US2668100A - Corrosion inhibitor for liquid hydrocarbons - Google Patents

Corrosion inhibitor for liquid hydrocarbons Download PDF

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US2668100A
US2668100A US256603A US25660351A US2668100A US 2668100 A US2668100 A US 2668100A US 256603 A US256603 A US 256603A US 25660351 A US25660351 A US 25660351A US 2668100 A US2668100 A US 2668100A
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glyoxalidine
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George W Luvisi
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ChampionX LLC
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National Aluminate Corp
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/232Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring

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  • This invention relates to hydrocarbon liquids, more particularly gasoline, diesel fuel oil and furnace oils containing acorrosion inhibitor, and to a method of inhibiting corrosion caused by the presence of water in such liquids.
  • R is -hydro'gen ora lower aliphatic; group containing not more than 6' carbon atoms, Y is hydrogen or a lower aliphatic group containing not more than 6 carbon atoms, and Z is'hydrogen or a lower alkyl group containing not more than 6 carbon atoms.
  • R is -hydro'gen ora lower aliphatic; group containing not more than 6' carbon atoms
  • Y is hydrogen or a lower aliphatic group containing not more than 6 carbon atoms
  • Z is'hydrogen or a lower alkyl group containing not more than 6 carbon atoms.
  • the preferred compounds employed for the purpose of the present invention are compounds of the class previously described which are viscous liquids or soft greases characterized by being soluble or dispersible inwater.
  • the preferred compounds-are also preferably soluble in aromatic oils when tested in the manner herein described. All of the compounds are sufiiciently soluble in the hydrocarbon liquids to be effective for the purpose of'the invention; Inthis connection it may be noted that the quantities required for the purpose of th invention" are relatively small and are preferably within the range of 25 to 100 parts of the glyoxali'dinc salicylic acid, salt per million parts 20 Claims. (01. 44-63) of hydrocarbon liquid.
  • the salicylic acid salts are prepared by mixing glyoxalidines and salicylic acid in equimolecular proportions in the cold or by warming the two together at temperatures upto C. for 5 to 15 minutes, with or without a catalyst.
  • the glyoxalidines are made by well knownprocedures by reacting a fatty acid with an aliphatic polyamine with the elimination of water asdescribed for example, in Wilson, U. $2,267,965, and Wilkes et al., U. S. 2,268,273.
  • the salicylic acid salts of glyoxalidines with which the invention is particularly concerned are those salicylic acid salts in which the glyoxalidine portion of the molecule is derived byreacting together one of the acids from the group consisting of lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid with an aliphatic polyamine from the group consisting of aminoethylethanolamine, diethylenetriamine, and triethylenetetramine.
  • the glyoxalidine is derived from aninoethylethanolamine the resultant product contains a hydroxy ethyl group in the 1-position.
  • the resultant product contains an aminoethyl group in the 1-position
  • the resultant product contains a (2-aminoethyl)aminoethy1 group in the .l-position.
  • the number of carbon atoms in the aliphatic hydrocarbon group in the 2-position is always one less than that in the aliphatic carboxylic acid from which the glyoxalidine is derived.
  • glyoxalidines that can be reacted with salicylic acid in preparing salts suitable for the purpose of the invention are: l-(2-hydroxyethyl) -2-undecy1 glyoxalidine, 1- (2- hydroxyethyD-2-tridecyl glyoxalidine, 1-(2-hydroxyethyD-2-pentadecyl glyoxalidine, l-(Z-hydroxyethyl) -2-heptadecyl glyoxalidine, 1- (2-hydroxyethyl) -2-heptadecenylglyoxalidine, 1- (2- aminoethyl) -2-undecyl glyoxalidine, l-(2-aminoethyl) -2-tridecy1 glyoxalidine, 1- (2-aminoethyl) Z-pentadecyl glyoxalidine, 1-(2-amino
  • Solubility React-ants ggg g Description g igg m in Aroa matlc Oil l-(2-hydtoxyethyl) -2-heptadecenyl 3.5 slightly cloudyglyoxalidine. Pgggg$ icams copiously; soluble. Salicylic acid 1. 38 homogen u 81 very nscous eosyeawamous: g figgfigiz g methyl glyomhdme g log viscous liqlut ionf; fairly Do. ui llcavy 0am. l-[2- (2- aminoeth yl) -amlnoethyl] 2- 3.
  • glyoxalidine viscous oil quite viscous; soluble. 2,5-dicbloro-salicylic acid 2.07 lots of foam.
  • the solubility test of the glyoxalidine salt in water was conducted by adding one drop of the salt to ml. of water and agitating and observing the resulting solution.
  • the solubility of the glyoxalidine salt in oil was determined by adding one drop of the salt to 10 ml. of an aromatic oil such as the catalytically cracked product marketed by Shell Oil Company under the trade name of Shells medium aromatic oil with a boiling range of 430 F. to 620 F. and a flash point of 225 F. (Cleve land open cup).
  • an aromatic oil such as the catalytically cracked product marketed by Shell Oil Company under the trade name of Shells medium aromatic oil with a boiling range of 430 F. to 620 F. and a flash point of 225 F. (Cleve land open cup).
  • Example I The glyoxalidine salicylic acid salt was prepared for use as a 10% by weight concentrate in a suitable solvent, for example, xylene and/or naphtha.
  • test specimens were hot rolled mild steel rods x 2%" of which a 2%" length was polished with #3/0 emery cloth.
  • test medium for example, gasoline
  • 25 x 150 mm. screw cap tube was placed in a 25 x 150 mm. screw cap tube. ml. of the test medium were added first the inhibitor solution previously described and after mild agitation 10% by volume of distilled water which had been equilibrated with air. The capped tube was then mechanically agitated at room temperature (75 F.) for six hours by end over end tumbling.
