US3637356A - Diesel fuel composition - Google Patents

Diesel fuel composition Download PDF

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Publication number
US3637356A
US3637356A US472365A US3637356DA US3637356A US 3637356 A US3637356 A US 3637356A US 472365 A US472365 A US 472365A US 3637356D A US3637356D A US 3637356DA US 3637356 A US3637356 A US 3637356A
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United States
Prior art keywords
barium
additive
fuel
smoke
percent
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Expired - Lifetime
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US472365A
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English (en)
Inventor
Andre Jacques Emi Vanderlinden
Gilbert Jules Ghislain Stubbe
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Total Petrochemicals and Refining USA Inc
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Cosden Oil and Chemical Co
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    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • 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
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1886—Carboxylic acids; metal salts thereof naphthenic acid
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the additive compounds of this invention are particularly useful in diesel fuel oils which commonly evolve a smoky and often noxious exhaust and comprise gasoils which may have a substantial sulfur content. Moreover, the additive compounds improve the power output while reducing carbon deposits and other common effects associated with smoky exhaust.
  • the primary object of this invention is to reduce the smoke present in combustion gases produced by combustion of liquid fuels by adding to the fuel a compound having the formula RY-Ba-CO (Ba-CO )x-BaY'R wherein R is an organic radical imparting oil solubility to the compound, usually high molecular weight aliphatic, alicyclic, aromatic or mixed-type hydrocarbon usually having at least l carbon atoms, Y is CO;, or SO radicals, Y is CO and x is an integer having a value in the range of 0 through 8, preferably 0 to 6.
  • a smoky exhaust is usual, especially in diesel and similar devices often burning unrefined or only moderately refined burning oils such as fuel oils or pot oils.
  • smoky combustion often occurs.
  • diesel fuels with variable conditions of acceleration with large fuel feed during rapid acceleration for increased power the fuel being then injected in greater than a critical quantity
  • combustion normally occurs with large discharge of black smoke.
  • increase in power of a diesel engine is not proportional to the increase in fuel consumption.
  • emission of smoke is troublesome under any conditions, and particularly so in confined spaces.
  • the smoky combustion indicates increased and wasted fuel consumption due to the incomplete combustion, and, besides the noxious fouling of the air, fouling of engine parts is also a common and undesirable result.
  • our preferred additives are the mixed barium carbonate salts of an organic sulfonic acid or an organic carboxylic acid such as barium sulfonatocarbonate or barium naphthenatocarbonate and mixtures of these barium salts in which the organic sulfonato radical is preferably a higher alkyl such as keryl benzene sulfonate or a petroleum sulfonate, and the naphthenato radical is derived from a petroleum naphthenic acid, usually mixed petroleum naphthenic acids.
  • the compounds are known types but are preferably formed, according to the present invention, by dissolving the organic acid in a carrier oil such as gasoil or an oil of the same character as the fuel with which the additive is to be treated, or an oil carrier readily miscible with the combustible oil to be treated.
  • a carrier oil such as gasoil or an oil of the same character as the fuel with which the additive is to be treated, or an oil carrier readily miscible with the combustible oil to be treated.
  • the organic acid solution in said oil carrier is then reacted with a barium oxide solution in anhydrous methanol.
  • the product is converted to the carbonate by bubbling CO into the solution to substantial neutrality.
  • the methanol may be evaporated and the liquid product solution of the barium salt in the carrier oil may be filtered. A slight quantity of water sometimes improves the fluidity of the product.
  • the preferred naphthenic and sulfonic acids give an improved fluidity to the final product.
  • While other carboxylic and sulfonic acids are useful and react with the barium oxide in the same way, these often produce an undesirably thick product, which would require expensive blending equipment for dissolving in the fuel.
  • the product may be formed in situ in the fuel to be treated up to the useful quantity stated, it is preferred first to form a concentrate of 30 to 60 percent of barium compound in the liquid fuel carrier as described, and use such concentrated solution in a suitably small quantity as an additive base supplied to the fuel being treated, so that the concentrate is diluted to the requisite concentration of barium compound in the fuel.
  • additive is formed as a concentrate in a gasoil, diesel oil or kerosene of somewhat lower viscosity as the carrier oil, 30 to 50 percent of barium sulfonatocarbonate or barium naphthenatocarbonate formed as described being dissolved in the oil, the balance of 50 to 70 percent of the composition being the carrier gasoilor the like.
  • the composition of such additive would comprise 10 to 25 weight-percent of barium ion, 2 to 9 weight-percent of CO ion and l0 to 30 weight-percent of RY ion.
