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
  • C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
  • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
  • Y10S516/06—Protein or carboxylic compound containing

Definitions

• U. S. Pat. No. 2,400,543 discloses the use of aliphatic and aromatic amines which are water insoluble or only slightly water soluble to inhibit foam in boiler water.
• U. S. Pat. No. 2,460,259 discloses the use of primary aliphatic amines as corrosion inhibitors in boiler systems.
• U. S. Pat. No. 2,712,531 discloses the use of a blend of octadecylamine and octadecylamine acetate as a corrosion inhibitor.
• 2,882,171 discloses aliphatic amines with or without a non-ionic surface active dispersant used as a corrosion inhibitor.
• U. S. Pat. No. 2,947,703 discloses a method of inhibiting acid corrosion of ferrous metals by addition of higher alkyl substituted nitrogen bases, including amines and thiourea or alkyl substituted thioureas.
• U. S. Pat. No. 2,956,889 discloses an aqueous emulsion of an aliphatic amine with an ethylene oxide/high molecular weight aliphatic amine condensate used as a corrosion inhibitor.
• 3,088,796 discloses an emulsion of an aliphatic amine with an ethylene amine salt or a polyoxyethylene amino compound used as a corrosion inhibitor.
• U. S. Pat. No. 3,239,470 discloses the combination of a primary aliphatic amine having 14-22 carbon atoms, an ethoxylated amine condensate, and a phenolic lignin sulfonate used as a corrosion inhibitor.
• U. S. Pat. No. 3,418,253 discloses an aqueous dispersion of a straight chain aliphatic hydrocarbon primary amine with an ethoxylated guide used as a corrosion inhibitor.
• U. S. Pat. No. 3,418,254 discloses an aqueous dispersion of a straight chain aliphatic hydrocarbon primary amine with an ethoxylated alcohol used as a corrosion inhibitor.
• the fatty amines noted above are useful in inhibiting corrosion in boiler systems and the like due to their unique balance of hydrophilic/hydrophobic properties and relatively high molecular weight.
• Fatty amines possess very desirable film forming properties, which enable them to escape the aqueous phase and deposit as nearly insoluble protective films on all surfaces inside a boiler system or the like.
• the insolubility of fatty amines in water makes the initial application throughout the system unusually difficult. In order to be fed uniformly into the boiler water, these film forming fatty amines must first be thoroughly emulsified in water.
• U. S. Pat. No. 2,156,193 discloses that guanyl and biguanyl compounds including guanylisothiourea possess considerable wetting and dispersing action.
• U. S. Pat. No. 2,302,762 discloses a process of forming isothioureas and that they may be used as emulsifying agents.
• U. S. Pat. No. 2,302,885 discloses hydrohalides of substituted isothioureas and their preparation.
• U. S. Pat. No. 2,323,075 discloses a method of preparing thiouronium salts.
• U. S. Pat. No. 2,332,401 discloses the use of S-alkyl (long chain) isothiourea hydrochloride as a plasticizer.
• U. S. Pat. No. 2,640,079 discloses alkylbenzylthiouronium salts for use as bactericides and fungicides.
• U. S. Pat. No. 2,717,826 discloses the use of S-benzylisothiourea as an additive to fuel oil to retard deterioration.
• U. S. Pat. No. 2,840,610 discloses a phenol substituted amine/carbon disulfide reaction yielding an alkylamine thiouronium salt for use as a corrosion inhibitor.
• U. S. Pat. No. 2,947,703, discussed above, discloses a higher alkyl substituted organic nitrogen base/thiourea emulsion, used for acid corrosion inhibition of ferrous metals.
• 3,088,849 discloses a protective surface coating formed by interacting a fluorocarbon-substituted isothiouronium halide with an alkali.
• U. S. Pat. No. 3.093,666 discloses the use of high molecular weight isothiouronium compounds per se for inhibiting corrosion to metallic surfaces.
• U. S. Pat. No. 3,1 16,327 discloses gamma-dimethylaminopropyl isothiourea and its salts for use as a pharmaceutical.
• U. S. Pat. No. 3,123,636 discloses the use of n-thiouronium halides as surfactants.
• 3,155,645 discloses the use of an isothiouronium salt of a bromohydrin ether as a dyestuff.
• U. S. Pat. No. 3,260,748 discloses S-(4-vinylbenzyl) isothiourea and its chloride salt for use as a fungicide and as an intermediate for making 4-(rnercaptomethyl) styrene.
• U. S. Pat. No. 3,31 1,639 discloses a process for making hydrochloride salts of S- methylisothiourea compounds for use as pharmaceuticals and as chemical intermediates.
• 3,321,519 discloses a process for making substituted aminoalkyl isothiouronium salts for use as a pharmaceutical.
• U. S. Pat. No. 3,407,229 discloses phenolcarbamoylethyl isothioureas for use as a pharmaceutical.
• U. S. Pat. No. 3,407,230 discloses benzamidoalkylisothioureas for use as a pharmaceutical.
• novel composition claimed in this invention uses an emulsifier which degrades, upon continued heating, into volatile fractions, which thus do not accumulate within the boiler water.
• novel cationic fatty amine emulsions which are stable until subjected to heating, at which time they break down to allow the fatty amine to enter the vapor phase and thus be carried throughout the boiler system, coating all exposed metallic surfaces thereof with a corrosion inhibiting film.