  • the inhibitor materials were generally tested at 50 p. p. m. (parts per million) of test medium with the concentration being varied whenever further testing was warranted.
  • the salicylic acid salt of 1-(2-hydroxyethyD- Z-heptadecenyl glyoxalidine when tested under the foregoing conditions in Standard Red Crown gasoline was efiective in inhibiting corrosion in three tests at a concentration of 25 p. p. m., in two tests at a concentration of 40 p. p. m. and in one test at a concentration of 50 p. p. m. At concentrations of 5 and 10 p. p. m. with this material the test specimens showed slight corrosion. At concentrations of and p. p. m. six test results showed no corrosion to vary slight corrosion. In all of these tests the test medium contained 10% distilled water.
  • Example II The testing procedure was the same as that described in Example I using Standard Red Crown gasoline and 10% distilled water in the medium.
  • I-(Z-aminoethyl) -2-tridecyl glyoxalidine salicylic acid salt was efiective in inhibiting corrosion at concentrations of p. p.-m. and p. p. m. of test medium. At a concentration of 10 p. p. m. the corrosion was slight to moderate at the end of the test period of '72 hours.
  • Example III Using the test procedure described in Example I with Standard Red Crown gasoline and 10% by volume of distilled water in the test medium the l (2 aminoethyl) 2 pentadecyl glyoxalidine salicylic acid salt gave substantially the same. .re sults as those described in Example II. V
  • Example IV Example V Using the test procedure described in Example I with Standard Red Crown gasoline and by volume distilled water in the test medium the 1 -'[2 (2 aminoethyl) aminoethyl] 2- heptadecenyl glyoxalidino salicylic acid salt was effective in preventing corrosion at a concentration of 50 p. p. m. in the test medium. At a concentration of p. p. m. the test specimens showed slight corrosion at the end of the 72-hour test.
  • Example VI The test procedure was the same as that described in Example I except that Stanolind diesel fuel oil was used in place of the Standard Red Crown gasoline and the quantity of water added to the test medium was 10% by volume.
  • the salicylic acid salt described in Example I was completely effective in preventing corrosion in the diesel fuel oil samples at a concentration of x 100 p. p. m. in the test medium.
  • Example VII The test procedure was the same as that used in Example I except that .Stanolex furnace oil containing 10% by volume distilled water was used as the test medium.
  • the salicylic acid salt described in Example I was effective as a corrosion inhibitor at p. p. in. in the test medium. At a concentration of 25 p. p. in. very slight corrosion of the test specimens was observed at the end of the 72-hour test period.
  • Example VIII The 1-(2 hydroxyethyi)-2(3,5,5 trimethylpentyl) glyoxalidine salicylic acid salt was prepared by adding 39.5 grams of 8,5,5-trimethylhexanoic acid and 26 grams of aminoethylethanolamine to 220 cc. of xylene and heating at a temperature of 161 C. to 169 C. for approximately 20 hours with the elimination or" 3.9 cc. of water. The xylene was removed by distillation and the residuewas distilled at l to 2 mm. pressure at a temperature of 169 C. to 190 C. The resultant glyoxalidine was a greenish yellow viscous liquid. Equimolecular proportions'of this product and salicylic acid were reacted by heating on a steam bath for 15 minutes to produce the salicylic acid salt.
  • the resultant salt was found to be insoluble in Indocene 90 (a Standard Oil of Indiana petroleum fraction high in aromatic compounds and 'naphthenes) and therefore was dissolved as a 10% solution in the mono'outyl other of diethyl ene glycol.
  • This solution was added to Stanolinrl diesel fuel oil and testing according to the procedure described in Example I.
  • At a concentration of 100 p. p. m. of the salicylic acid salt effective corrosion inhibition was obtained in the ,waterphase. :In the oil phase there was no corrosionof the test specimens at concentrations as low as 10 p. p. m.
  • a comparative test with the solvent material the monobutyl ether of diethylene glycol
  • the solvent material the monobutyl ether of diethylene glycol
  • eiieotive corrosion inhibiting ingredient is employed in accordance with the invention in very small amounts, it is desirable to prepare it the form of a solution contain ing about 5 to 15% of the effective ingredient, the remainder being a suitable solvent. Any solvent which is miscible with the corrosion inhibiting ingredient and the medium to which it is to be added can be employed for the purpose of the invention. [is an illustration, where the corrosion inhibiting ingredient is to be added to gasoline a suitable concentrate has the following composition:
  • compositions can be prepared using as a solvent either naphtha alone or Xylene alone or other suitable solvents such as diethylene glycol monobutyl ether and mixtures thereof naphtha and/or xylene.
  • the solvent should have characteristics compatible with those of the diesel fuel oil or the furnace oil.
  • the diesel fuel oil or the furnace oil has been used as the solvent in the concentrate.
  • Indocene has been employed very satisfactorily as a solvent for the salicylic acid salt in concentrates used as additives for furnace oils and diesel fuel oil except in those instances where the salicylic acid salt is insoluble in this solvent as in Example VIII.
  • the dosage required for eiiective corrosion inhibition is very often different in gasoline and heavier hydrocarbon liquids such as diesel oil and furnace oil.
  • the corrosion inhibitor be effective at concentrations of not more than parts per million parts by weight of the hydrocarbon liquid.
  • the introduction of large amounts of the corrosion inhibitor could have very adverse effects,
  • compositions containing hydrocarbon liquids and water appear to-occur inthe water phase where there is a separation of the water.
  • Many closely related materials were tested and found to be ineffective at concentrations where the compositions of the present invention are efifective, for example at 50 p. p. m.
