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Publication numberUS3116129 A
Publication typeGrant
Publication dateDec 31, 1963
Filing dateJul 29, 1960
Priority dateJul 29, 1960
Publication numberUS 3116129 A, US 3116129A, US-A-3116129, US3116129 A, US3116129A
InventorsJohn H Udelhofen
Original AssigneeStandard Oil Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Fuel oil composition
US 3116129 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States No Drawing. Filed July 20, 1960, Ser. No. 46,109 9 Claims. (Ci. 44--7S) This invention relates to novel corrosion and/ or rust inhibitors particularly adapted for use in preventing corrosion of metals especially iron, steel and ferrous alloys by liquids containing corrosive compounds such as, for example, petroleum fuel oil and to the method of preventing such corrosion.

The rusting of steel used in the transportation and storage of petroleum fuel oils has always presented a serious problem. The presence of sediment and rust as a result of corrosion and the carry-over of the sediment into the fuel burning installations presents a serious operating problem. In addition to the possibility of storage tank rusting through with the consequent loss of fuel oil, there is the additional danger that the furnace filters and furnace fuel lines may become clogged, thus causing the failure of the heating system.

The problem of corrosion or rusting is associated with the presence of moisture in the oil products caused by entrainment, condensation and solution. In most cases, the problem is accentuated by the presence of a separate water phase. Thus, in the storage and bulk shipment of fuel oil, it is common practice to maintain a water layer as tank bottoms. Even where a separate water layer is not maintained as tank bottoms, a separate water phase may be formed by repeated condensation of moisture associated with tank breathing or the repeated expansion and contraction of the bulk due to temperature changes unless special precautions are taken. Complete protection against rusting, therefore, requires a corrosion inhibitor which is effective in both the oil and water phase.

It is an object of the present invention to provide a corrosion and/or rust inhibitor adapted for use in preventing the corrosion and/ or rusting of metals by liquids containing corrosive compounds associated with oleaginous materials such as petroleum fuel oils. It is a further object of this invention to provide a normally liquid nonlubricating hydrocarbon fuel oil composition having improved rust inhibiting properties for the protection of metal surfaces of oil storage and/or handling equipment whether metal surfaces be exposed to the oil or to the Water phase. Other objects and advantages of the invention will become apparent from the following description thereof.

I have now discovered certain new corrosion inhibitors which find utility as a corrosion inhibitor for fuel oils. The corrosion inhibitor is represented by the following structural formula:

ate 1 3,llb,l2 Patented Dec. 31, 1963 "ice wherein R is the group having the formula:

OOOH R 0 l R is selected from the class consisting of hydrogen and methyl, and R is an aliphatic hydrocarbon group having from 6 to 22 and preferably from about 12 to 18 carbon atoms. R R and R preferably are open chain aliphatic hydrocarbon groups and advantageously may contain from 0 to 2 unsaturated linkages; preferably they are saturated.

The corrosion inhibitors of this invention may be used to form a fuel oil composition containing a major proportion of a distillate fuel oil and a small or minor amount of the corrosion inhibitor. Such distillate fuel oil compositions may comprise a distillate fuel oil containing from about 0.0001 to about 5 weight percent and preferably from about 0.001 to about 0.05 Weight percent of the corrosion inhibitor. The corrosion inhibitor may also be formulated as an addition agent concentrate in a suitable organic solvent as more particularly described below. This concentrate may be used by further dilution with the distillate fuel oil to form the distillate fuel oil composition. The corrosion inhibitors of the present invention are advantageously oil-soluble.

The corrosion inhibitors of this invention may be prepared by reacting the corresponding hydroxyalkyl amine in the presence of an inert solvent with trirnellitic anhydride. The reaction may be carried out in the presence of a solvent such as benzene, ethanol, n-butanol, isobutanol, xylene, etc. An acceptable temperature for the reaction may be in the range of from about 50 F. to about 200 F. although higher or lower temperatures may be used.

Examples of specific materials which may be used in accordance with the hereinabove mentioned method and formula are illustrated in Table I.