  • a liquid concentrate of barium naphthenatocarbonate and barium sulfonatocarbonate may be formed or by dissolving mixed organic acids, naphthenic and alkyl benzene sulfonic, in the carrier oil whereby a mixed salt comprising barium naphthenatocarbonate and barium sulfonatocarbonate is formed in solution therein.
  • the separately formed solutions as first described can be mixed to form a composite blend of both types of mixed barium salt.
  • Gasoils typically used for diesel fuel, often contain substantial quantities of sulfur. Because of this sulfur content, the barium is converted into barium sulfate. Even when the barium compound is used at a concentration of 0.25 percent in the diesel fuel, all of the barium would be discharged as barium sulfate if the fuel only contain 0.057 percent of sulfur. Commercial diesel fuels usually contain much more sulfur.
  • barium sulfate Compared to the combustion products of other additives that have been proposed in the art for smoke reduction, barium sulfate is substantially inert, noncorrosive, nontoxic and, being quite heavy, it settles very rapidly rather than remain as a suspended dust to pollute the atmosphere.
  • the barium appears to be present in quite high concentration with respect to the rest of the organic molecule and perhaps for this reason exhibits such high smoke-inhibiting effect, quite superior in the same concentration to other proposed smoke-inhibiting compounds used at much higher concentrations.
  • the barium sulfonatocarbonate may be produced in powder form and shows no sign of crystallinity upon analysis by X-ray diffraction, thereby proving that the product is not a dispersion of barium carbonate particles nor a simple suspension thereof in the oil.
  • the substance comprising the additive of this invention appears to have an amorphous polymeric structure, which may explain the ease with which it dissolves in the carrier oil even when applied thereto for dissolution from a preformed powder form.
  • this additive product decomposes with large CO release which may possibly result in better atomization of the gasoil droplets with which it is associated during combustion whereby the catalytic smoke-reducing action of the dispersed barium is so fully achieved.
  • the additive hereof does not unduly increase the viscosity of the liquid fuel with which it is blended.
  • a diesel gasoil with a barium content of 20 percent resulting from dissolving a substantial concentration of the additive herein still remains within 10 and 20 centistokes at l00 F., a solution substantially as fluid as the untreated diesel fuel.
  • a 17 percent solution of neutral barium sulfonate in the same diesel fuel would have a viscosity of about 112 centistokes at 210 F., a quite viscous liquid.
  • the additive compound hereof in this quantity would contain nine times as much barium as the 17 percent neutral barium sulfonate solution. The latter would contain only 2.2 percent barium.
  • the mixed sulfo-carbonated compound of barium comprises an additive which may be EXAMPLE 1
  • EXAMPLE 1 Four additives were prepared from the same petroleum (keryl) benzene sulfonic acid with a mean molecular weight of 452. The final additives had the following characteristics:
  • the additives were incorporated separately in a commercial Diesel fuel at various concentrations expressed as weight-percentage of metal in the gasoil, the Ca concentrations being 3.4 times less than those of Ba.
  • the tests were carried out with a Petter AVl Diesel engine following the oil test procedure CEC/AT4 slightly modified to rapidly determine the activity of the additives, at high full consumption, the gasoil consumption being increased from 1,088 gjhour to l,l48 gJhour.
  • Measurement of the exhaust smoke was carried out with the Hartridge smokemeter which measures the decrease of intensity of a light beam passing through the smoke moving in a conduit. The Hartridge smokemeter is calibrated from to 100, the lower values corresponding to the least opaque exhaust.
  • Table IV summarizes the test results and shows that the activity of the Ba naphthenatocarbonate used alone or in mixture with Ba sulfonatocarbonate is very close to that of the Ba sulfonatocarbonate and that the Ba naphthenatocarbonate similarly improves the Diesel gasoil combustion.
  • EXAMPLE 4 A good additive should maintain its activity during long periods of time.
  • the tests carried out in examples I and 3 may be modified to show the duration of the activity of the different additives, and the results are summarized in the followmg:
  • Curve No. 7 illustrates the H. I. effect on the gasoil using barium sulfonatocarbonate in quantity to impart 0.05 weightpercent of barium to the gasoil.
  • the curves show, moreover, that the antismoke activity of the additives of the present invention operate at a markedly high level for effective smoke reduction for test periods that have been run up to 240 hours with the same Petter ABI Diesel engine, the Hartridge Index varying between the very low limits of 5 and l l EXAMPLE 5 Bench test have been carried out with a six-cylinder Leyland engine type 0/400, consuming the gasoil as in example I and the same gasoil containing the Ba sulfonatocarbonate at a 'lAltlil l llai'trirlgvv IlllliK Neutral a sul- Neutral Ila naph- (ia sul lonatu- Ha snltluniatofonatu carbonate lonatrv vnrlnmate lia sulfu- (0.015% w (0.015% w (0.05% w (1105",, w natui
  • Hartridge Index is plotted against the duration of the test for each of the compositions tested.
  • Curve No. 1 illustrates the effect of the Hartridge Smoke Index operating on untreated gasoil.
  • Curve No. 2 illustrates the H. I. effect on this gasoil treated with neutral calcium sulfonate added in quantity of 0.015 weight-percent based upon the weight of the calcium.