  • gasoline the acetate and benzoate salts of the glyoxalidines containing an aliphatic hydrocarbon chain having eight or more carbon atoms in the 2-position were ineffective.
  • the salicylate of the glyoxalidine derived by reacting diethylenetriamine with ethylhexanoic acid and which contains a seven carbon atom alkyl group in the 2-position was ineiiective.
  • the glyoxalidines derived by reacting diethylenetriamine with lauric acid; diethylenetriamine with myristic acid; diethylenetriamine with palmitic acid; triethylenetetramine with oleic acid; aminoethylethanolamine with oleic acid; and diethylenetriamine with nonoic acid were ineffective in inhibiting corrosion under the test conditions previously described.
  • a hydrocarbon liquid containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2- position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the l-position is linked to a memher from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the -position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
  • Gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the 4-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carnon atoms in the eiand 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
  • a diesel fuel oil containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2- position is, linked to a higher aliphatic hydrocarcon group containing at least 8 carbon atoms, the carbon atom in the e-position is linked to a memher from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
  • a furnace fuel oil containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the 4-position is linkedto a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to a member from the group consisting oi hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
  • Gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing 13 to 1'7 carbon atoms, inclusive, in an acyclic chain, the carbon atoms in the 4- and 5-positions are linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms and the nitrogen atom in the 1-position is linked to a Z-hydroxyethyl group.
  • Gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing 13 to 1'? carbon atoms, inclusive, in an acyclic chain, the carbon atoms in the 4- and to a, member from the roup consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms and the nitrogen atom in the l-position is linked to a Z-(aminoethyl) -aminoethyl group.
  • a hydrocarbon liquid containing a corrosion inhibiting amount of l-(2-hydroxy-ethyl) -2- heptadecenyl glyoxalidine salicylic acid salt containing a corrosion inhibiting amount of l-(2-hydroxy-ethyl) -2- heptadecenyl glyoxalidine salicylic acid salt.
  • a method of inhibiting corrosion of ferrous metals by hydrocarbon liquids containing water which comprises bringing said metals into contact-with said liquids .containinga corrosion inhibiting amount of a salicylic acid salt of a glyoggalidine wherein the carbon atom in the 2,-po'sition is linked to a higher aliphatic hydrocarbon group containingat least 8 carbon atoms,
  • the carbon atom in the e-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms
  • the carbon atom in the -position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the iand 5-positions
  • the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
  • a method of inhibiting corrosion of ferrous metals by gasoline contaminated with moisture which comprises bringing said metals into contact with said gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the ls-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
  • a method of inhibiting corrosion of ferrous metals by a diesel fuel oil contaminated with moisture which comprises bringing said metals into contact with said diesel fuel oil containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the 4-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the'o-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
  • a method of inhibiting corrosion of ferrous metals by a furnace fuel oil contaminated with moisture which comprises bringing said metals into contact with said furnace fuel oil containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 3 carbon atoms, the carbon atom in the l-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
  • a method of inhibiting corrosion of ferrous metals by a hydrocarbon liquid containing water which comprises bringing said metals into contact with said liquid containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine having the following general formula wherein R is a higher aliphatic group containing 13 to 17 carbon atoms, inclusive, in an acyclic chain, R, is a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, Y is a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, and Z is a member from the group consisting of hydrogen and lower alkyl groups containing not more than 6 carbon atoms.
  • a method of inhibiting corrosion of ferrous metals by gasoline contaminated with moisture which comprises bringing said metals into contact with said gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing 13 to 17 carbon atoms, inclusive, in an acyclic chain, the carbon atoms in the 4- and 5-positions are linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms and the nitrogen atom in the 1-position is linked to a Z-hydroxyethyl group,
  • a method of inhibiting corrosion of ferrous metals by gasoline contaminated with moisture which comprises bringing said metals into contact with said gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing 13 to 1'? carbon atoms, inclusive, in an acyclic chain, the carbon atoms in the 4- and 5-positions are linked to a member from the '1'! group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms and the nitrogen atom in the 1-position is linked to a Z-aminoethyl group.
  • a method of inhibiting corrosion of ferrous metals by gasoline contaminated with moisture which comprises bringing said metals into contact with said gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing 13 to 17 carbon atoms inclusive in an acyclic chain, the carbon atoms in the 4- and 5-positions are linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms and the nitrogen atom in the 1-position is linked to a 2-(aminoethyl) -aminoethyl group.
  • a method of inhibiting corrosion of ferrous metals by a hydrocarbon liquid containing water which comprises bringing said metals into contact with said liquid containing a corrosion inhibiting amount of 1- (Z-hydroxy-ethyl) -2heptadecenyl glyoxalidine salicylic acid salt.
  • a method of inhibiting corrosion of ferrous metals by gasoline contaminated with water which comprises bringing said metals into contact with said gasoline containing about to about parts per million of 1-(2-hydroxyethyl) -2-heptadecenyl glyoxalidine salicylic acid salt.

Description

Patented Feb. 2, 1954 UNITED STATES PATENT OFFICE CORROSION INHIBITOR FOR LIQUID HYDROCARBONS George W. Luvisi, Chicago, Ill., assignor to National Aluminate Corporation, Chicago, 111., a.
corporation of Delaware No- Drawing. Application November 15, 1951, Serial No. 256,603
This invention relates to hydrocarbon liquids, more particularly gasoline, diesel fuel oil and furnace oils containing acorrosion inhibitor, and to a method of inhibiting corrosion caused by the presence of water in such liquids.
