Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.


  1. Advanced Patent Search
Publication numberUS3183070 A
Publication typeGrant
Publication dateMay 11, 1965
Filing dateJan 25, 1963
Priority dateApr 28, 1961
Also published asUS3123634
Publication numberUS 3183070 A, US 3183070A, US-A-3183070, US3183070 A, US3183070A
InventorsJohn H Udelhofen
Original AssigneeStandard Oil Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Rust inhibited oil containing aliphaticaminoalkylsuccinates
US 3183070 A
Abstract  available in
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent 6 Claims. (Cl. 44-71) This invention relates to chemical compounds and their use as rust inhibitors and corrosion inhibitors in normally liquid oleaginous compositions. This invention further relates to and provides normally liquid oleaginous compositions, especially in the presence of water, inhibited against rust and corrosion by the inclusion therein of certain hydroxyamine esters of succinic acid provided herein.

This is a division of application Serial No. 106,196, filed April 2-8, 1961, which issued as US. 3,123,634 on March 3, 1964, and is entitled N-Aliphatic-N,=NDi(Alkyl Monosuccinate)Amine.

In the handling and storage of many normally liquid bydrocarbons and hydrocarbon products, serious problems of corrosion are encountered particularly corrosion to ferrous metal parts. Under conditions of handling the storage of normally liquid hydrocarbons, water often becomes included with the hydrocarbon through seepage, condensation or even from processing of the hydrocarbon. Also present in the hydrocarbon in many instances are acidic and/ or caustic substances in small amounts resulting from prior treatment of the hydrocarbons, e.g. from acid treating and/or caustic treating of fuel oils and lubricating oils. Such acidic and/ or caustic materials are corrosive toward metal parts such as storage tank walls, valves, pipelines, tank car walls, burners, gasoline tanks, crankcases, etc. Other corrosive substances may be formed through oxidative deterioration of the hydrocarbon in the presence of oxygen particularly if the hydrocarbon is stored for substantial periods of time or stored or supported under adversely high temperature conditions. The water present in the hydrocarbon often causes the formation of two Separate phases, i.e. a hydrocarbon phase and an aqueous phase. The corrosive materials become distributed throughout both the hydrocarbon and aqueous phases and it becomes desirable, if not necessary, to protect against corrosion of metal parts from both phases. The presence of the water phase also, of course, promotes rusting of metal parts such as tank walls, pipes, etc. The present invention provides normally liquid hydrocarbon compositions which have imparted thereto the ability to protect against rust and corrosion of both phases by the inclusion therein of certain corrosion inhibiting agents.

The compounds of this invention have the structural formula:

wherein R is an open-chain (non-cyclic) aliphatic hydrocarbon group containing from 8 to 22 carbon atoms and R and R are selected from the class consisting of hydrogen, methyl and ethyl. R may be saturated mono-unsatuated, di-unsaturated or poly-unsaturated, preferably saturated, mono-unsaturated or di-unsaturated. In the preferred embodiments, R contains from 12 to 13 :arbon atoms and R and R" are each hydrogen.

The compounds may be termed monoesters of succinic acid or diesters of an N,N-di(hydroxyallryl)-N-aliphatic amine but are more descriptively referred to herein as N-aliphatic-N,N-di(alkyl monosuccinate) amine or, more simply, as aliphaticaminoalkylsuccinates.

The aliphaticaminoalkylsuccinates may be used in accordance herewith in a normally liquid hydrocarbon'in amounts suflicient to inhibit corrosion and more desirably in amounts sufficient to inhibit corrosion caused by the presence of water in a separate phase in contact with the normally liquid hydrocarbon. More advantageously, the corrosion inhibitors may be used in amounts of from about 0.00005 to about 10 weight percent in a normally liquid hydrocarbon and preferably in amounts of about 0.001 to about .01 weight percent. The salts, e.g. the amine salts and especially the substituted-imidazolinium salts, of the aliphaticaminoalkylsuccinates can also be prepared for use as effective corrosion inhibitors by reacting sufficient substituted imidazoline therewith to neutralize one ,or both carboxylic acid groups.

The R group of the compounds apparently serves two functions. The hydrocarbon chain provides the property of oil-solubility and also provides a sufficiently thick mononuclear layer for the purpose of protecting metal surfaces against rust and corrosion.

More specific examples of compounds of this invention are listed below. 'For simplicity in nomenclature, the listed examples are identified with reference to the structural formula set out above by identification of the R, R and R" groups.

