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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
  • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites

Definitions

• This invention relates to the improvement of nonlubricating 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 metal salts of nitrated hydrocarbons 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 metal salt of a nitrated paraflinic hydrocarbon, said nitrated hydrocarbon being produced by reacting a paraffinic hydrocarbon having between about 12 carbon atoms and about 34 carbon atoms with nitric acid, at a temperature of between atent O about 175 C. and about 195 C., and said metal being from groups HA and IIB of the periodic chart of the elements.
• the addition agents of this invention are metal salts of nitrated p-araflinic hydrocarbons.
• the parafiinic hydrocarbons utilizable herein are panaffinic hydrocarbons having between about 12 carbon atoms and about 34 carbon atoms per molecule.
• These paraflins can be relatively pure hydrocarbons or they can be mixtures of paratlinic hydrocarbons, such as a paraflin wax and predominantly paraflinic petroleum fractions.
• the paraflinic hydrocarbons can be straight-chain or branched-chain.
• Non-limiting examples of these hydrocarbons are dodecane; 2,4,5,7tetramethyloctane; tridecane; tetradecane; 4,5-dipropyloctane; hexadecane; 3-ethyltetradecane; octadecane; eicosane; 2,6,11,IS-tetramethylhexadecane; heneicosane; docosane; Z-methyltricosane; isohexacosane; triacontane; and tetratriacontane.
• paraffin waxes are utilizable. These waxes melt between about 40 C. and about 72 C. and include paraffin wax, ozokerite, ceresin wax, slack wax, and scale wax.
• the paraflinic hydrocarbon is nitrated. This is effected by reacting the hydrocarbon with nitric acid; with the hydrocarbon in the liquid phase and the nitric acid in the vapor phase, i.e., at temperatures between about 175 C. and about 195 C.
• the nitric acid can be of a concentration varying between about 70 percent and about percent.
• an inert gas such as nitrogen
• the salts of the 'aforedescribed nitro-paraflins that are utilizable in the fuel oil compositions of this invention are the salts of the metals of groups 11A and HE of the periodic chart of the elements. Salts of magnesium, barium, calcium, and zinc are especially preferred. These compounds are prepared by the reaction between the aciform nitro-paraffin (which reacts as a carboxyl group) and a solution of the group 11 metal.
• inorganic salts or alcoholates such as, by way of nonlimiting example, barium methylate or ethylate, magnesium methylate or ethylate, zinc chloride in methanol or ethanol, calcium chloride in methanol or ethanol, and the like.
• the metal salts of nitro parafiins are obtained by gradually heating a mixture of nitro-paraflin and an alcoholic solution of metal alkoxide in oil or kerosene as solvent to 175 C. to drive oil? the alcohol. maintained at 175 C. from 1 to 3 hours to complete the formation of the metal salts.
• the fuel oils that are improved in accordance with this invention are hydrocarbon fractionshaving an initial boiling point of at least about 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, catalytical- Patented July 18, 1961' The temperature is 1y or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight-run distillate fuel 011s, 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 hmits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.
• fuel oils 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 D975-48T.
• Typical jet fuels are defined in Military Specification MIL-F-5624B.
• nitro-parafiin salt additive that is added to the distillate fuel oil in accordance with this invention will depend, of course, upon the intended purpose and the particular 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 vary between 10 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.
• concentrations as low as about 25 p.p.m., i.-e., about 5 pounds of additive per thousand barrels of oil are effective.
• the amount of nitro-paraffin salt that can be added to the distillate fuel oil in order to achieve a beneficial result, will vary generally between about 5 pounds per thousand barrels of oil and about 200 pounds per thousand barrels of oil. Preferably, it will vary between about 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.
• EXAMPLE 1 maintained at 175-185 C.thr0ughout the addition period (4 hours). At the operating temperature the nitric acid vaporized and bubbled through the paraffin wax through the porous plate. A stream of nitrogen was used in the coil to prevent nitric acid vapor from backing up into the coil and to remove water from the nitric acid and the reaction. The nitro-parafiin wax, thus obtained, had a nitrogen content of 1.89 percent, by weight.
• EXAMPLE 2 A mixture of 161 grams of nitrated wax (Example 1), 29.8 grams of barium in the form of barium methylate solution in methanol, and 322 grams of paraffinic oil SSU at 100 F.) as a diluent was agitated and heated gradually to 175 C. The temperature was then maintained at about 175 C. for 3 hours to drive off the methanol. The reaction product which contained 63 percent oil was then filtered through filtering clay (diatomaceous earth). The fluid filtrate product was an oil solution of barium salt of nitro-parafiin wax, containing 5.9 weight percent barium and 0.59 weight percent nitrogen.