In copending application, Serial No. 186,929, of which the present application is a continuationin-part, there are disclosed compounds which can be described as carbocyclic monocarboxy acid The said application also a The carbocyclic monocarboxy acid salts of gly oxalidiiies .With which. the invention is particularly concerned have the following general formula wherein R is a higher aliphatic hydrocarbon radi- :.calucont aining at least 8, preferablylS. to 17 car- "bon atoms. inclusive, in anacyclic chain, R is -hydro'gen ora lower aliphatic; group containing not more than 6' carbon atoms, Y is hydrogen or a lower aliphatic group containing not more than 6 carbon atoms, and Z is'hydrogen or a lower alkyl group containing not more than 6 carbon atoms. These compounds may also be described generally as salicylic acid salts of .glyoxalidines.
The preferred compounds employed for the purpose of the present inventionare compounds of the class previously described which are viscous liquids or soft greases characterized by being soluble or dispersible inwater. The preferred compounds-are also preferably soluble in aromatic oils when tested in the manner herein described. All of the compounds are sufiiciently soluble in the hydrocarbon liquids to be effective for the purpose of'the invention; Inthis connection it may be noted that the quantities required for the purpose of th invention" are relatively small and are preferably within the range of 25 to 100 parts of the glyoxali'dinc salicylic acid, salt per million parts 20 Claims. (01. 44-63) of hydrocarbon liquid. Even in amounts as low as ten parts per million som of these compounds are efiective in inhibiting sludge formation in certain types of heavier oils where the formation of sludge is a problem, for example, in burning oils such as are used in locomotives and in diesel fuel oils.
The salicylic acid salts are prepared by mixing glyoxalidines and salicylic acid in equimolecular proportions in the cold or by warming the two together at temperatures upto C. for 5 to 15 minutes, with or without a catalyst. The glyoxalidines are made by well knownprocedures by reacting a fatty acid with an aliphatic polyamine with the elimination of water asdescribed for example, in Wilson, U. $2,267,965, and Wilkes et al., U. S. 2,268,273.
The salicylic acid salts of glyoxalidines with which the invention is particularly concerned are those salicylic acid salts in which the glyoxalidine portion of the molecule is derived byreacting together one of the acids from the group consisting of lauric acid, myristic acid, palmitic acid, oleic acid and stearic acid with an aliphatic polyamine from the group consisting of aminoethylethanolamine, diethylenetriamine, and triethylenetetramine. When the glyoxalidine is derived from aninoethylethanolamine the resultant product contains a hydroxy ethyl group in the 1-position. When the glyoxalidine is derived from diethylenetriamine the resultant product contains an aminoethyl group in the 1-position, and when the glyoxalidine is derived from triethylenetetramine the resultant product contains a (2-aminoethyl)aminoethy1 group in the .l-position.
The number of carbon atoms in the aliphatic hydrocarbon group in the 2-position is always one less than that in the aliphatic carboxylic acid from which the glyoxalidine is derived.
Specific examples of glyoxalidines that can be reacted with salicylic acid in preparing salts suitable for the purpose of the invention are: l-(2-hydroxyethyl) -2-undecy1 glyoxalidine, 1- (2- hydroxyethyD-2-tridecyl glyoxalidine, 1-(2-hydroxyethyD-2-pentadecyl glyoxalidine, l-(Z-hydroxyethyl) -2-heptadecyl glyoxalidine, 1- (2-hydroxyethyl) -2-heptadecenylglyoxalidine, 1- (2- aminoethyl) -2-undecyl glyoxalidine, l-(2-aminoethyl) -2-tridecy1 glyoxalidine, 1- (2-aminoethyl) Z-pentadecyl glyoxalidine, 1-(2-aminoethyD-2- heptadecyl glyoxalidine, 1- (2-aminoethyl) 2-heptadecenyl glyoxalidine, l-[(2-aminoethyl)-aminoethyll -2-undecyl glyoxalidine, l- (2-aminoethyl) -aminoethyll -2-tridecyl glyoxalidine, J l- [(2-aminoethyl) -aminoethyll -2-pentadecyl glyoxalidine, 1 (2 aminoethyl) aminoethyl] 2- heptadecyl glyoxalidine, 1 [(2 aminoethyl) aminoethyll 2 heptadecenyl glyoxalidine, i methyl-2-undecyl glyoxalidine, 4methyl-2tri decyl glyoxalidine, imethyl2-pentadecyl glyoxalidine, 4-methyl-2-heptadecenyl glyoxalidine 4-methyl-2-heptadecenyl glyoxalidine. V V
The following table contains some of the properties of glyoxalidine salicylates that have been employed in accordance with the invention:
was then evaluated on the extent of visible corrosion. Each test was made in duplicate. If both specimens were not visibly corroded the material was classed as effective and if both appeared to be corroded the material was called inefiective. Wherever one of the pairs was uncorroded and the other corroded the test was repeated. If, after retesting, either specimen was corroded the material was judged to be ineffective at the tested concentration. This criterion is identical with that used in ASTM D665-49T.
. Solubility React-ants ggg g Description g igg m in Aroa matlc Oil l-(2-hydtoxyethyl) -2-heptadecenyl 3.5 slightly cloudyglyoxalidine. Pgggg$ icams copiously; soluble. Salicylic acid 1. 38 homogen u 81 very nscous eosyeawamous: g figgfigiz g methyl glyomhdme g log viscous liqlut ionf; fairly Do. ui llcavy 0am. l-[2- (2- aminoeth yl) -amlnoethyl] 2- 3. 93 horn ogeneous deep clear gelatinous soheptadecenyl-glyoxalidine. yellow viscous lution; very insoluble. Salicylic acid 1.38 liquid. mlrigagy [calm 2-heptadecenyl 4-methyl glyoxalidine- 3. 2 clear amber vis- 1 so non; Salicylic acid 2.76 cous liquid. gg' fg heavy 1 [2 (aminoethyl) aminoethyl] 2 3.93 clc-ir solution' excloudy amber sattii iiii ffiTilt 2. 76 f wiry-like liquidliit hem 1- (2-hydroxycthyl) -2-heptadecenyl 3. hazy solution;
glyoxalidine. viscous oil quite viscous; soluble. 2,5-dicbloro-salicylic acid 2.07 lots of foam.
