載の蒸気復水系の防食方法。 3. The steam condensate anticorrosion method according to claim 1 or 2, wherein the emulsion obtained by emulsifying the vegetable oil is added so that the concentration of the vegetable oil in the condensed water is in the range of 0.05 to 50 mg / L.
  4. 　植物系油脂が、（i）紅花油、（ii）オリーブ油、又は（iii）紅花油、オリーブ油、及び菜種油から選ばれる１種と、ひまわり油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種以上との組合せを含む混合油である、請求項１～３のいずれかに記載の蒸気復水系の防食方法。 Plant oil is (i) safflower oil, (ii) olive oil, or (iii) safflower oil, olive oil, and rapeseed oil, sunflower oil, cottonseed oil, palm oil, palm kernel oil, palm oil, The steam condensate anticorrosion method according to any one of claims 1 to 3, which is a mixed oil containing a combination of at least one selected from rice bran oil, linseed oil, and peanut oil.
  5. 　ボイラ及び／又は他の蒸発発生プラントにおける蒸気復水系の防食剤であって、紅花油、オリーブ油、ひまわり油、菜種油、綿実油、パーム油、パーム核油、やし油、こめ油、アマニ油、及び落花生油から選ばれる１種又は２種以上を含む植物系油脂を乳化してなるエマルションであることを特徴とする防食剤。 Steam condensate anticorrosive in boilers and / or other evaporation generating plants, including safflower oil, olive oil, sunflower oil, rapeseed oil, cottonseed oil, palm oil, palm kernel oil, palm oil, rice bran oil, linseed oil, and An anticorrosive agent, which is an emulsion obtained by emulsifying a plant-based fat or oil containing one or more selected from peanut oil.
  6. 　植物系油脂が、植物由来のエステル系乳化剤で乳化されてなる、請求項５に記載の防食剤。 The anticorrosive agent according to claim 5, wherein the plant oil is emulsified with a plant-derived ester emulsifier.
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