Example N o. R R R Octadecyl Hy-drogen Hydrogen- Tallow d0 Methyl.

do Ethyl.

0. Hydrogen.

.do Ethyl. Docosyl Hydrogen Hexadecadienyl Ethyl. Heptadecyl 1 Methyl. Oleyl -do Hydrogen. Octyl do D0 Ethyl. Hydrogen. o.

Ethyl. Hydrogen.

The designations coco, soybean and tallow are used to designate aliphatic groups derived from coco amines, soybean amines and tallow amines respectively. The coco, soybean and tallow amines are derived from the coconut fatty acids, soybean fatty acids and tallow fatty acids by reaction of the fatty acids with ammonia resulting in the formation of mixtures of amines having varying molecular weights. The amines prepared from the fatty acids are available commercially under the trade name Armeen. The Armeens may advantageously be used as a source of primary aliphatic amines in preparing N,N-di(beta-hydroxyalkyl) N-aliphatic amines for use in preparing compounds of this invention. Examples of the Armeens are Armeen T (derived from tallow fatty acids and containing about 2 0 tetradecyl amine, 24% hexadecyl amine, 28% octadecyl amine and 46% octadecenyl amine) and Armeen 12 (containing 2% decyl amine, dodecyl amine and 3% tetradecyl amine). Other amines from which the N,N-di(beta-hydroxyalkyl) -N-aliphatic amines may be derived are the Alamines such as Alamine 26 (a mixture of saturated, mono-unsaturated and di-unsaturated C primary amines) and Alamine 21D (distilled primary coco amine).

The compounds of this invention may be conveniently prepared by reacting equirnolar amounts of the corresponding N,N-di(beta-hydroxyalkyl) N-aliphatic amine With succinic anhydride. The reaction may be conveniently carried out at normal esterification temperatures preferably in the range of 100-200 C. or higher if desired. The reaction proceeds at a more rapid rate at higher temperates and at a slower rate at lower temperatures. The reaction is terminated, e.g. by removal of heat upon completion of the desired esterification, 2 to 8 hours usually being sufficient for completion of the reaction. Succinic acid may be used in lieu of the anhydride, if desired, but the anhydride is preferred. Where the acid is used in lieu of the anhydride, the water formed may be removed by distillation, but removal of water is not necessary where the anhydride is used.

The reactions in forming the compounds useful in this invention may conveniently be carried out using a solvent in the reaction medium. Useable solvents are the aromatic hydrocarbons and particularly the lower boiling hydrocarbons such as benzene, toluene, xylene, ethylbenzene and the like. It is usually not particularly desirable to remove the solvent after the reaction, especially where the solvent is an aromatic hydrocarbon which may be permitted to be incorporated into the normally liquid hydrocarbon to which the aliphaticaminoalkylsuccinates are added. The lower boiling aromatic hydrocarbons are preferred because they boil within the most desirable reaction temperature ranges. The solvents may function in controlling reaction temperature in that the reaction may be carried out at the reflux temperature of the solvent.

The iN,N-di(beta-hydroxyalkyl) N-aliphatic amines may be prepared by the reaction of two moles of the corresponding alkylene oxide with one mole of the corresponding primary aliphatic amine. The alkylene oxide-primary amine reaction is well known to the art. Useable alkylene oxides, for example, are ethylene oxide, propylene oxide, butylene oxide, etc. Examples of useable primary amines are the amines having the formula RNH wherein R is as identified above. These include, as more specific examples,

7 all of the primary amines having R as specifically identified in the table of examples set out above.

As a typical preparation of an aliphaticaminoalkylsuccinate, 18.60 grams of bis-(beta-hydroxyethyl)-octadecylamine dissolved in 200 m1. of benzene were added slowly with stirring to 1 0.00 grams of succinic anhydride in 100 ml. of benzene. The mixture was refluxed for four hours. The solvent was removed by vacuum distillation leaving 28 grams of N-octadecyl-N,N-di(ethyl monosuccinate) amine, having the formula:

(I) o on oniodomomiion n ar omenzor omonn lon as a viscous liquid product.