The solubility test of the glyoxalidine salt in water was conducted by adding one drop of the salt to ml. of water and agitating and observing the resulting solution.
The solubility of the glyoxalidine salt in oil was determined by adding one drop of the salt to 10 ml. of an aromatic oil such as the catalytically cracked product marketed by Shell Oil Company under the trade name of Shells medium aromatic oil with a boiling range of 430 F. to 620 F. and a flash point of 225 F. (Cleve land open cup).
The corrosion inhibiting properties of these new compounds will be further illustrated by the following examples.
Example I The glyoxalidine salicylic acid salt was prepared for use as a 10% by weight concentrate in a suitable solvent, for example, xylene and/or naphtha.
The test specimens were hot rolled mild steel rods x 2%" of which a 2%" length was polished with #3/0 emery cloth.
The test medium, for example, gasoline, was placed in a 25 x 150 mm. screw cap tube. ml. of the test medium were added first the inhibitor solution previously described and after mild agitation 10% by volume of distilled water which had been equilibrated with air. The capped tube was then mechanically agitated at room temperature (75 F.) for six hours by end over end tumbling.
removed, rinsed with acetone and air dried. It
The inhibitor materials were generally tested at 50 p. p. m. (parts per million) of test medium with the concentration being varied whenever further testing was warranted.
The salicylic acid salt of 1-(2-hydroxyethyD- Z-heptadecenyl glyoxalidine when tested under the foregoing conditions in Standard Red Crown gasoline was efiective in inhibiting corrosion in three tests at a concentration of 25 p. p. m., in two tests at a concentration of 40 p. p. m. and in one test at a concentration of 50 p. p. m. At concentrations of 5 and 10 p. p. m. with this material the test specimens showed slight corrosion. At concentrations of and p. p. m. six test results showed no corrosion to vary slight corrosion. In all of these tests the test medium contained 10% distilled water.
Similar tests conducted with the 1-(2-hydroxyethyl) -2-heptadecenyl glyoxalidine salicylic acid salt in the same test medium containing 1% by volume of distilled water gave results similar to those obtained with 10% by volume of distilled water.
All of the foregoing tests were made at room temperatures of approximately 75 F. The water saturated gasoline did not corrode the steel specimens during a test period of six weeks.
Example II The testing procedure was the same as that described in Example I using Standard Red Crown gasoline and 10% distilled water in the medium. I-(Z-aminoethyl) -2-tridecyl glyoxalidine salicylic acid salt was efiective in inhibiting corrosion at concentrations of p. p.-m. and p. p. m. of test medium. At a concentration of 10 p. p. m. the corrosion was slight to moderate at the end of the test period of '72 hours.
Example III Using the test procedure described in Example I with Standard Red Crown gasoline and 10% by volume of distilled water in the test medium the l (2 aminoethyl) 2 pentadecyl glyoxalidine salicylic acid salt gave substantially the same. .re sults as those described in Example II. V
Example IV Example V Using the test procedure described in Example I with Standard Red Crown gasoline and by volume distilled water in the test medium the 1 -'[2 (2 aminoethyl) aminoethyl] 2- heptadecenyl glyoxalidino salicylic acid salt was effective in preventing corrosion at a concentration of 50 p. p. m. in the test medium. At a concentration of p. p. m. the test specimens showed slight corrosion at the end of the 72-hour test.
Example VI The test procedure was the same as that described in Example I except that Stanolind diesel fuel oil was used in place of the Standard Red Crown gasoline and the quantity of water added to the test medium was 10% by volume. The salicylic acid salt described in Example I was completely effective in preventing corrosion in the diesel fuel oil samples at a concentration of x 100 p. p. m. in the test medium.
Example VII The test procedure was the same as that used in Example I except that .Stanolex furnace oil containing 10% by volume distilled water was used as the test medium. The salicylic acid salt described in Example I was effective as a corrosion inhibitor at p. p. in. in the test medium. At a concentration of 25 p. p. in. very slight corrosion of the test specimens was observed at the end of the 72-hour test period.
Example VIII The 1-(2 hydroxyethyi)-2(3,5,5 trimethylpentyl) glyoxalidine salicylic acid salt was prepared by adding 39.5 grams of 8,5,5-trimethylhexanoic acid and 26 grams of aminoethylethanolamine to 220 cc. of xylene and heating at a temperature of 161 C. to 169 C. for approximately 20 hours with the elimination or" 3.9 cc. of water. The xylene was removed by distillation and the residuewas distilled at l to 2 mm. pressure at a temperature of 169 C. to 190 C. The resultant glyoxalidine was a greenish yellow viscous liquid. Equimolecular proportions'of this product and salicylic acid were reacted by heating on a steam bath for 15 minutes to produce the salicylic acid salt.
The resultant salt was found to be insoluble in Indocene 90 (a Standard Oil of Indiana petroleum fraction high in aromatic compounds and 'naphthenes) and therefore was dissolved as a 10% solution in the mono'outyl other of diethyl ene glycol. This solution was added to Stanolinrl diesel fuel oil and testing according to the procedure described in Example I. At a concentration of 100 p. p. m. of the salicylic acid salt effective corrosion inhibition was obtained in the ,waterphase. :In the oil phase there was no corrosionof the test specimens at concentrations as low as 10 p. p. m. A comparative test with the solvent material (the monobutyl ether of diethylene glycol) at 900 p. p. m. showed that the solvent did not provide any protection in the water phase even at this relatively large concentration.