The following procedures illustrate the method of preparing specific examples set forth in Table I.

solvent was removed by vacuum distillation thus leaving 8.5 g. of N,N,N'-tri-[2-(2,5-dicarboxybenzoxy) propyl1- N-ta1low-1,3-propanediamine having the formula:

Procedure A I? A mixture of 21.28 g. of N,N,N'-tri (Z-hydroxy) ethyl- T N-tallow-1,3-propanediamine, 23.04 g. of trimellitic ann, hydride, and 250 ml. of acetone solvent were placed in (IJHZ COOH a reactor. The reactor was heated to the reflux temperatture of the acetone and refluxed for a period of 3 hours. (3H2 H 46 g. of N,N,N-tri-[2-(2,4-dicarboxybenzoxy) ethyl]-N'- C0011 tallow-l,3-propanediamine having the following formula I- were recovered: (30 OH 2 (I311: C H2 I CH2 0 Procedure B The corrosion inhibitors defined herein, such as those prepared as described above as well as those set forth in the above examples are usable in minor amounts from about 0.0001 to about 5 weight percent and preferably from about 0.001 to about 0.05 weight percent in distillate fuel oils.

The distillate fuel oil may be virgin or cracked petroleum distillate fuel oil. The fuel oil may boil in the range of from about 200 to about 750 F., and preferably in the range of 350 to 650 F. The distillate fuel oil may contain or consist of cracked components such as, for example, those derived from cycle oils or cycle oil cuts boiling heavier than gasoline, usually in the range of from about 450 to 750 F. and may be derived by catalytic or thermal cracking. The distillate oil may contain other components such as addition agents used for a particular function such as, for example, pour point depressants, combustion improvers, or the like.

The distillate fuel oil is preferably a heating oil in which the corrosion inhibitors of this invention are used in accordance herewith. These oils are intended for use by burning to obtain heat such as is intended for furnace or heater fuel use as opposed to internal combustion C O OH engine fuel wherein the explosiveness of the fuel in a com- 0113 0 bustion chamber is of prime importance. Examples of hh' '1 h 1 'd 1r1 R N CH2CH 0 C COOH 811C eating 01 S are a eavy industna IfiSl ua L16 (e.g. L 2 Bunker C), a heater oil fraction, :1 gas oil, a furnace oil,

Procedure C kerosene, or any other light oil intended for furnace or heater fuel use.

The rust inhibiting properties of the above described compositions were evaluated by the following test:

INDIANA CONDUCTOMETRIC TEST (STATIC) This test, which quantitatively measures corrosion rates, depends upon the measurement of the change in electrical resistance of a steel test strip immersed in the corrosive medium. The change in resistance is simply related to the decrease in the thickness of the test specimen caused by corrosion. In the test, specimen holders are designed to make electrical connections to two steel strips suspended in large glass test tubes. A mixture is prepared using six parts of fuel oil containing the rust inhibitor and four parts double distilled water. The corrosion test strips are first immersed in the fuel oil containing the rust inhibitor for a period of one-half hour and subsequently suspended in the mixture such that approximately one-half of the specimen is above the oilwater interface and the remaining half of the specimen is below the oil-water interface. The strips are maintained in the mixture for a period of 24 hours at a temperature of 25 C. The corrosion rates are calculated on a quantative basis from the observed change in electrical resistance.

The data obtained by subjecting the products of this invention to the above test are tabulated in the following table and demonstrate the effectiveness of the herein de scribed products in inhibiting rust in fuel oil compositions.

Note-The above test conditions used virgin gas oil and double distilled water for the blank and test samples.

The corrosion inhibitors of the present invention may, for convenience, be prepared as an addition agent concentrate. Accordingly, the corrosion inhibitor is prepared in or dissolved in a suitable organic solvent therefor in amounts greater than and preferably from about to about 65%. The solvent, in such concentrate, may conveniently be present in amounts of from about to about 75%. The organic solvent preferably boils within the range of from about 100 F. to about 700 F. For the preferred heating oil use, the organic solvents may advantageously be hydrocarbon solvents, for example, petroleum, petroleum fractions, such as naphtha, heater oil, mineral spirits and the like, because of their clean burning properties. The solvents selected should, of course, be selected with regard to beneficial or adverse affects it may have on the ultimate fuel oil composition. Thus, the solvent should preferably burn without leaving a residue and should be non-corrosive with regard to metal, and especially ferrous metals. Other desirable properties are obvious from the intended use of the solvent.

