US2742351A - Stabilized heating oil - Google Patents

Stabilized heating oil Download PDF

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Publication number
US2742351A
US2742351A US230443A US23044351A US2742351A US 2742351 A US2742351 A US 2742351A US 230443 A US230443 A US 230443A US 23044351 A US23044351 A US 23044351A US 2742351 A US2742351 A US 2742351A
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US
United States
Prior art keywords
oil
salts
petroleum
sodium
heating oil
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US230443A
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English (en)
Inventor
Dilworth T Rogers
Harry W Rudel
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE511937D priority Critical patent/BE511937A/xx
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US230443A priority patent/US2742351A/en
Priority to GB9969/52A priority patent/GB727155A/en
Priority to FR1055483D priority patent/FR1055483A/fr
Priority to DEST4916A priority patent/DE961481C/de
Application granted granted Critical
Publication of US2742351A publication Critical patent/US2742351A/en
Anticipated expiration legal-status Critical
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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 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
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium

Definitions

  • This invention concerns a fuel oil composition particularly characterized by the inclusion of salts of phosphorous, arsenic, antimony or bismuth, maintained in the fuel oil by means of a suitable detergent.
  • the invention concerns cracked fuel oil compositions containing sodium phosphate dissolved in the oil with the aid of a detergent such as sodium petroleum sulfonate.
  • the fuel oil compositions of this invention are advantageous in that they are effectively stabilized by inclusion of the additives indicated.
  • the invention is of application to hydrocarbon mixtures generally known as fuel oils. Such hydrocarbon mixtures are employed in various burner systems as diesel fuels or as domestic and industrial heating oils.
  • Fuel oils may be derived from petroleum by'a variety of methods including the straight distillation from crude petroleum oil and thermal or catalytic cracking of petroleum oil fractions.
  • this invention is of particular application to the preparation of fuel oil compositions which are made up at least in part of constituents derived from cracking operations. Such compositions may be effectively stabilized by employing additives herein disclosed.
  • Heating oils which may be stabilized by these additives are hydrocarbon mixtures of which more than about 10% consist of stocks derived from thermal or catalytic cracking operations. More precisely still, the base stocks may be characterized as petroleum fractions containing a proportion of cracked stocks greater than 10% and falling within A. S. T. M. specification D-975-48T for diesel fuel oils (grades Nos. 1-D to 4-D inclusive) and A. S. T. M. specification D-396-48T for fuel oils (grades Nos. 1 to 6 inclusive).
  • a small amount of a salt of certain of the group elements is employed in the fuel oil to be stabilized.
  • Salts of phosphorus, arsenic, antimony and bismuth may be employed.
  • the alkali metal, alkaline earth or ammonium salts of these particular metals are to be employed.
  • the benefits of this invention may be obtained in part by dispersing the indicated salts in finely divided form so as to permit the salts to remain in suspension in the oil.
  • I H alkali or alkaline earth metal sulfonate' which is oil s01 uble is effective in solubilizing the salts to be employed.
  • the preferred detergents are the alkali and alkaline earth metal sulfonates which areoil soluble.
  • the oil'soluble petroleum sulfonates of sodium and calcium are particularly contemplated for use. 'In thecase of the alkaline earth metal sulfonates, the sulfonates of bariuin,-calcium, strontium and magnesium .are particularly preferred.
  • Other detergents may be employed such as the metal soaps of the C16 to C24 fatty acids or'of naphthenic acids.
  • the preferred salts are the'salts of phosphorus, and particularly the sodium salts of phosphorus.
  • Na'3PO4 presently appears to be the best of the sodium phosphates although NQZHPOd, NaHzPOi, NatPzOi and NasPOs have all been found to stabilize ,fuel oil.-
  • the present invention will bedesc'ribed with particular reference to the use of tri-sodium' phospliate However, in the preferred practice of this invention, the
  • a salt of arsenic, bismuth, antimony or phosphorus is to be included in the fuel oil.
  • the proportion to be used may vary from as little as about 0.0001 wtjpe'rcen't up to about 0.1 wt. percent.
  • the salt of phosphorus, arsenic, bismuth or' antimony is added to the fuel oil in the form of a complex with an alkali or alkaline earth metal petroleum sulfonate containing from about 2% to 20% of the salt of one of these metals; In this case about 0.0005 to 5.0 wt. percent of this complex may be employed.