Since the eiieotive corrosion inhibiting ingredient is employed in accordance with the invention in very small amounts, it is desirable to prepare it the form of a solution contain ing about 5 to 15% of the effective ingredient, the remainder being a suitable solvent. Any solvent which is miscible with the corrosion inhibiting ingredient and the medium to which it is to be added can be employed for the purpose of the invention. [is an illustration, where the corrosion inhibiting ingredient is to be added to gasoline a suitable concentrate has the following composition:
Weight per cent 1- (Z-hydroxyethyl) -2-heptadecenyl glyoxali dine salicylic acid salt 12 Naphtha (flash point F. to 105 F.) 68 Xylene 20 Similarly, other compositions can be prepared using as a solvent either naphtha alone or Xylene alone or other suitable solvents such as diethylene glycol monobutyl ether and mixtures thereof naphtha and/or xylene.
Where the concentrate is to be added to a diesel fuel oil or a furnace oil the solvent should have characteristics compatible with those of the diesel fuel oil or the furnace oil. In some cases the diesel fuel oil or the furnace oil has been used as the solvent in the concentrate. Indocene has been employed very satisfactorily as a solvent for the salicylic acid salt in concentrates used as additives for furnace oils and diesel fuel oil except in those instances where the salicylic acid salt is insoluble in this solvent as in Example VIII.
The dosage required for eiiective corrosion inhibition is very often different in gasoline and heavier hydrocarbon liquids such as diesel oil and furnace oil. In general, it is desired for the purpose of the invention that the corrosion inhibitor be effective at concentrations of not more than parts per million parts by weight of the hydrocarbon liquid. Especially in gasoline the introduction of large amounts of the corrosion inhibitor could have very adverse effects,
such as gum formation. In actual tests using in one case a composition composed of 12% of the salicylate described in Example I and 88% of Indocene 90 and in another case a composition composed of 12% of the salicylate described in Example 68% or Staniscl Stoddard solvent and 20 xylene there was only a slight increase in gum formation in the first instance and a decrease in the second instance at concentrations of 25 p. m. and 12.5 p. p. m. of the salicylates, respectively.
The best results in the, prevention of corrosion in. were obtained with the glyoxalidine salicyl c salt described in Example I and purified thereof. This salt is insoluble in the monobutyl ether of diethylene glycol, soluole in 100% ethanol, soluble in Indocene 90, soluble in 99% iscpropanol, soluble in xylene, insoluble in Stanisol Stoddard solvent and insoluhis in virgin gas oil.
In general, the greatest corrosion produced by compositions containing hydrocarbon liquids and water appears to-occur inthe water phase where there is a separation of the water. Many closely related materials were tested and found to be ineffective at concentrations where the compositions of the present invention are efifective, for example at 50 p. p. m. In gasoline the acetate and benzoate salts of the glyoxalidines containing an aliphatic hydrocarbon chain having eight or more carbon atoms in the 2-position were ineffective. At the same concentration in gasoline the salicylate of the glyoxalidine derived by reacting diethylenetriamine with ethylhexanoic acid and which contains a seven carbon atom alkyl group in the 2-position was ineiiective. Likewise, at the same concentration in gasoline the glyoxalidines derived by reacting diethylenetriamine with lauric acid; diethylenetriamine with myristic acid; diethylenetriamine with palmitic acid; triethylenetetramine with oleic acid; aminoethylethanolamine with oleic acid; and diethylenetriamine with nonoic acid were ineffective in inhibiting corrosion under the test conditions previously described.
The invention is hereby claimed as follows:
1. A hydrocarbon liquid containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2- position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the l-position is linked to a memher from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the -position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
2. Gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the 4-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carnon atoms in the eiand 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
3. A diesel fuel oil containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2- position is, linked to a higher aliphatic hydrocarcon group containing at least 8 carbon atoms, the carbon atom in the e-position is linked to a memher from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
4. A furnace fuel oil containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the 4-position is linkedto a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to a member from the group consisting oi hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
5. A hydrocarbon liquid containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine having the folowing general formula wherein R is a higher aliphatic group containing 13 to 1'7 carbon atoms, inclusive, in an acyclic chain, B is a member from the group consisting of hydrogen and lower aliphatic group-s containing not more than 6 carbon atoms, Y is a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, and Z is a member from the group consisting of hydrogen and lower alkyl groups containing not more than 6 carbon atoms.
6. Gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing 13 to 1'7 carbon atoms, inclusive, in an acyclic chain, the carbon atoms in the 4- and 5-positions are linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms and the nitrogen atom in the 1-position is linked to a Z-hydroxyethyl group.
'7. Gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing 13 to 17 carbon atoms, inclusive, in an acyclic chain, the carbon atoms in the 4- and 5-positions are linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms and the nitrogen atom in the 1-position is linked to a 2-aminoethy1 group.
3. Gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing 13 to 1'? carbon atoms, inclusive, in an acyclic chain, the carbon atoms in the 4- and to a, member from the roup consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms and the nitrogen atom in the l-position is linked to a Z-(aminoethyl) -aminoethyl group.
9. A hydrocarbon liquid containing a corrosion inhibiting amount of l-(2-hydroxy-ethyl) -2- heptadecenyl glyoxalidine salicylic acid salt.
10. Gasoline containing about 20 to about 50 parts per million of 1-(2-l1ydroxyethyl) heptadecenyl glyoxalidine salicylic acid salt.