The normally liquid hydrocarbons include those hydrocarbons boiling in the gasoline through lubricating oil range and preferably those normally liquid hydrocarbons boiling in the gasoline distillation range. Examples of normally liquid hydrocarbons are gasoline, heater oil, jet fuel, kerosene, mineral lubricating oils, synthetic hydrocarbon lubricating oils, furnace oils, residual heating oils, fuel oil blends containing residual and distillate fuel oils, e.g. Bunker C, gas oils and other residual and distillate fuel oils. The normally liquid hydrocarbons may contain other non-hydrocarbon components, e.g. sulfur, normally present in diesel fuels. The lubricating oils may be sulfur extracted if desired. The normally liquid hydrocarbons may be virgin hydrocarbons or may be processed, e.g, by cracking, alkylation, reforming, isomerization and the like.

The rust inhibitors of this invention are believed to be especially effective in petroleum hydrocarbons and their preferred use is in combination with normally liquid hydrocarbons boiling in the gasoline distillation range.

In order to illustrate the rust and corrosion inhibition properties of the compositions of this invention, examples of compositions of this invention were prepared and subjected to rust and corrosion test as follows:

Indiana Conductometric Rust Test (station) .-This test tests for corrosion inhibition and rust inhibition properties in the presence of corrosive acidic and caustic substances. The test was run using the hydrocarbon phases as identified in the table below. In accordance with the procedure of the test, samples of 0.00073 weight percent (2 pounds per thousand barrels) of N-octadecyl-N,N-di(ethyl monosuccinate) amine, the compound identified as Example 1, above, in the hydrocarbon phase identified in the table below were prepared. Each sample was placed with an equal volume of Water containing added caustic and/or acidic substances in a test tube and stirred briefly to permit the addition agent to become distributed within both the hydrocarbon and aqueous phases. An S-shaped steel test strip, having an electrical terminal at each end of the S was immersed in the hydrocarbon phase to reach adsorption equilibrium and the electrical resistance is noted as a control resistance value. The steel strip was then lowered into the aqueous phase and after 24 hours the change in electrical resistance was taken as a measure of rusting and corrosion in both the aqueous and hydrocarbon phases during the 24-hour period. A determination of rusting and corrosion inhibition was made in terms of corrosion rate measured in mils penetration per day times 10 The mils penetration per day were converted to percent reduction in corrosion by the following equation:

X l00=percent reduction in corrosion r =corrosion rate of steel strip in fuel with inhibitor. r =corrosion rate of steel strip in fuel with no inhibitor.

The percent reduction in corrosion is reported in the following table:

Table Percent Hydrocarbon Aqueous Phase Reduction Phase in Corrosion Gasoline 10- MHCL" r 96. 2 Do--- 10- MNaOH- 95. 4 D0.-- 0.1% NaOl 99. 3 Do--- 0.1% NaGl plus 10- MNaOH 97. 3 Virgin Gas Oil. Deionized Water Alone 94. 7 Do 10- MNazSOi plus 10- MNaOH 93. 8 10- MHCl- 96. 3 10- MNaOH 80. 2 0.1% NaOL. 83. 2

The data of the table indicate the ability of the compositions of this invention to inhibit rust and corrosion even in concentrations lower than .0008 weight percent. in comparison with the control (containing no additive) the compositions of this invention demonstrated an excellent ability in inhibiting rust and corrosion in both the aqueous and hydrocarbon phases in the presence of water and under caustic and acidic conditions.

It is evident from the foregoing that I have provided compounds useful in normally liquid hydrocarbon oils f the prevention of rust and/ or corrosion.

I claim:

1. A normally liquid hydrocarbon composition comprising a major amount of normally liquid hydrocarbon containing a minor amount, sufiicient to inhibit corrosion, of a compound having the structural formula:

wherein R is an open-chain aliphatic hydrocarbon group having 8 to 22 carbon atoms and R and R" are selected from the class consisting of hydrogen, methyl and ethyl.

2. The composition of claim 1 wherein said minor amount is in the range of from about 0.0001 to about 0.1 Weight percent.