  • the indicated complex is used in weight proportions of about 0.005% to 0.02%, based on the weight of the oil. Since these proportions are based on the use of anhydrous salts of these metals in the event a hydrated salt is employed, the proportionsmust be compensated in accordance with the water of hydration.
  • a preferred procedure for incorporating the salt in heating oil is to prepare a complex with an oil soluble metallic sulfonate, e. g. of petroleum derivation and to dissolve the complex in mineral oil. This is accomplished by adding an aqueous solution of the salt, such as sodium phosphate to anoil soluble petroleum sulfonate, e. g. sodium or calcium sulfonate. Thereafter, the mixture is heated to a temperatureof about 300, F. to completely dehydrate it.
  • the phosphate in this case is in actual solution in the oil and no separation of the salt from the oil occurs until a critical concentration of the phosphate in the sulfonate is reached.
  • a sodium sulfonate concentrate (for example, 65% sulfonate, 35% oil) can absorb up to about 20% of Na'sPO4.12H20.
  • a 30% concentration of calcium sub fonate' can absorb about the same quantity of the salt".
  • a concentrate of the sodium sulfonate phosphate com plex prepared as indicated may then be employed in stabilizing fuel oil in the proportions formerly indicated.
  • Mild steel strip maintained in contact with oil sample containing water for 52 days at toom temperature.
  • sodium phosphate maintained in the oil as a complex with sodium petroleum sulfonate was effective in all concentrations reported in stabilizing the fuel oil.
  • sodium sulfonate complex was effective in eliminating the corrosive properties of the fuel oil in the water phase. It is particularly significant that these data show that sodium petroleum sulfonate alone is not effective in overcoming the instability of the fuel oil, but the combination of sodium phosphate and sodium petroleum sulfonate is required.
  • oil in the form of a 50% concentrate of the phosphate salt in a lubricating oil vehicle oil in the form of a 50% concentrate of the phosphate salt in a lubricating oil vehicle.
  • an alkali, alkaline earth metal or ammonium salt of phosphorus, antimony, arsenic or bismuth is to be incorporated in a cracked fuel oil in minor proportions. It is preferred to maintain one or more of these salts in the fuel oil by means of a solubilizer or a detergent.
  • the preferred detergent constitutes an alkali or alkaline earth metal oil soluble petroleum sulfonate.
  • other compounds may be included in the heating oil composition such as an alkaline earth metal alkyl phenol sulphide. It is apparent that other conventional additives ordinarily employed in a fuel oil may also be incorporated in the fuel oil compositions of this invention.
  • a heating oil composition comprising a petroleum fraction containing a proportion of cracked stocks greater than 10% and falling within A. S. T. M. specification D-97548T and A. S. T. M. specification D-396-48T, and containing about 0.0005 to 5 weight percent of a compound selected from the group consisting of the oilsoluble alkali and alkaline earth metal petroleum sulfonates, and including about 2% to 20% of trisodium phosphate based on the said sulfonate.
  • a composition consisting essentially of a distillate heating oil containing more than about 10% of cracked constituents and containing about 0.0001 to 0.1 Weight percent of a compound selected from the group consisting of the alkali metal, alkaline earth metal, and ammonium phosphates, arsenites, arsenates, and bismuthates, together with a minor and solubilizing proportion of a compound selected from the group consisting of the alkali metal and alkaline earth metal oil-soluble petroleum sulfonates.

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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)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)
US230443A 1951-06-07 1951-06-07 Stabilized heating oil Expired - Lifetime US2742351A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE511937D BE511937A (en, 2012) 1951-06-07
US230443A US2742351A (en) 1951-06-07 1951-06-07 Stabilized heating oil
GB9969/52A GB727155A (en) 1951-06-07 1952-04-21 Improvements in or relating to stabilized heating oil
FR1055483D FR1055483A (fr) 1951-06-07 1952-05-06 Huile combustible stabilisée
DEST4916A DE961481C (de) 1951-06-07 1952-06-06 Verfahren zum Stabilisieren von Heizoelen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US230443A US2742351A (en) 1951-06-07 1951-06-07 Stabilized heating oil

Publications (1)

Publication Number Publication Date
US2742351A true US2742351A (en) 1956-04-17

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US230443A Expired - Lifetime US2742351A (en) 1951-06-07 1951-06-07 Stabilized heating oil