11. A method of inhibiting corrosion of ferrous metals by hydrocarbon liquids containing water which comprises bringing said metals into contact-with said liquids .containinga corrosion inhibiting amount of a salicylic acid salt of a glyoggalidine wherein the carbon atom in the 2,-po'sition is linked to a higher aliphatic hydrocarbon group containingat least 8 carbon atoms,
the carbon atom in the e-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the -position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the iand 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
12. A method of inhibiting corrosion of ferrous metals by gasoline contaminated with moisture which comprises bringing said metals into contact with said gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the ls-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
13. A method of inhibiting corrosion of ferrous metals by a diesel fuel oil contaminated with moisture which comprises bringing said metals into contact with said diesel fuel oil containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the 4-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the'o-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
14. A method of inhibiting corrosion of ferrous metals by a furnace fuel oil contaminated with moisture which comprises bringing said metals into contact with said furnace fuel oil containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 3 carbon atoms, the carbon atom in the l-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.
15. A method of inhibiting corrosion of ferrous metals by a hydrocarbon liquid containing water which comprises bringing said metals into contact with said liquid containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine having the following general formula wherein R is a higher aliphatic group containing 13 to 17 carbon atoms, inclusive, in an acyclic chain, R, is a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, Y is a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, and Z is a member from the group consisting of hydrogen and lower alkyl groups containing not more than 6 carbon atoms.
16. A method of inhibiting corrosion of ferrous metals by gasoline contaminated with moisture which comprises bringing said metals into contact with said gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing 13 to 17 carbon atoms, inclusive, in an acyclic chain, the carbon atoms in the 4- and 5-positions are linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms and the nitrogen atom in the 1-position is linked to a Z-hydroxyethyl group,
17. A method of inhibiting corrosion of ferrous metals by gasoline contaminated with moisture which comprises bringing said metals into contact with said gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing 13 to 1'? carbon atoms, inclusive, in an acyclic chain, the carbon atoms in the 4- and 5-positions are linked to a member from the '1'! group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms and the nitrogen atom in the 1-position is linked to a Z-aminoethyl group.
18. A method of inhibiting corrosion of ferrous metals by gasoline contaminated with moisture which comprises bringing said metals into contact with said gasoline containing a corrosion inhibiting amount of a salicylic acid salt of a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing 13 to 17 carbon atoms inclusive in an acyclic chain, the carbon atoms in the 4- and 5-positions are linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms and the nitrogen atom in the 1-position is linked to a 2-(aminoethyl) -aminoethyl group.
19. A method of inhibiting corrosion of ferrous metals by a hydrocarbon liquid containing water which comprises bringing said metals into contact with said liquid containing a corrosion inhibiting amount of 1- (Z-hydroxy-ethyl) -2heptadecenyl glyoxalidine salicylic acid salt.
20. A method of inhibiting corrosion of ferrous metals by gasoline contaminated with water which comprises bringing said metals into contact with said gasoline containing about to about parts per million of 1-(2-hydroxyethyl) -2-heptadecenyl glyoxalidine salicylic acid salt.
GEORGE W. LUV'ISI.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,553,183 Caron May 15, 1951

Claims (1)

1. A HYDROCARBON LIQUID CONTAINING A CORROSION INHIBITING AMOUNT OF A SALICYLIC ACID SALT OF A GLYOXALIDINE WHEREIN THE CARBON ATOM IN THE 2POSITION IS LINKED TO A HIGHER ALIPHATIC HYDROCARBON GROUP CONTAINING AT LEAST 8 CARBON ATOMS, THE CARBON ATOM IN THE 4-POSITON IS LINKED TO A MEMBER FROM THE GROUP CONSISTING OF HYDROGEN AND LOWER ALIPHATIC GROUPS CONTAINING NOT MORE THAN 6 CARBON ATOMS, THE CARBON ATOM IN THE 5-POSITION IS LINKED TO A MEMBER FROM THE GROUP CONSISTING OF HYDROGEN AND LOWER ALIPHATIC GROUPS CONTAINING NOT MORE THAN 6 CARBON ATOMS, THERE BEING AT LEAST ONE HYDROGEN ATOM ON EACH OF THE CARBON ATOMS IN THE 4- AND 5-POSITONS, AND THE NITROGEN ATOM IN THE 1-POSITON IS LINKED TO A MEMBER FROM THE GROUP CONSISTING OF HYDROGEN AND LOWER ALIPHATIC GROUPS CONTAINING NOT MORE THAN 6 CARBON ATOMS, THERE BEING AT LEAST ONE HYDROGEN ATOM ATTACHED TO SAID NITROGEN ATOM.
