Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
  • C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/12—Partial amides of polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/135—Steam engines or turbines

Definitions

• This invention relates to the improvement of non-lubricating petroleum fractions. It is more particularly concerned with distillate fuel oils containing additives adapted to inhibit the appearance of sediment during prolonged storage periods, to prevent screen-clogging, and to prevent rusting of ferrous metal surfaces;
• a broad object of this invention to provide a fuel oil having properties improved with a minimum number of addition agents. Another object is to provide a fuel oil having a single additive adapted to inhibit sedimentation, to prevent screen clogging, and to prevent rusting of ferrous metal surfaces with which it comes in contact. A specific object is to provide a fuel oil that contains certain amic acids or amine salts thereof that achieve these results. Other objects and advantages of this invention will become apparent to those skilled in the art from the following detailed description.
• the present invention provides a distillate fuel oil containing a minor amount, suflicient to inhibit sedimentation and screen clogging and to prevent rusting of ferrous metal surfaces in contact therewith, of a compound selected from the group consisting of '(1) a succinamic acid having the formula:
• R is an aliphatic hydrocarbon radical of an aliphatic primary amine having between about 4 and about 30 carbon atoms per radical, and the amine salt of these amic acids with an aliphatic primary amine having between about 4 and about 30 carbon atoms per molecule.
• the amic acids contemplated herein can be made by any method for preparing such compounds that is known to the art. They are produced, preferably, by Warming succinic acid anhydride or maleic acid anhydride, respectively, with an aliphatic primary amine having between about 4 and about 30 carbon atoms per molecule to form the monoamide of the acid.
• the amic acids can be prepared by the controlled reaction between succinic or maleic acid and the amine, with the elimination of one mole of water per mole of amic acid produced. Care must be exercised to avoid the elimination of two moles of water to form the cyclic imide.
• the salt thereof can be made readily by warming equimolar quantities of the amic acid with an aliphatic primary amine having between about 4 and about 30 carbon atoms per molecule.
• the salt-forming amine can be the same amine used in making the amic acid, or it can be a different amine.
• the salt can be made by heating two moles of amine with one mole of acid anhydride under temperatures whereby water is not evolved.
• the amines utilizable in forming the amic acids and the salts thereof are the primary aliphatic amines having between about 4 and about 30 carbon atoms per molecule. These are the monoamines having a single open chain hydrocarbon group attached to a nitrogen.
• the aliphatic radical can be saturated or unsaturated, and branched-chain or normal chain. Likewise mixtures of these amines, as well as pure amines, can be employed.
• a very useful and readily available class of primary amines are the tertiary alkyl, primary, monoamines in which a primary amino (-NH group is attached to a tertiary carbon atom; and mixtures thereof. These amines all contain the terminal group,
• Non-limiting examples of the amine reactants are t-butyl primary amine, t-hexyl primary amine, n-hexylamine, noctylamine, n-octenylamine, t-octyl primary amine, 2- ethylhexylamine, t-decyl primary amine, n-decylamine, tdodecyl primary amine, n-undecylamine, dodecenylamine,
• the amine reactants can be prepared in several ways well known to those skilled in the art. Specific methods of preparing the t-alkyl primary amines are disclosed in the Journal of Organic Chemistry, vol. 20, page 295 et seq.
• Mixtures of such amines can be made from a polyolefin fraction (e.g., polypropylene and polybutylene cuts) by first hydrating with sulfuric acid and water to the corresponding alcohol, converting the alcohol to alkyl chloride with dry hydrogen chloride, and finally condensing the chloride with ammonia, under pressure, to produce a t-alkyl primary amine mixture.
• a polyolefin fraction e.g., polypropylene and polybutylene cuts
• the fuel oils that are improved in accordance with this invention are hydrocarbon fractions having an initial boiling point of at least about 100 F. and an end boiling point no higher than about 750 F., and boiling substantially continuously throughout their distillation range.
• Such fuel oils are generally known as distillate fuel oils. It is to be understood, however, that this term is not restricted to straight-run distillate fractions.