• the said composition comprises a water soluble emulsion of a fatty amine with one or more cationic emulsifiers.
• an ethoxylated straight chain aliphatic acid may be added as an emulsion stabilizer.
• Useful fatty amines include saturated nalkyl amines containing 12' to 22 carbon atoms; unsaturated n-alkyl amines having a saturated backbone containing 12 to 22 carbon atoms with l or 2 unsaturated moieties on the backbone; branched alkyl amines containing 12 to 22 carbon atoms; mixtures of any or all of the above; and hydrogenated mixtures of any of the above unsaturated amines.
• Examples of useful fatty amines include,
• dodecylamine tridecylamine; tetradecylamine; pentadecylamine; hexadecylamine; heptadecylamine; octadecylamine; nonadecylamine;
• R is an alkyl hydrocarbon of C1042 and R is chloride, bromide, acetate or sulfate.
• use ful cationic emulsifiers include, but are not limited to: dodecyl isothiouronium bromide, octadecyl isothiouronium chloride, eicosyl isothiouronium sulfate, hydroxymethyldodecyl isothiouronium acetate, triethyl-tridecyl isothiouronium bromide,
• the preferred cationic emulsifiers for utilization in this invention are dodecyl isothiouronium chloride and paraffin wax isothiouronium chloride.
• the cationic emulsifi er will be present in the composition of this invention in from about 1 to about 7 parts by weight, and preferably from 1 to about 4 parts by weight. 7 V
• a straight chain aliphatic acid of C which has been ethoxylated with from 2 to 30 moles of ethylene oxide may be added to the emulsifier.
• the preferred stabilizer additive is octadecanoic acid ethoxylated with from about 5 to about 25 moles of ethylene oxide.
• the emulsion stabilizer will be present in the composition of this invention in from O to about 7 parts by weight and preferably from O to about 3 parts by weight. It should be noted that the preferred emulsion stabilizer is difficult to dissolve in water and therefore is not suitable for use as an emulsifier in the composition of this invention.
• the steam-corrosion inhibiting composition may be utilized in the following novel manner. Said composition is added to the water in the boiler system by direct addition to the water storage tank, by feeding into' water being added to the water storage tank, or by any other means, so that a ratio of from about 0.10 percent to about 2.0 percent by weight of said composition to the weight of the boiler water is maintained.
• the boiler water is then heated sufficiently to break down the emulsion into its component parts. Further heating of the boiler water will cause the fatty amine component to enter its vapor phase and become dispersed throughout the boiler system, whereupon it will become deposited as a film upon all exposed metallic interior surfaces of the system. Said film will then inhibit corrosion of the said surfaces caused by the steam passing across them.
• the film-coating process is independent of the steam generation, it is most frequently conducted simultaneously therewith.
• the temperature at which the boiler system is functioning is not of importance as long as it is sufficient to break down the emulsion and vaporize the fatty amine.
• the fatty amine will enter the vapor phase at a lower temperature and conversely, in a high pressure system, a higher temperature will be required to vaporize the fatty amine.
• a mixture of C -dodecyl chloride this is a mixture of C chains which is predominantly C and sold as such, 61.6 g., thiourea, 57 g., and ethyl alcohol,
• Octadecylamine, 18 g. was blended with the product of Example I, 2 g., (net, i.e. after evaporation of the alcoholic solvent) and subsequently ground in a porcelain mortar until the two components were thoroughly mixed. Distilled water, 80 g., was then added dropwise and the grinding procedure continued until a uniform white emulsion was obtained. Care was taken to avoid the generation of foam during the later stages of the emulsification process. The emulsion was then divided into 2 parts and diluted to 16.6 and 7 percent solids, respectively, and the samples used for evaluation purposes. At 7 percent solids, the emulsion was very liquid, almost comparable to milk, and could be diluted infinitely with distilled water. No sign of phase separation occurred in 0.5 percent solutions of this emulsion in distilled water. The 16.6 percent emulsion had a cream-like appearance and showed the same characteristics as the 7 percent emulsion.
• Example llI Emulsification of hydrogenated tallow amine with dodecyl isothiouronium chloride.
• Example IV(a) Preparation of a modified version of dodecyl isothiouronium chloride.
• Dodecyl chloride C (This is a mixture of C chains which is predominantly C and sold as such.) 218.5 g., thiourea, 152.2 g., and ethyl alcohol, 400 g., were allowed to interact at 80C under reflux conditions until the water-solubility test" carried out with small samples of the reaction mixture according to the procedure described in Example IV(b) indicated that dodecyl chloride was converted nearly completely into soluble isothiouronium salts. The product was then isolated as described in Example I for C1218 dodecyl chloride.
• EXAMPLE IV(b) Water-solubility test This test was developed as a control method for the production of dodecyl isothiouronium chloride from dodecyl chloride and thiourea, and is based on the water-insolubility of dodecyl chloride.