The terms coco, soybean, tallow, and the like as used herein denote that the group so identified is derived from a particular source. The coco groups are derived rom rrixtures of coco fatty acids; the soybean groups are derived from soybean fatty acids; the tallow groups are derived from tallow fatty acids. Such coco, soybean and tallow fatty acids are derived from coconut, soybean and tallow oils and are marketed commercially. Each such group is usually a mixture of carbon chains differing slightly in length and/ or configuration. For example, the tallow groups are a mixture of C to C groups predominating in stearyl and palmityl groups. The groups are wel known in the additive art.

Wherever percentages are given herein, weight percentages are intended unless otherwise indicated.

t is evident from the foregoing that I have provided new and useful corrosion inhibitors for distillate fuel oils and particularly in distillate heating oils.

1 claim:

1. A distillate fuel oil composition comprising a major proportion of a hydrocarbon oil fraction in the fuel oil distillation range and from about 0.0O01% to about 5% of a compound having the general formula:

a wherein R is the group having the formula:

COOH B4 II wherein R is selected from the class consisting of R and an aliphatic hydrocarbon group having from 6 to 22 carbon atoms and R is selected from the class consisting of an aliphatic hydrocarbon group having from 6 to 22 carbon atoms and the group having the formula:

COOH 4 wherein R is selected from the class consisting of R and an aliphatic hydrocarbon group having from 12 to 18 carbon atoms and R is selected from the class consisting of an aliphatic hydrocarbon group having from 12 to 18 carbon atoms and the group having the formula:

wherein R is selected from the class consisting of R and a saturated aliphatic hydrocarbon group having from about 12 to about 18 carbon atoms, R is selected from the class consisting of a saturated aliphatic hydrocarbon group having from about 12 to about 18 carbon atoms and the group having the formula:

wherein R is selected from the class consisting of hydrogen and methyl, and R is a saturated aliphatic hydrocarbon group having from 12 to about 18 carbon atoms.

4. A fuel oil composition comprising a major proportion of a hydrocarbon oil fraction in the fuel oil distilla- 7 tion range from about 0.0001 to about 5% by weight of a N,N,N' tri [2 (2,5 dicarboxybenzoxy)propyl] N tallow-1,3 -prop-anediamine.

5. A fuel oil composition comprising a major proportion of a hydrocarbon oil fraction in the fuel oil distillation range from about 0.001 to 0.05% by weight of a N,N,N' tri [2 (2,5 dicarboxybenzoxy)propyl] N tallow-1,3 -propanediamine.

6. A fuel oil composition comprising a major proportion of a hydrocarbon oil fraction in the fuel oil distillation range from about 00001 to 5% by weight of a N,N-di

[2- 2,4-dicarboxybenzoxy propyl] -tallow amine.

7. A fuel oil composition comprising a major proportion of a hydrocarbon oil fraction in the fuel oil distillation range from about 0.001 to 0.05% by weight of a 15 N,N-di [2- 2,4-dicarboxybenzoxy propyl] -tallow amine.

10 tallow-1,3-propanediamine.

References Cited in the file of this patent UNITED STATES PATENTS

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2368604 *Feb 8, 1943Jan 30, 1945Shell DevAnticorrosive
US2830019 *Sep 29, 1954Apr 8, 1958Standard Oil CoAdditive for mineral oil
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3183070 *Jan 25, 1963May 11, 1965Standard Oil CoRust inhibited oil containing aliphaticaminoalkylsuccinates
US4490155 *Aug 17, 1983Dec 25, 1984Texaco Inc.Mannich reaction products of diaminopropanes with formaldehyde and salicyclic acids
US4508541 *Jul 5, 1983Apr 2, 1985Texaco Inc.Mannich reaction product and a motor fuel composition containing same
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
EP0561947A1 *Dec 2, 1991Sep 29, 1993Mobil Oil CorporationMultifunctional additives to improve the low-temperature properties of distillate fuels and compositions containing same
Classifications
U.S. Classification44/391, 252/392
International ClassificationC10L1/222
Cooperative ClassificationC10L1/2225
European ClassificationC10L1/222B2