• the distillate fuel oils can be straight-run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight-run distillate fuel oils, naphthas and the like, with cracked distillate stocks.
• such fuel oils can be treated in accordance with well known commercial methods, such as, acid or caustic treatment, hydrogenation, solvent refining, clay treatment, etc.
• distillate fuel oils are characterized by their relatively low viscosities, pour points, and the like.
• the principal property which characterizes the contemplated hydrocarbons, however, is the distillation range. As mentioned hereinbefore, this range will lie between about 100 F. and about 750 F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.
• fuel oils are Nos. 1, 2, and 3 fuel oils used in heating and as diesel fuel oils, and the jet combustion fuels.
• the domestic fuel oils generally conform to the specifications set forth in ASTM Specifications D396-48T.
• Specifications for diesel fuels are defined in ASTM Specifications D97548T.
• Typical jet fuels are defined in Military Specification MIL-F-5624B.
• amic acid or amine salt of amic acid additives that is added to the distillate fuel oil in accordance withthis invention will depend, of course, upon the intended purpose and the particular amic acid or salt selected, as they are not all equivalent in their activity. Some may have to be used in greater concentrations than others to be effective. In most cases, in which it is desired to obtain all three beneficial results, namely, to inhibit sedimentation, to reduce screen clogging, and to prevent rusting of ferrous metal surfaces, additive concentrations varying between pounds per thousand barrels of oil and about 200 pounds per thousand barrels of oil will be employed. It may not always be desired, however, to accomplish all three aforementioned results. In such cases, where it is desired to effect only one or two results, lower concentrations can be used.
• the amount of amic acid or of amine salt of amic acid that can be added to the distillate fuel oil in order to achieve a beneficial result, will vary generally between about one pound per thousand barrels of oil and about 200 pounds per thousand barrels of oil. Preferably, it will vary between about 10 and about 200 pounds per thousand barrels of oil.
• the fuel oil compositions can contain other additives for the purpose of achieving other results.
• foam inhibitors and ignition and burning quality improvers are silicones, dinitropropane, amyl nitrate, metal sulfonates, and the like.
• Amine A is a mixture of primary amines having a carbon atom of a tertiary butyl group attached to the amino (--NH group and containing 12 to 15 carbon atoms per amine molecule and averaging 12 carbon atoms per molecule.
• This mixture contains, by weight, about 85 percent tertiary-dodecyl primary amine, about 10 percent tertiarypentadecyl primary amine, and relatively small amounts, i.e., less than about 5 percent of amines having less than 12 or more than 15 carbon atoms.
• Amine B is a mixture of tertiary-alkyl primary amines containing 18 to 24 carbon atoms per molecule and averaging about 20 carbon atoms per molecule. It has a tertiary carbon atom attached to the --NH group and contains, by weight, about 40 percent tertiary-octadecyl primary amine, about 30 percent tertiary-eiscosyl primary amine, about 15 percent tertiary-docosyl primary amine, about 10 percent tertiary-tetracosyl primary amine, and a small amount, less than 5 percent, other amines as high as tertiarytriacontyl primary amine.
• Amine C, Amine D, and Amine E are mixtures of normal aliphatic primary amines having the weight percent compositions set forth in Table I.
• Example 2 A mixture of 150 grams (0.5 mole) of Amine D, 50 grams (0.5 mole) of succinic acid anhydride, and l00 grams xylene diluent was heated at C. with agitation for 3 hours to form a succinamic acid.
• Example 3 A mixture of 79 grams (0.615 mole) of Amine C, 61.5 grams (0.615 mole) succinic acid anhydride, and 140 grams of xylene diluent was heated at C. with stirring for 3 hours to form a succinamic acid.
• Example 4 A mixture of grams (0.5 mole) of Amine A, 49 grams (0.5 mole) of maleic acid anhydride, and 75 grams of xylene diluent was heated at 65- 75 C. with agitation for 2 hours to form a maleamic acid.