  • Curve No. 3 illustrates the H. 1. effect on this gasoil treated with calcium sulfonatocarbonate.
  • Curve No. 5 illustrates the H. I. effect on this gasoil using barium naphthenatocarbonate in quantity of 0.05 weight-percent barium.
  • FIG. 2 particularly shows curves based upon the test data set forth in table Vi which illustrate that as the engine is operated more rapidly at a higher r.p.m. the horsepower increases, as more fuel is burned, but so does the Hartridge lndex smoke effect.
  • table Vi which illustrates that as the engine is operated more rapidly at a higher r.p.m. the horsepower increases, as more fuel is burned, but so does the Hartridge lndex smoke effect.
  • the additive is present for moderate horsepowers up to 1 10
  • the smoke production is almost completely inhibited.
  • the Hartridge index is much lower, hardly higher than the best smoking condition of the untreated fuel at the low power output.
  • the effect to reduce smoke with increased horsepower in a diesel oil containing the additive is most marked.
  • the power output is obviously increased, but whatever the power, the Hartridge Index is at least 50 percent lower with gasoil which contains the additive.
  • P10. 3 plots the fuel consumption against the horsepower of the engine. it compares in two curves the untreated gasoil with the gasoil plus the additive. For any given consumption of fuel, the power output of the engine is much greater in the fuel containing the additive.
  • Liquid hydrocarbon fuel containing a small quantity sufficient as a smoke-reducing additive to impart 0.02 to 0.25 weight-percent of barium metal in compound form to the fuel, said additive consisting essentially of a mixed barium salt of carbonic acid and an oil-soluble organic acid selected from the group consisting of carboxylic alkyl acid and benzene sulfonic acid.
  • Liquid hydrocarbon fuel containing a small quantity sufficient as a smoke-reducing additive to impart 0.02 to 0.25 weight percent of barium metal in compound form to the fuel, said additive consisting essentially of a mixed barium salt of carbonic acid and an oilsoluble organic acid mixture of carboxylic acid and sulfonic acid.
  • a liquid diesel fuel comprising a sulfur-containing gasoil v normally producing a substantial quantity of smoke on combustion and containing a small quantity, sufficient as a smokereducing additive, to impart 0.02 to 0.25 weight-percent based on the barium metal content of the fuel, said additive comprising a mixed barium salt of carbonic acid and an oil-soluble organic acid mixture of carboxylic acid and sulfonic acid.
  • a concentrate useful as a smoke-reducing additive upon dilution in a liquid fuel to a concentration in the range of about 0.01 to 0.25 percent by weight based upon the barium metal content imparted to the liquid fuel said concentrate consisting of from 30 to 50 percent by wei ht of a mixed barium salt of carbonic acid and an oil-so uble organic acid selected from the group consisting of carboxylic acid and alkyl benzene sulfonic acid, and the balance, 50 to percent, being substantially hydrocarbon oil.
  • a method of burning a diesel fuel tending to produce smoke comprising burning said fuel in the presence of a small quantity, sufficient to reduce smoke, of an additive comprising a mixed basic barium salt of carbonic acid and an oil-soluble organic carboxylic acid.
  • a method of burning a diesel fuel tending to produce smoke comprising burning said fuel in the presence of a small quantity, sufficient to reduce smoke, of an additive comprising a mixed basic barium salt of carbonic acid and alkyl benzene sulfonic acid.
  • a method of burning a diesel fuel tending to produce smoke comprising burning said fuel in the presence of a small quantity, sufficient to reduce smoke, of an additive comprising a mixed barium salt of carbonic acid and an oil-soluble organic acid mixture of carboxylic acid and sulfonic acid.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)
US472365A 1965-03-31 1965-07-15 Diesel fuel composition Expired - Lifetime US3637356A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3798012A (en) * 1971-06-09 1974-03-19 Lubrizol Corp Combustion process and fuel compositions
WO1999003953A1 (en) * 1997-07-15 1999-01-28 Infineum Usa L.P. Improved fuel oil compositions
US5919276A (en) * 1997-02-07 1999-07-06 Ethyl Petroleum Additives Limited Use of mixed alkaline earth-alkali metal systems as emissions reducing agents in compression ignition engines

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3493354A (en) * 1967-02-27 1970-02-03 Monsanto Chemicals Diesel fuel additive
US3615292A (en) * 1968-11-26 1971-10-26 Cities Service Oil Co Smoke suppressant compositions for petroleum fuels

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3256186A (en) * 1963-02-12 1966-06-14 Lubrizol Corp Process for producing carbonated basic metal compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3256186A (en) * 1963-02-12 1966-06-14 Lubrizol Corp Process for producing carbonated basic metal compositions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3798012A (en) * 1971-06-09 1974-03-19 Lubrizol Corp Combustion process and fuel compositions
US5919276A (en) * 1997-02-07 1999-07-06 Ethyl Petroleum Additives Limited Use of mixed alkaline earth-alkali metal systems as emissions reducing agents in compression ignition engines
WO1999003953A1 (en) * 1997-07-15 1999-01-28 Infineum Usa L.P. Improved fuel oil compositions
US6652609B1 (en) 1997-07-15 2003-11-25 Exxon Chemical Patents Inc Fuel oil compositions

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