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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2839371A (en) * 1954-04-08 1958-06-17 California Research Corp Gasoline composition
US2854322A (en) * 1954-12-30 1958-09-30 Petrolite Corp Stabilization of organic materials
DE1042808B (en) * 1956-01-18 1958-11-06 Shell Res Ltd Lubricating oil
US2907646A (en) * 1955-09-29 1959-10-06 American Oil Co Rust inhibitor for fuel fractions of mineral oil
US2915376A (en) * 1956-05-28 1959-12-01 Shell Dev Perfluoroalkylimidazolines and compositions containing the same
US2945821A (en) * 1956-10-24 1960-07-19 Nalco Chemical Co Process of inhibiting corrosion
DE1088647B (en) * 1957-09-13 1960-09-08 Socony Mobil Oil Co Inc Grease
US2965459A (en) * 1958-03-03 1960-12-20 Standard Oil Co Gasoline containing borated oxazolines
DE1103713B (en) * 1955-09-27 1961-03-30 Nalco Chemical Co Anti-corrosive agents
US2993765A (en) * 1958-03-03 1961-07-25 Standard Oil Co Gasolines containing acid-treated borated oxazolines
US2994596A (en) * 1956-10-24 1961-08-01 Nalco Chemical Co Hydrocarbon liquids inhibited against corrosion
DE1121760B (en) * 1958-03-12 1962-01-11 Bataafsche Petroleum Grease
US3033664A (en) * 1957-12-24 1962-05-08 British Petroleum Co Hydrocarbon distillate fuels
DE1130247B (en) * 1955-07-27 1962-05-24 Standard Oil Co Use of polycarboxylic acid salts of a 1,2-disubstituted imidazoline as a corrosion inhibitor
US3098727A (en) * 1958-03-03 1963-07-23 Standard Oil Co Motor fuel composition
DE1264209B (en) * 1954-02-05 1968-03-21 Petrolite Corp Anti-corrosive agents
US4256664A (en) * 1973-03-12 1981-03-17 Colgate-Palmolive Company Substantive sunscreen agents
US4421659A (en) * 1982-06-30 1983-12-20 Mobil Oil Corporation Zwitterionic quaternary ammonium sulfates and lubricants containing same
US5062992A (en) * 1988-09-23 1991-11-05 Betz Laboratories, Inc. Emulsion minimizing corrosion inhibitor for naphtha/water systems
US5104578A (en) * 1988-09-23 1992-04-14 Betz Laboratories, Inc. Emulsion minimizing corrosion inhibitor for naphtha/water systems
US5174957A (en) * 1988-09-23 1992-12-29 Betz Laboratories, Inc. Emulsion minimizing corrosion inhibitor for naphtah/water systems
US10221368B2 (en) 2015-07-27 2019-03-05 Instituto Mexicano Del Petroleo Method of inhibiting corrosion using a corrosion inhibitor derived from vegetable oils
EP3456868A1 (en) 2017-07-27 2019-03-20 INDIAN OIL CORPORATION Ltd. Corrosion inhibitor composition for pipelines
US11866666B1 (en) 2023-01-20 2024-01-09 Saudi Arabian Oil Company Methods for corrosion reduction in petroleum transportation and storage

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Publication number Priority date Publication date Assignee Title
US2553183A (en) * 1948-07-03 1951-05-15 Shell Dev Fuel oil composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
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US2553183A (en) * 1948-07-03 1951-05-15 Shell Dev Fuel oil composition

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1264209B (en) * 1954-02-05 1968-03-21 Petrolite Corp Anti-corrosive agents
US2839371A (en) * 1954-04-08 1958-06-17 California Research Corp Gasoline composition
US2854322A (en) * 1954-12-30 1958-09-30 Petrolite Corp Stabilization of organic materials
DE1130247B (en) * 1955-07-27 1962-05-24 Standard Oil Co Use of polycarboxylic acid salts of a 1,2-disubstituted imidazoline as a corrosion inhibitor
DE1103713B (en) * 1955-09-27 1961-03-30 Nalco Chemical Co Anti-corrosive agents
US2907646A (en) * 1955-09-29 1959-10-06 American Oil Co Rust inhibitor for fuel fractions of mineral oil
DE1042808B (en) * 1956-01-18 1958-11-06 Shell Res Ltd Lubricating oil
US2915376A (en) * 1956-05-28 1959-12-01 Shell Dev Perfluoroalkylimidazolines and compositions containing the same
US2945821A (en) * 1956-10-24 1960-07-19 Nalco Chemical Co Process of inhibiting corrosion
US2994596A (en) * 1956-10-24 1961-08-01 Nalco Chemical Co Hydrocarbon liquids inhibited against corrosion
DE1088647B (en) * 1957-09-13 1960-09-08 Socony Mobil Oil Co Inc Grease
US3033664A (en) * 1957-12-24 1962-05-08 British Petroleum Co Hydrocarbon distillate fuels
US2993765A (en) * 1958-03-03 1961-07-25 Standard Oil Co Gasolines containing acid-treated borated oxazolines
US3098727A (en) * 1958-03-03 1963-07-23 Standard Oil Co Motor fuel composition
US2965459A (en) * 1958-03-03 1960-12-20 Standard Oil Co Gasoline containing borated oxazolines
DE1121760B (en) * 1958-03-12 1962-01-11 Bataafsche Petroleum Grease
US4256664A (en) * 1973-03-12 1981-03-17 Colgate-Palmolive Company Substantive sunscreen agents
US4421659A (en) * 1982-06-30 1983-12-20 Mobil Oil Corporation Zwitterionic quaternary ammonium sulfates and lubricants containing same
US5062992A (en) * 1988-09-23 1991-11-05 Betz Laboratories, Inc. Emulsion minimizing corrosion inhibitor for naphtha/water systems
US5104578A (en) * 1988-09-23 1992-04-14 Betz Laboratories, Inc. Emulsion minimizing corrosion inhibitor for naphtha/water systems
US5174957A (en) * 1988-09-23 1992-12-29 Betz Laboratories, Inc. Emulsion minimizing corrosion inhibitor for naphtah/water systems
US10221368B2 (en) 2015-07-27 2019-03-05 Instituto Mexicano Del Petroleo Method of inhibiting corrosion using a corrosion inhibitor derived from vegetable oils
EP3456868A1 (en) 2017-07-27 2019-03-20 INDIAN OIL CORPORATION Ltd. Corrosion inhibitor composition for pipelines
US10563114B2 (en) 2017-07-27 2020-02-18 Indian Oil Corporation Limited Corrosion inhibitor composition for pipelines
US11866666B1 (en) 2023-01-20 2024-01-09 Saudi Arabian Oil Company Methods for corrosion reduction in petroleum transportation and storage

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