3. The composition of claim 1 wherein said normally liquid hydrocarbon boils in the gasoline distillation range.

4-. As a composition of matter, a normally liquid hydrocarbon in contact with an amount of water normally sufficient to promote corrosion of metal parts and containing an amount, from about 0.00005 to about 10 Weight percent, sufiicient to inhibit said corrosion of the compound having the structural formula:

References Cited by the Examiner UNITED STATES PATENTS 2,368,604 1/45 White 4471 2,490,744 12/49 Trigg 252-392 XR 2,614,980 10/52 Lytle 252-392 XR 2,638,449 5/53 White 252-392 XR 2,805,201 9/57 Fischer 252 392 XR 2,977,309 3/61 Godfrey 252392 XR 3,003,960 10/61 Andress 252-393 XR 3,037,051 5/62 Stromberg 44-71 XR 3,060,007 10/62 Freedman 447l XR 3,095,286 6/63 Andress 4471 3,116,129 12/ 63 Udelhofen 44--71 DANIEL E. WYMAN, Primary Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2368604 *Feb 8, 1943Jan 30, 1945Shell DevAnticorrosive
US2490744 *Feb 8, 1947Dec 6, 1949Socony Vacuum Oil Co IncAntirust agent
US2614980 *Apr 3, 1950Oct 21, 1952Standard Oil Dev CoProcess for inhibiting corrosion in oil wells
US2638449 *Dec 30, 1949May 12, 1953Socony Vacuum Oil Co IncReaction products of fatty acids, dialkanolamines, and alkenyl succinic acid anhydrides
US2805201 *Jul 19, 1954Sep 3, 1957Union Oil CoCorrosion prevention in oil wells
US2977309 *Nov 14, 1957Mar 28, 1961Monsanto ChemicalsLubricating oil containing branched chain alkyl amine derivatives of dicarboxylic acids
US3003960 *Jun 10, 1959Oct 10, 1961Socony Mobil Oil Co IncGlycine amic acids in turbine oil
US3037051 *Aug 1, 1958May 29, 1962Petrolite CorpEster-amide-acid compounds
US3060007 *Jul 7, 1959Oct 23, 1962Standard Oil CoHydrocarbon oils containing reaction products of imidazolines and alkylene iminodiacetic acids
US3095286 *May 7, 1958Jun 25, 1963Socony Mobil Oil Co IncStabilized distillate fuel oil
US3116129 *Jul 29, 1960Dec 31, 1963Standard Oil CoFuel oil composition
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3458444 *Nov 17, 1967Jul 29, 1969Texaco IncRust inhibiting composition
US4020000 *Sep 5, 1975Apr 26, 1977American Cyanamid CompanyControl of corrosion and scale in circulating water systems by means of partial esters of polyfunctional organic acids
US4781730 *Jun 5, 1987Nov 1, 1988The Lubrizol CorporationFuel additive comprising a hydrocarbon soluble alkali or alkaline earth metal compound and a demulsifier
US5352377 *Feb 8, 1993Oct 4, 1994Mobil Oil CorporationCarboxylic acid/ester products as multifunctional additives for lubricants
US5456731 *Jun 29, 1994Oct 10, 1995Mobil Oil CorporationCarboxylic acid/ester products as multifunctional additives for fuels
US5964907 *Aug 14, 1996Oct 12, 1999Akzo Nobel N.V.Fuel compositions containing esteramines
US6001141 *Nov 12, 1996Dec 14, 1999Ethyl Petroleum Additives, Ltd.Fuel additive
US6013115 *Aug 19, 1998Jan 11, 2000Akzo N.V.Fuel additive compositions for simultaneously reducing intake valve and combustion chamber deposits
US6371999Aug 21, 1996Apr 16, 2002Basf AktiengesellschaftPolyisobutylaminoalcohols and fuels for internal combustion engines containing these products
EP0464489A1 *Jun 20, 1991Jan 8, 1992BASF AktiengesellschaftEster containing fuels, for spark ignition- and diesel engines
EP0486097A1 *Nov 8, 1991May 20, 1992EURON S.p.A.Process for preparing detergent additive for fuels
EP0561947A1 *Dec 2, 1991Sep 29, 1993Mobil Oil CorporationMultifunctional additives to improve the low-temperature properties of distillate fuels and compositions containing same
EP0773279A1 *Nov 13, 1996May 14, 1997Ethyl Petroleum Additives LimitedFuel additive
WO1995034616A1 *Jun 13, 1994Dec 21, 1995Mobil Oil CorpCarboxylic acid/ester products as multifunctional additives for lubricants
U.S. Classification44/391, 252/392, 508/476, 507/939, 507/244
International ClassificationC23F11/14, C10L1/22, C10L1/222
Cooperative ClassificationY10S507/939, C10M2215/042, C10L1/2225, C10M1/08, C10N2230/12, C23F11/144
European ClassificationC10L1/222B2, C23F11/14B, C10M1/08