EP2197992A1 - Verfahren zur verringerung von entflammbarem kreosot und anderen organischen ablagerungen in brennkammern - Google Patents

Verfahren zur verringerung von entflammbarem kreosot und anderen organischen ablagerungen in brennkammern

Info

Publication number
EP2197992A1
EP2197992A1 EP08831100A EP08831100A EP2197992A1 EP 2197992 A1 EP2197992 A1 EP 2197992A1 EP 08831100 A EP08831100 A EP 08831100A EP 08831100 A EP08831100 A EP 08831100A EP 2197992 A1 EP2197992 A1 EP 2197992A1
Authority
EP
European Patent Office
Prior art keywords
accelerant
composition
manganese
hydrocarbon
creosote
Prior art date
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.)
Withdrawn
Application number
EP08831100A
Other languages
English (en)
French (fr)
Other versions
EP2197992A4 (de
Inventor
John Cook
Silas P. Cook
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Timburn Inc
Original Assignee
Timburn Inc
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
Application filed by Timburn Inc filed Critical Timburn Inc
Publication of EP2197992A1 publication Critical patent/EP2197992A1/de
Publication of EP2197992A4 publication Critical patent/EP2197992A4/de
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/04Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/06Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L9/00Treating solid fuels to improve their combustion
    • C10L9/10Treating solid fuels to improve their combustion by using additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • C10L1/1616Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/188Carboxylic acids; metal salts thereof
    • C10L1/1881Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/188Carboxylic acids; metal salts thereof
    • C10L1/1886Carboxylic acids; metal salts thereof naphthenic acid
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/24Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters

Definitions

  • the present invention relates to a composition and method for reducing flammable creosote and other organic deposits in fireboxes.
  • creosote builds up on the walls of the chimney or flue, and can reach dangerous levels if not cleaned on a regular basis.
  • transition metals have been shown to catalyze the breakdown of creosote and inhibit the flammability of the material.
  • Most of these metals form inorganic salts that are soluble in aqueous solutions, but not in common fire accelerants. Though these metals may be effective in reducing creosote, they are difficult to transport up the flue, necessitating methods such as spraying an aqueous solution containing metals up the flue prior to use.
  • U.S. Patent Nos. 2, 141,848 and 3,007,781 disclose soot removers which are soluble in oil for controlling soot in oil burning furnaces, but do not deal with solid fuel which produces deposits fundamentally different from oil.
  • the present invention relates to hydrophobic metal additives for combination with a fire accelerant and their use in the ignition of solid fuels and preventing, removing, and/or inhibiting creosote deposits resulting from the burning of solid fuels. Additionally, according to certain embodiments, the compositions may inhibit corrosion of metal flues in addition to creosote deposits.
  • the metal salts are added to an accelerant at effective concentrations, the combination delivers the metal catalyst to the lining of the exhaust system upon combustion to effectively breakdown creosote residue and inhibit the buildup of new creosote deposits.
  • the metal salts are homogenously dispersed in the accelerant, and do not need to be agitated prior to use. As such, the metals are conveniently and efficiently transported up the flue.
  • the present invention provides hydrophobic metal salts which can be combined with a fire accelerant for preventing, inhibiting and/or removing creosote deposits resulting from the burning of solid fuels.
  • the present invention combines a metal component which provides creosote control, with organic counterions, such as sulfates, nitrates, acetates, etc. which confer hydrocarbon solubility upon the metal catalyst. Additionally, a subset of these counterions themselves can act as corrosion inhibitors of ferrous and non-ferrous metal exhaust systems. Therefore, according to certain embodiments, the composition may contain a metal salt which has a dual role of creosote and corrosion control. According to an alternate embodiment, the composition combines creosote inhibiting salts with corrosion inhibiting salts.
  • the creosote and/or corrosion control additive composition of the present invention comprises a hydrocarbon soluble transition metal salt, having a chemical structure of the formula: wherein X is a transition metal having an ionic charge of +m,
  • Preferred transition metals include Mn, Zn, Ti, V, Cr, Fe Co, Ni, and Cu; with Mn being the most preferred.
  • Other possible transition metals include, but are not limited to Zr, Mo, Ru, Rh, Pd, Ta, W, Re, Ir, Pt, Au and Pb.
  • Other transition metals may also be possible, as will be understood by one skilled in the art, but the above mentioned are believed to be the most ideal.
  • Preferred anions include carboxylate (RCOO ) or sulfonate (RSOs ) hydrocarbons.
  • Other possible anionic groups include, but are not limited to phosphonates (RPOa H or RPO3 2 ), sulfmates (RSO2 ), sulfenate (RSO “ ), alkoxides (RO ), sulfides (RS ), amides (of the type RN R), amides (of the type RCON Ri), and acetoacetates (RCOCO2R 2 ).
  • RPOa H or RPO3 2 phosphonates
  • RSO2 sulfmates
  • RSO " sulfenate
  • alkoxides RO
  • sulfides RS
  • amides of the type RN R
  • amides of the type RCON Ri
  • acetoacetates RCOCO2R 2
  • Other anions may also be possible, as will be understood by one skilled in the art, but the above mentioned are
  • R and R' can each be a hydrocarbon group which may include H, aliphatic alkyl, alkenyl, alkynyl, and hydrocarbon chains containing halogens, nitrogen, oxygen, phosphorus, sulfur, etc., aromatics and cycles (including heterocycles, carbocycles, etc.) as well as ambiphilic chains (heteroatom containing chains) of suitable organic solubility.
  • Creosote control is primarily addressed through the metal component, while the hydrocarbon solubility is provided by the aliphatic anion. Additionally, certain organic anions can also function as corrosion inhibitors. For a list of organic anions known to be efficient corrosion inhibitors for a wide variety of metals see "Corrosion Inhibitors - An Industrial Guide” 2nd Edition; Flick, Ernest W. ® 1993 William Andrew Publishing/Noyes). Calcium dinonylnaphthalene sulfonate is one example of an oil-soluble organic counterion suitable for both ferrous and non- ferrous applications. The mechanism of inhibition for any single corrosion inhibitor is almost certainly a complex set of multiple pathways resulting in the macroscopic effect of corrosion inhibition.
  • organic sulfates, acetates and nitrates form a passivation layer which inhibits the oxidation or reduction portion of the redox corrosion system (system dependent) and buffers the pH of the system thereby preventing proton reduction.
  • the organic solubilizing characteristics of the counterion also allow diffusion into the organic creosote deposits providing access to the underlying metal exhaust system.
  • the metal salts may be effective when added to the accelerant at a concentration of above approximately 0.01 % (w/v).
  • the salts are added to the accelerant at concentration of between approximately 0.1-25 % (w/v) and more preferably at approximately 1-5 % (w/v).
  • the fire accelerant which can include any commercially available accelerant, is preferably composed of saturated hydrocarbons that may be a mixture of branched, straight chain or saturated cyclic structures whose flash point is around 74 ° C (165 0 F). For typical application in solid fuel fire starting, approximately 1-5 ounces of the composition of the invention is applied to the solid fuel prior to ignition.
  • a first embodiment of the invention is a hydrocarbon-soluble creosote inhibitor composition, comprising a hydrocarbon-soluble manganese salt being diluted with a mixture of saturated hydrocarbons to form an additive mixture having flammability characteristics for ignition of solid fuels in which said composition includes about:
  • a second embodiment of the invention is a hydrocarbon-soluble creosote and corrosion inhibitor composition, comprising a hydrocarbon-soluble manganese dinonylnaphthalene sulfonate salt being diluted with a mixture of saturated hydrocarbons to form an additive mixture having the flammability characteristics for ignition of solid fuels in which said composition includes about:
  • dinonylnaphthalene could first be prepared by aluminum chloride-catalyzed alkylation at 60 ° C using fractionally distilled 1- ⁇ -nonenes derived from trimerization of propylene. A heart cut of the dinonylnaphthalene fraction could then be sulfonated with Sulfan B at -8 °C and titrated to neutralization with sodium hydroxide.
  • a third embodiment of the invention is a hydrocarbon-soluble creosote and corrosion inhibitor composition, comprising a creosote inhibiting hydrocarbon- soluble Manganese 2-ethylhexanoate salt and a corrosion inhibiting sulfonate salt being diluted with a mixture of saturated hydrocarbons to form an additive mixture having flammability characteristics for ignition of solid fuels in which said composition includes about: Manganese 2-ethylhexanoate 2% (w/v)
  • the metal salts are mixed into the accelerant until homogenously dispersed. Once evenly dispersed, the compositions need not be agitated prior to use.
  • the inventive composition was field tested using wood-burning devices containing steel flues with no adverse effects in performance.
  • Identical wood- burning stoves were constructed and fitted with identical steel stove-pipe flues. The stoves were fueled with equal quantities of wood continuously over a period of at least twelve days.
  • the first "control" stove was treated with 1-2 ounces of Drakesol 165TM every 24 hour period.
  • the second competing stove was treated with 1-2 ounces of Drakesol 165TM containing manganese 2-ethylhexanoate (1 % w/v) every 24 hours. After a twelve day period, the stove pipe sections were removed and analyzed.
  • the manganese treated stove pipe was 20% lighter than the control stove pipe, and contained ⁇ 50% the creosote.
  • creosote present on the control stove pipe was instantly ignited (thereby causing a controlled chimney fire) using a butane/air flame (— 1200 0 C), while the manganese treated creosote was incapable of ignition even after long exposure (60 seconds) to the same flame source.
  • the formulation proved efficacious down to 0.1 % w/v manganese, lower concentrations should also be viable.
  • the system and compositions of the present invention may be used with any common solid fuel burning systems including, but not limited to, wood, charcoal, peat, coal, and pellets made from wood, corn, wheat, rye and other grains. Furthermore, the invention can be useful for treating creosote deposits in any kind of flue including masonry and metal.
  • the composition can further be used to periodically clean or reduce combustibility of a flue system where solid fuel is regularly burned.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Prevention Of Fouling (AREA)
  • Incineration Of Waste (AREA)
EP08831100A 2007-09-13 2008-09-12 Verfahren zur verringerung von entflammbarem kreosot und anderen organischen ablagerungen in brennkammern Withdrawn EP2197992A4 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US99386007P 2007-09-13 2007-09-13
PCT/US2008/010654 WO2009035658A1 (en) 2007-09-13 2008-09-12 Method for reducing flammable creosote and other organic deposits in fireboxes