• Example 5 A mixture of 95 grams /a mole) of Amine E, 33 grams /3 mole) of maleic acid anhydride,
• Example 6 A mixture of 50 grams (0.25 mole) of Amine A, grams (0.25 mole) of succinic acid anhydride, and 67 grains of xylene diluent was stirred at 85 C. for 1.5 hours to form a succinarnic acid. To the succinamic acid, at room temperature, were added grams (0.25 mole) of Amine A to form the amine salt. The product was then stirred at 85-90 C. for an additional 1.5 hours.
• Example 7 A mixture of 67 grams (0.33 mole) of Amine A, 33 grams (0.33 mole) of succinic acid anhydride, and 100 grams of kerosine (B.R. 343-519 F.), as a diluent, was heated, with agitation, for 2 hours at 90 C. to form a succinamic acid. At room temperature, 100 grams (0.33 mole) of Amine D were added to form the amine salt. The material was then stirred at 90 C. for 2 more hours.
• Example 8 A mixture of 100 grams (0.5 mole) of Amine A, 50 grams (0.5 mole) of succinic acid anhydride, and 100 grams of xylene diluent was stirred at 75 C. for 2 hours to form a succinamic acid. At room temperature, 64.5 grams (0.5 mole) of Amine C were added to form the amine salt. The product was stirred at C. for 2 hours.
• Example 9 A mixture of 50 grams (0.25 mole) of Amine A, 24.5 grams (0.25 mole) of maleic acid anhyd-ride, and 62 grams of xylene diluent was stirred at C. for one hour to form a maleamic acid. To the maleamic acid was added at room temperature 50 grams (0.25 mole) of Amine A to form the amine salt. The material was then stirred at 75 C. for 2 hours.
• Example 10 A mixture of 49 grams (0.5 mole) of maleic acid anhydride and 118 grams (0.5 mole) of a technical grade of Amine A was stirred at 81 C. for 2 hours to form the maleainic a'oid. The product was viscous at room temperature. Thus, it was diluted with 167 grams of paraflinic oil (100 SSU at 100 F.).
• Example 11 A mixture of 303 grams (1.0 mole) of Amine B, 98 grams (1.0 mole) of maleic acid anhydride, and 200 grams of xylene diluent was stirred at C. for two hours to form the maleamic acid.
• Example 12 A mixture of 175 grams (0.57 mole) of Amine B, 57 grams (0.57 mole) of succinic acid anhydride, and 100 grams of xylene diluent was stirred at 90" C. for two hours to form the succinamic acid.
• Example 13 A mixture of 100 grams (0.5 mole) of Amine A and 50 grams (0.5 mole) of succinic acid anhy- ;dride was stirred at 90 C. for two hours to form the succinamic acid. To this acid, were added 151 grams (0.5 mole) of Amine B to form the amine salt. The material was stinred for 1.5 hours at C.
• the test used to determine the sedimentation characteristics of the fuel oils is the 110 F. storage test.
• a SOD-milliliter sample of the fuel oil under test is placed in a co-nyvected oven maintained at 110 F. for a period of 12 weeks. Then, the sample is removed from the oven and cooled. The cooled sample is filtered through a tared asbestos filter (Gooch crucible) to remove insoluble matter. The weight of such matter in -milligrarns is reported as the amount of sediment.
• a tared asbestos filter Gooch crucible
• sample of the blanlg uninhibited oil is run along with a fuel oil blend under test.
• the effectiveness of a fuel oil containing an inhibitor is determined by comparing the weight of sediment formed in the inhibited oil with that formed in the uninhibited oil.
• Example 14 Additional additive described in Examples 1 6 of 60 percent distillate stock obtained from continuous catalytic cracking and 40 percent straight-run distillate stock. It has a boiling range of between about 320 F. and about 640 F. and is a typical No. 2 fuel oil.
• a i 50 D s a A l 100 54 0 18 100 s 0 49 100 17 0 6 v 2g 2 Succinic...- B
• the anti-screen clogging characteristics of a fuel oil were determined as follows: The test is conducted using a Sundstrand V3 or S1 home fuel oil burner pump with a self-contained 100'-mesh Monel metal screen. About 0.05 percent, by weight, of naturally-formed fuel oil sediment, composed of fuel oil, water, dirt, rust, and organic sludge is mixed with 10 liters of the fuel oil. This mixture is circulated by the pump through the screen for 6 hours. Then, the sludge deposit on the screen is washed off 'With normal pentane and filtered through a tared Gooch crucible.