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US (1) US2742351A (en, 2012)
BE (1) BE511937A (en, 2012)
DE (1) DE961481C (en, 2012)
FR (1) FR1055483A (en, 2012)
GB (1) GB727155A (en, 2012)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2860040A (en) * 1955-05-25 1958-11-11 Exxon Research Engineering Co Petroleum distillate fuels
US3046224A (en) * 1957-06-10 1962-07-24 Socony Mobil Oil Co Inc High barium content complex salts of sulfonic acids and petroleum fractions containing the same
US3234898A (en) * 1963-03-08 1966-02-15 Combustion Eng Furnace operation utilizing additives of a new and improved type for retarding high temperature corrosion and ash bonding
US3290342A (en) * 1961-08-18 1966-12-06 Plains Chemical Dev Co Organophosphorus-vanadium compounds and methods for preparing and using the same
US3765848A (en) * 1971-01-22 1973-10-16 G Brent Motor fuel composition
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
WO2004033602A1 (en) * 2002-10-08 2004-04-22 Chimec S.P.A. A fuel oil additive comprising alkaline-earth metal salts of alkylbenzene sulphonic acid
US20050028434A1 (en) * 2003-06-23 2005-02-10 Envirofuels, L.P. Additive for hydrocarbon fuel and related process
US20060101710A1 (en) * 2004-11-15 2006-05-18 Envirofuels L.P. Additive for solid hydrocarbon fueled direct fired burners, furnaces, open flames and related processes

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2137727A (en) * 1937-03-27 1938-11-22 Edward F Quirke Materials for treatment of hydrocarbons
US2301370A (en) * 1941-02-26 1942-11-10 American Cyanamid Co Stabilization of tetraethyl lead
US2409687A (en) * 1943-05-10 1946-10-22 Standard Oil Dev Co Sulfur and metal containing compound
US2527987A (en) * 1948-03-29 1950-10-31 Shell Dev Fuel oil composition
US2623016A (en) * 1949-01-17 1952-12-23 Union Oil Co Lubricating oil composition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1302094A (en) * 1914-10-24 1919-04-29 Charles J Skidmore Process of separating oil.

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2137727A (en) * 1937-03-27 1938-11-22 Edward F Quirke Materials for treatment of hydrocarbons
US2301370A (en) * 1941-02-26 1942-11-10 American Cyanamid Co Stabilization of tetraethyl lead
US2409687A (en) * 1943-05-10 1946-10-22 Standard Oil Dev Co Sulfur and metal containing compound
US2527987A (en) * 1948-03-29 1950-10-31 Shell Dev Fuel oil composition
US2623016A (en) * 1949-01-17 1952-12-23 Union Oil Co Lubricating oil composition

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2860040A (en) * 1955-05-25 1958-11-11 Exxon Research Engineering Co Petroleum distillate fuels
US3046224A (en) * 1957-06-10 1962-07-24 Socony Mobil Oil Co Inc High barium content complex salts of sulfonic acids and petroleum fractions containing the same
US3290342A (en) * 1961-08-18 1966-12-06 Plains Chemical Dev Co Organophosphorus-vanadium compounds and methods for preparing and using the same
US3234898A (en) * 1963-03-08 1966-02-15 Combustion Eng Furnace operation utilizing additives of a new and improved type for retarding high temperature corrosion and ash bonding
US3765848A (en) * 1971-01-22 1973-10-16 G Brent Motor fuel composition
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
WO2004033602A1 (en) * 2002-10-08 2004-04-22 Chimec S.P.A. A fuel oil additive comprising alkaline-earth metal salts of alkylbenzene sulphonic acid
US20050028434A1 (en) * 2003-06-23 2005-02-10 Envirofuels, L.P. Additive for hydrocarbon fuel and related process
US7604672B2 (en) * 2003-06-23 2009-10-20 Envirofuels, Llc Additive for hydrocarbon fuel and related process
US20060101710A1 (en) * 2004-11-15 2006-05-18 Envirofuels L.P. Additive for solid hydrocarbon fueled direct fired burners, furnaces, open flames and related processes

Also Published As

Publication number Publication date
GB727155A (en) 1955-03-30
DE961481C (de) 1957-04-04
BE511937A (en, 2012)
FR1055483A (fr) 1954-02-18

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