Publications (2)

Publication Number Publication Date
EP2197992A1 true EP2197992A1 (de) 2010-06-23
EP2197992A4 EP2197992A4 (de) 2011-12-14

Family

ID=40452347

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08831100A Withdrawn EP2197992A4 (de) 2007-09-13 2008-09-12 Verfahren zur verringerung von entflammbarem kreosot und anderen organischen ablagerungen in brennkammern

Country Status (3)

Country Link
EP (1) EP2197992A4 (de)
JP (1) JP2010539281A (de)
WO (1) WO2009035658A1 (de)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2141848A (en) * 1938-12-27 Soot remover
US3007781A (en) * 1960-04-04 1961-11-07 Socony Mobil Oil Co Inc Chemical cleaning of oil heating systems
US4287090A (en) * 1979-07-30 1981-09-01 Pfefferle William C Method of treating flue deposits and composition therefor
DE3729930A1 (de) * 1987-09-07 1989-03-16 Dieter Georg Mueller Fluessige katalysator-komplexe
EP1431372A2 (de) * 2002-12-18 2004-06-23 Ethyl Corporation Anwendung von Manganverbindungen zur Unterdrückung der Nieder- und Hochtemperaturkorrosion in Industrieöfen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5944858A (en) * 1990-09-20 1999-08-31 Ethyl Petroleum Additives, Ltd. Hydrocarbonaceous fuel compositions and additives therefor
US6464899B1 (en) * 1999-06-11 2002-10-15 Henkel Loctite Corporation Putty composition containing a vapor phase corrosion inhibitor
US6843812B2 (en) * 2001-01-05 2005-01-18 Prodromos Pericles Stephanos Lighter fluid composition
US7540890B2 (en) * 2003-02-28 2009-06-02 Clark Schaefer Creosote and soot destroying fire log
DE102005032119A1 (de) * 2005-07-07 2007-01-18 Octel Deutschland Gmbh Russarm verbrennendes Heizöl

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2141848A (en) * 1938-12-27 Soot remover
US3007781A (en) * 1960-04-04 1961-11-07 Socony Mobil Oil Co Inc Chemical cleaning of oil heating systems
US4287090A (en) * 1979-07-30 1981-09-01 Pfefferle William C Method of treating flue deposits and composition therefor
DE3729930A1 (de) * 1987-09-07 1989-03-16 Dieter Georg Mueller Fluessige katalysator-komplexe
EP1431372A2 (de) * 2002-12-18 2004-06-23 Ethyl Corporation Anwendung von Manganverbindungen zur Unterdrückung der Nieder- und Hochtemperaturkorrosion in Industrieöfen

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Material Safety Data Sheet - Manganese (II) 2-ethylhexanoate, 40% w/w in mineral spirits", , 16 August 2002 (2002-08-16), XP55011353, Retrieved from the Internet: URL:http://www.labseeker.com/ChemicalBiotech/msds\Alfa\38000\38607.pdf [retrieved on 2011-11-07] *
See also references of WO2009035658A1 *

Also Published As

Publication number Publication date
WO2009035658A1 (en) 2009-03-19
JP2010539281A (ja) 2010-12-16
EP2197992A4 (de) 2011-12-14

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