• the material in Gooch crucible is washed with a 50 -50 (volume) acetone-methanol mixture.
• the total organic sediment is obtained by evaporating the pentane and the acetone-methanol filtrates. Drying and Weighing the Gooch crucible yields the amount .of inorganic sediment.
• the sum of the organic and inorganic deposits on the screen can be reported in milligrams recovered or converted into percent screen clogging.
• Example 15 using the test fuel oil described in Example 14, blends of additives of Examples 1 through 13 in this fuel were prepared. Each blend was subjected.
• Test results are set forth in Table HI.
• the other test is a static rust test which simulates conditions encountered in storage tanks, such as, the home fuel oil storage tank.
• a strip of 16-20 gauge sand blasted steel plate is placed in a clear quart bottle. The length of the strip is suificient to reach from the bottom of the bottle into the neck of the bottle without interfering with the cap.
• One hundred cc. of synthetic sea water with pH adjusted to (ASTM D-6 65) and 750 cc. of test oil are placed in the bottle. The bottle is capped tightly, shaken vigorously for one minute, and permitted to stand quietly at 80- F. for 21 days.
• the amount of rust that occurs on the surface of the plate immersed in the water is used as a measure of effectiveness of the fuel to inhibit rusting in storage vessels. It is generally preferred that no more than 5 percent of the surface should be rusted. This test is much more severe than the ASTM rust test. Many additive compositions that pass the ASTM test fail in the static test. On the other hand materials that pass the static test always pass the ASTM test.
• Example 16Blends of additives described in EX- amples 1 through 13 in the fuel oil of Example 14 were subjected to the ASTM Rust Test D-665. Pertinent data are set forth in Table IV.
• Example 17 The' additives described in Examples 1, 2, 3, 5, 6, 7, 8, and 13' were each blended with portions of the fuel oil of Example 14. The blends were subjected to the static rust test. Pertinent data are set forth in Table V.
• R is a monovalent aliphatic hydrocarbon radical having between about 4 and about 30 carbon atoms;
• R is a monovalent aliphatic hydrocarbon radical having between about 4 and about 30 carbon atoms;
• a maleamic acid having the formula:
• R is a monovalent aliphatic hydrocarbon radical having between about 4 and about 30 carbon atoms; and (3) the salts of (1) and (2) with unsubstituted aliphatic primary amines having between about 4 and about 30 carbon atoms per molecule.
• H C
• R is a monovalent alkyl radical containing between about 12 and about 15 carbon atoms and having a tertiary carbon atom directly attached to the nitrogen atom.
• R is a mixture of 10 percent hexadecyl, 10 percent octadecyl, 35 percent octadecenyl, and 45 percent octadecadienyl radicals.
• R is a monovalent alkyl radical containing between about 12 and about 15 carbon atoms and having a tertiary carbon atom directly attached to the nitrogen atom, with a primary monoalkyl amine wherein the alkyl group contains between about 12 and about 15 carbon atoms and having a tertiary carbon atom directly attached to the -NH group.
• R is a monovalent alkyl radical containing between about 12 and about 15 carbon atoms and having a tertiary carbon atom directly attached to the nitrogen atom, with a mixture of primary amines containing 10 percent hexadecyl, 10 percent octadecyl, percent octadecenyl, and percent octadecadienyl amines.

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• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Lubricants (AREA)

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  • BE BE568954D patent/BE568954A/xx unknown
• 1958
  • 1958-01-07 US US707472A patent/US3031282A/en not_active Expired - Lifetime
  • 1958-06-06 GB GB18215/58A patent/GB896375A/en not_active Expired
  • 1958-06-23 FR FR1197418D patent/FR1197418A/fr not_active Expired
  • 1958-12-22 DE DES61101A patent/DE1149843B/de active Pending

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