Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
• • 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
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
  • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
  • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic 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
  • Y10S507/00—Earth boring, well treating, and oil field chemistry
  • Y10S507/933—Acidizing or formation destroying
  • Y10S507/934—Acidizing or formation destroying with inhibitor

Definitions

• This invention relates to corrosion inhibiting compositions and processes, and more particularly to compositions and methods for inhibiting corrosion and pitting caused by aqueous solutions of pickling and cleaning acids, such as sulfuric, sulfamic, phosphoric, citric, etc. acids.
• a primary object is to provide a composition and process meeting safety hazard requirements and providing effective protection against corrosion by aqueous acid solutions.
• a further object is to provide a composition which eliminates the need for solvents while at the same time having a high flash point providing for the utmost of safety in use.
• a further object is to provide a composition in which the active materials are effectively dispersed for yielding high efiiciency in use.
• Yet another object is to provide a composition in which the quaternary ammonium compound may be one hundred percent active.
• dibutylthiourea is mixed with a compound having the following structure:
• R is an aliphatic hydrocarbon radical having between 6 and 22 carbon atoms
• R is an alkylene radical having between 2 and 3 carbon atoms
• R" is an alkyl radical having between 1 and 3 carbon atoms
• X is a halogen
• x and y are integers having a sum total varying between 2 and 50.
• ethylene oxide or propylene oxide it is preferred to employ in combination with the dibutylthiourea, an ethoxylated quaternary ammonium compound or a propoxylated quaternary ammonium compound, and the range of moles for the ethylene oxide or propylene oxide is 2 to 50 moles. I prefer to employ 2 to 25 moles of the ethylene oxide or propylene oxide. Best results have been obtained when there are about 2 to 15 moles of the ethylene oxide or propylene oxide.
• the ethoxylated quaternary ammonium compound or propoxylated quaternary ammonium compound may be used with the dibutylthiourea in varying proportions, the preferred range being -50% by weight of the dibutylthiourea to 90-50% by weight of the ethoxylated quaternary ammonium compound. Best results have been obtained where the dibutylthiourea is 25% and the ethoxylated ammonium compound is 75% by weight.
• the new formulation or composition may contain a active quaternary ammonium compound.
• composition consisting of the ethoxylated quaternary ammonium compound and the dibutylthiourea may be used without further additives.
• the com position may be usefully employed with a dispersant material, such as a cationic or non-ionic surface active agent, including a polyethoxylated fatty acid, polyeth oxylated diamines, etc.
• a dispersant material such as a cationic or non-ionic surface active agent, including a polyethoxylated fatty acid, polyeth oxylated diamines, etc.
• a cationic or non-ionic surface active agent including a polyethoxylated fatty acid, polyeth oxylated diamines, etc.
• polyethoxylated rosin-fatty acids Usually good results have been obtained by the use of polyethoxylated rosin-fatty acids.
• Ethoquad C/25 ethoxylated quaternary ammonium compound of coco origin having 15 moles of ethylene oxide
• Ethofat 242/25 polyethoxylated 70% rosin-fatty acids having 15 moles of ethylene oxide
• Propoquad C/ 25 (quaternary ammonium compound from coco origin having 15 moles of propylene oxide) is substituted with equal results for Ethoquad C/25.
• compositions described may be employed with any of the pickling or cleaning acids, including sulfuric, phosphoric, sulfamic, citric, etc. acids.
• Example I Mild steel coupons were exposed to an acid at a previously determined concentration and at a given temperature for 6 hours. At the end of the test period, the coupon was removed from the acid, cleaned, and reweighed. The corrosion rate is calculated on a weight loss basis and expressed in lb./ft. /day.
• the mild steel coupons were wiped free of excess grease with a clean cloth, degreased in isooctane, and agitated in a ball mill in the presence of mesh Alundum powder for 3 days. Just before using, the coupons were removed from the ball mill, washed in hot alcohol, and dried in hot acetone.
• compositions were prepared and tested in a 15% sulfuric acid solution; 0.25% inhibitor concentration (basis acid concentration), and at a temperature of 200 F., using the mild steel coupons described above.
• the compositions were as follows:
• composition was as in (1) except that Ethoquad C/ 12 (ethoxylated quaternary ammonium compound of coco origin having 2 moles of ethylene oxide) was substituted for Ethoquad C/ 25 (3)
• Propoquad C/ 12 propoxylated quaternary ammonium compound of coco origin having 2 moles of propylene oxide was substituted for Ethoquad C/ 25.
• composition was as in 1) except that for the Ethoquad C/ 25, Propoquad C/25 (propoxylated quaternary ammonium compound of coco origin having 15 moles of propylene oxide) was substituted.
• composition was as in (1) except that for 3 the Ethoquad C/25, Propo'quad HT/12 (propoxylated quaternary ammonium compound of hydrogenated tallow origin having 2 moles of propylene oxide) was substituted.