• the product/salt mixture yields a cloudy white solution at room temperature; as product concentration increases however, a precipitate will form in larger quantities.
• the graduated tube containing the product/salt mixture is then heated in a water bath until a clear solution is obtained. If any unreacted dodecyl chloride is present in the reaction mixture, it will reveal itself by forming a separate layer on the surface of the water/salt solution. Measuring the volume of unreacted' dodecyl chloride thus affords a semi-quantitative estimate of the progress of the reaction. In the final stage, no dodecyl chloride will separate out at 5060C. The mixture can then be centrifuged in order to facilitate the detection of any residual amounts of dodecyl chloride, which may have escaped the natural gravimetric separation. All samples are compared to a blank obtained by mere physical blending of the reagents mentioned above.
• Octadecylamine, 9 g. was blended with the product of Example IV(a), l g. (net, i.e. after evaporation of the alcoholic solvent), and subsequently ground in a porcelain mortar until the two components were thoroughly mixed. Distilled water, g., was then added dropwise and the grinding procedure continued until a uniform white-creamy" emulsion was obtained. Care was taken to avoid the generation of foam during the later stages of the emulsification process. No sign of phase separation occurred in 0.5 percent solution of this emulsion in distilled water.
• Octadecylamine, 10 g. was blended with the product of Example VI, 2.5 g., and subsequently ground in a porcelain mortar until the two components were thoroughly mixed. Distilled water, 90 g., was then added dropwise and the grinding procedure continued until a uniform creamy-white emulsion was obtained. Great care was taken to avoid the generation of foam during the later stages of the emulsification process. No sign of phase separation occurred in 0.5 percent solution of this emulsion in distilled water.
• the stability tests were carried out by placing between one to ten parts of weight of the emulsion into approximately 100 grams of the test medium which was distilled water, tap water, cold and hot (80C) salt solution and observing the effects of this dilution upon the emulsion. Then the consistency of the final mixture was observed. Where stability upon dilution with distilled water was not obtained, it was concluded that the initial emulsification of the amine was incomplete.
• compositions on occasion requires stability under more severe conditions, such as T tap water D distilled water ODAM octadecylamine B mechanical blender 5 M mortar and pestle HT Heat and agitate LTM-N lauryl trimethylene ammonium chloride CPA Nonionic polyacrylamide cationized with N- methyIoI dimethylamine STO ethoxylated stearic acid of 39 percent by weight ethylene oxide IMD imidazoline which is the reaction product of equimolar amounts of hydroxyethyl ethylenediamine and oleic acid.
• LAO lauryl alcohol ethoxylated with 12 moles of ethylene oxide LAO lauryl alcohol ethoxylated with 12 moles of ethylene oxide.
• compositions of the Phosphate emulsified amines were also tested for their stability Perccm y Wmght of Sodium hydroxlde towards inorganic salts and towards hot salt solutions In 050 9 y Welght of Sodium Sulfite the tables, the following symbols or abbreviations are P y Welght of ethylene dlamme tetraacetic acid used. 40
• a steam-corrosion inhibiting composition comprising an aqueous emulsion containing from about 1 percent to about 25 percent by weight of solids consisting of:
• B from about 1 to about 7 parts by weight of a cationic emulsiiier having the general formula where R is a alkyl hydrocarbon having from about 10 to about 22 carbon atoms and R is one of a group consisting of an acetate, a bromide, a chloride, and a sulfate; and C. from O to about 7 parts by weight of an emulsion stabilizer consisting of an ethoxylated straight chain unsubstituted acid containing from about 14 to about 20 carbon atoms in the chain.
• said fatty amine is octadecylamine.
• composition according to claim 1 in which said fatty amine is hydrogenated tallow amine.
• composition according to claim 1 in which said cationic emulsifier is paraffin wax isothiouronium chloride.
• composition according to claim 1 in which the emulsion stabilizer is present in up to 7 parts by weight.
• composition according to claim 6 in which said emulsion stabilizer is octadecanoic acid ethoxylated with from about 5 to about 25 moles of ethylene oxide.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Colloid Chemistry (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=22076905

Family Applications (1)

Country Status (5)

Cited By (3)

Families Citing this family (2)

Citations (5)

• 1970
  • 1970-08-27 US US00067570A patent/US3718604A/en not_active Expired - Lifetime
• 1971
  • 1971-08-26 BR BR5601/71A patent/BR7105601D0/pt unknown
  • 1971-08-26 FR FR7130955A patent/FR2103555B1/fr not_active Expired
  • 1971-08-26 DE DE19712142830 patent/DE2142830A1/de active Pending
  • 1971-08-26 GB GB4010671A patent/GB1354753A/en not_active Expired

Patent Citations (5)

Also Published As

Similar Documents

Legal Events