• EXAMPLE 4 A mixture of 23 grams of zinc chloride dissolved in i 100 cc. of methanol and 7.1 grams of sodium in the form of sodium methylate solution in methanol was refluxed at 65 C. for 3 hours to form zinc methylate. The reaction mixture which contained the zinc methylate and sodium chloride became turbid. To the reaction mixture was added at room temperature 50 grams of nitrated wax (Example 1) and 200 grams of kerosene (boiling range equal 343 to 519 F.) as a diluent. The mixture was gradually heated to 17 5 C. with agitation to drive off the methanol. The temperature was maintained at about 175 C. for 3 hours to complete the formation of zinc nitro-paraflin wax. The reaction mixture which contained approximately 76 percent kerosene was filtered through filtering clay, producing as the filtrate, a fluid kerosene solution of the zinc nitro-wax salt,
• EXAMPLE 5 A mixture of 19 grams of calcium chloride dissolved in cc. of methanol and 7.1 grams of sodium in the form of sodium methylate solution in methanol was refluxed at65 C. for 3 hours to form calcium methylate. The reaction mixture which contained the calcium methylate and sodium chloride became turbid. To the reaction mixture was added at room temperature 50 grams of nitrated wax (Example 1) and 100 grams of kerosene (boiling range equal 343 to 5 19' F.) as a diluent. The mixture was gradually heated to C. to drive off the methanol and maintained at about that temperature for 3 hours to complete the formation of the calcium nitroparaffin wax salt.
• the mixture which contained approximately 63 percent kerosene was filtered through filtering clay.
• the produce (filtrate) was a kerosene solution of a calcium salt of nitro-paraflin wax, containing 0.87 weight percent calcium and 0.49 weight percent nitrogen.
• EXAMBLE 6 In the apparatus described in Example 1, 27 grams of nitric acid (specific gravity equal 1.421) were added dropwise through the submerged coil to react with 50 grams of n-dodecane. The temperature was maintained at ISO-185 C. during addition. The final product, nitrated dodecane, contained 2.12 Weight percent nitrogen.
• EXAMPLE 7 A mixture of 25 grams of nitrated n-dodecane (Example 6), 5.2 grams of barium in the form of barium methylate solution in methanol, and 75 grams of kerosene diluent was gradually heated to 175 C. to drive off the methanol. The reaction was maintained at about 175 .C. for 3 hours to complete the formation of the barium salt of nitro-dodecane. The reaction mixture became gelatinous. A mixture of 80 grams of xylene and 70 grams of isopropanol was added. The reaction mixture became fluid. The reaction mixture which contained approximately 90 percent solvent was then filtered through filtering clay. The final product was a solution of the barium salt of nitro-dodecane, containing 2 weight percent barium and 0.2 weight percent nitrogen.
• EXAMPLE 8 A mixture of 25 grams of nitrated dodecane (Example 6), 2.76 grams of magnesium in the form of magnesium methylate solution in methanol, and 75 grams of kerosene diluent-was gradually heated to 175 C. to drive off the methanol and that temperature was maintained for 3 hours. Then, the mixture was filtered through filtering clay. The product filtrate was diluted with 50 grams of xylene. The final product was a solution of the magnesium salt of nitro-dodecane, containing 1.38 weight percent magnesium and 0.32 weight percent nitrogen.
• the test used todetermine the sedimentation characteristics of the fuel oils is the 110 F. storage test. Inthis test, a SOD-milliliter sample of the fuel oil under test is placed in a convected oven maintained at 110 F. for a period of 6 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 milligrams is reported as the amount of sediment. A sample of the blank, 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 mg./1iter Screen Clogging 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 0.05percent, 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. After drying, the material in Gooch crucible is washed with a 5050 (volume) acetone-methanol mixture.
• the total organic sediment is obtained by evaporating the pentane and the acetonemethanol filtrates. 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 10 Using the test fuel oil described in Example 9, blends of the additives of Examples 2 through 8 in this fuel were prepared. Each blend was subjected to the screen clogging test, as aforedescribed. Test results are set forth in Table II.

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• Chemical & Material Sciences (AREA)
• 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)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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Citations (4)

• 0
  • BE BE604320D patent/BE604320A/xx unknown
• 1958
  • 1958-02-07 US US713793A patent/US2992905A/en not_active Expired - Lifetime

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