• composition was as in except that Propoquad HT/25 (propoxylated quaternary ammonium compound having 15 moles of propylene oxide) was used in place of Propoquad HT/ 12.
• Example II Armohib 31 was made up of the following chemicals:
• the Ethoquad C/25 was acidulated to a pH of 4.55.5, as indicated by a pH meter, the acidulation being with concentrated sulfuric acid.
• the correct amounts of Ethofat 242/25 and dibutylthiourea were then added to the Ethoquad C/25 and the mixture heated to approximately 150 F. until the dibutylthiourea was melted. The mixture was stirred during the heating period. A test made after a 48-hour period showed that no unpleasant or offensive odor was developed.
• Example III The test was carried on as described in Example 11 except that phosphoric acid at temperatures of 165 F. and 200 F. and at acid percents varying from 20-10% was employed, the results in terms of lb./ft. /day being substantially less than .027
• Example IV Tests were made as described in Example II with citric acid at temperatures of 165 F. and at 200 F., with the citric acid being used at l0-20%, and with the results in the terms of lb./ft. /day being again substantially less than .027.
• Example V A further test was made using a mixture of phosphoric acid and sulfuric acid at room temperatures and with results comparable to those described in Example II.
• Example VI Tests employing a composition consisting of 25% dibutylthiourea and 75% Ethoquad C/25 were carried out as described in Example 11, no dispersant chemical being employed, and the corrosion rate was found to be substantially less than .027 lb./ft. /day.
• a composition for inhibiting corrosion of ferrous metals in contact with aqueous solutions of corroding acids consisting essentially of dibutylthiourea and from about 50 to 90 weight percent, based upon total weight of the composition, of a compound having the structure:
• R is an aliphatic hydrocarbon radical having between 6 and 22 carbon atoms
• R is an alkylene radical having between 2 and 3 carbon atoms
• R is an alkyl radical having between 1 and 3 carbon atoms
• X is a halogen
• x and y are integers having a sum total varying between 2 and 50.
• a composition for inhibiting corrosion of ferrous metals in contact with aqueous solutions of corroding acids consisting essentially of dibutylthiourea and an ethoxylated quaternary ammonium compound having an aliphatic hydrocarbon radical with between 6 and 22 carbon atoms in the ratio of 10-50% by weight of dibutylthiourea and 90-50% by weight of the ethoxylated quaternary ammonium compound.
• composition of claim 3 in which the proportion by weight of the dibutylthiourea is A to /s of the composition and the proportion by weight of the ethoxylated compound is about to of the composition.
• composition of claim 2 in which the proportion by weight of the dibutylthiourea is about 25 and that of the ethoxylated quaternary ammonium compound is about 75 of the composition.
• composition of claim 2 in which the ethoxylated quaternary ammonium compound is an ethoxylated quaternary ammonium compound having 2 to 50 moles of ethylene oxide.
• composition of claim 5 in which the ethoxylated compound has 2 to 15 moles of ethylene oxide.
• a composition for inhibiting corrosion of ferrous metals in contact with aqueous solutions of corroding acids consisting essentially of dibutylthiourea and a propoxylated quaternary ammonium compound having an aliphatic hydrocarbon radical of from 6 to 22 carbon atoms in the ratio of 50% by weight of dibutylthiourea and 9050% by Weight of the propoxylated quaternary ammonium compound, said quaternary ammonium compound being propoxylated with from 2 to 50 moles of propylene oxide.
• a corrosion inhibiting composition consisting essentially of dibutylthiourea and an ethoxylated quaternary ammonium compound having an aliphatic hydrocarbon radical with between 6 and 22 carbon atoms in the proportions of 105 0% by weight of dibutylthiourea and 90-50% of the ethoxylated quaternary ammonium compound.
• a corrosion inhibiting composition consisting essentially of dibutylthiourea and a propoxylated quaternary ammonium com pound having an aliphatic hydrocarbon radical with between 6 and 22 carbon atoms in the proportions of 10-- by Weight of dibutylthiourea and 50-90% of the propoxylated quaternary ammonium compound.
• a corrosion inhibiting composition In the preparation of a corrosion inhibiting composition, the steps of acidulating a propoxylated quaternary ammonium compound having an aliphatic hydrocarbon radical with between 6 and 22 carbon atoms to a pH of 4.5-5.5, and then mixing therewith dibutylthiourea in the proportions of about 1050% of the dibutylthiourea to 50-90% by weight of the propoxylated quaternary ammonium compound.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

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Cited By (17)

Citations (5)

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• 1962
  • 1962-06-27 US US205559A patent/US3294695A/en not_active Expired - Lifetime
• 1963
  • 1963-06-25 FR FR7787A patent/FR1362161A/fr not_active Expired
  • 1963-06-25 GB GB25304/63A patent/GB984329A/en not_active Expired
  • 1963-06-27 DE DE19631521655D patent/DE1521655B1/de active Pending

Patent Citations (5)

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