EP1600492A1 - Process and means for avoiding damage by corrosion during the combustion of low sulfur fuels - Google Patents

Process and means for avoiding damage by corrosion during the combustion of low sulfur fuels Download PDF

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Publication number
EP1600492A1
EP1600492A1 EP04011844A EP04011844A EP1600492A1 EP 1600492 A1 EP1600492 A1 EP 1600492A1 EP 04011844 A EP04011844 A EP 04011844A EP 04011844 A EP04011844 A EP 04011844A EP 1600492 A1 EP1600492 A1 EP 1600492A1
Authority
EP
European Patent Office
Prior art keywords
additive
combustion
fuel
ppm
oil
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Withdrawn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
EP04011844A
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German (de)
French (fr)
Inventor
Martin Dr. Müller
Ünal Karaagac
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.)
ERC Emissions-Reduzierungs-Concepte GmbH
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ERC Emissions-Reduzierungs-Concepte GmbH
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Filing date
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Application filed by ERC Emissions-Reduzierungs-Concepte GmbH filed Critical ERC Emissions-Reduzierungs-Concepte GmbH
Priority to EP04011844A priority Critical patent/EP1600492A1/en
Publication of EP1600492A1 publication Critical patent/EP1600492A1/en
Withdrawn legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23K—FEEDING FUEL TO COMBUSTION APPARATUS
    • F23K5/00—Feeding or distributing other fuel to combustion apparatus
    • F23K5/02—Liquid fuel
    • F23K5/08—Preparation of fuel
    • 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
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • 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
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2658—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) amine salts
    • 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
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation

Definitions

  • the invention relates to a method for avoiding Corrosion damage during combustion of fuels or fuels whose sulfur content has been reduced, or from low-sulfur fuel oil.
  • the invention is therefore based on the object for Fuels and fuels with reduced sulfur content, especially low-sulfur heating oils, an additive to create, with which the metal dusting prevents or is at least significantly reduced.
  • the object is achieved according to the invention in that the fuel before combustion phosphorus-containing additive is added.
  • a phosphorus-containing additive solves the problems of Corrosion, by simultaneously with the combustion introduced a compound in the combustion chamber of the fuel oil which contributes to extremely fast protective layer buildup very low rates of introduction.
  • the additive oil-soluble.
  • Common phosphorus compounds are phosphoric acids or their esters.
  • the former are among others in the Metalworking for phosphating purposes and the latter especially in the detergent or surfactant industry used.
  • lead phosphoric acids due to the acid character of the premature aging of the Fuel during storage; besides they are in Mineral oil insoluble.
  • phosphoric acid (partial) esters react with deposited sediments and thereby lead in a short time to disturbances of the fuel supply system.
  • the phosphorus-containing active ingredient is chosen from a group of substances that is considered neutralized phosphoric acid ester (mono- or di-ester) can describe.
  • the Neutralization by an amine compound but can also via further alcohols.
  • the ester residues are preferably, not as customary in surfactant chemistry, in non-ethoxylated form.

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

Abstract

Method for avoiding corrosion damage in combustion of fuel- or diesel oil (where sulfur content was reduced) or in low sulfur fuel oil, comprises adding phosphorus-containing additive to fuel-/diesel oil or heating oil before the combustion. An independent claim is also included for an additive for fuel oil to avoid the corrosion damage in the combustion of fuel- or engine oil (where sulfur content was reduced) or in the combustion of low-sulfur fuel oil, comprising a phosphorus-containing compound as active agent.

Description

Die Erfindung betrifft ein Verfahren zur Vermeidung von Korrosionsschäden bei der Verbrennung von Kraftstoffen oder Brennstoffen, deren Schwefelgehalt reduziert wurde, oder von schwefelarmem Heizöl.The invention relates to a method for avoiding Corrosion damage during combustion of fuels or fuels whose sulfur content has been reduced, or from low-sulfur fuel oil.

Der Einsatz von schwefelreduzierten Brenn- und Kraftstoffen mit einem Schwefelgehalt von weniger als 700 ppm und insbesondere weniger als 200 ppm oder 100 ppm, zum Beispiel schwefelarmem Heizöl gemäß DIN 51603-1 mit einem Schwefelgehalt von weniger als 50 ppm, ermöglicht neben dem Vorteil der Reduktion von SO2-Emissionen eine Verbrennung mit im Abgas-Kondensationsbetrieb, der einen höheren Wirkungsgrad gewährleistet. Bei der Verbrennung kommt es jedoch unter bestimmten Umständen zu einem unerwünschten Angriff des Metalls im Brennraum durch Ablagerung von unverbrannten Kohlenwasserstoffen (oder Ruß) und anschließender Korrosion, dem so genannten metal dusting. Dieses Phänomen tritt auf, weil sich ansonsten die bei der Verbrennung spontan bildende Sulfid-Schutzschicht bei geringem Schwefelgehalt nicht mehr schnell genug aufbauen kann. Damit wird ein Angriff der metallischen Oberflächen durch unverbrannte Anteile des Brennstoffes möglich.The use of sulfur reduced fuel and Fuels with a sulfur content of less than 700 ppm and in particular less than 200 ppm or 100 ppm, For example, low sulfur fuel oil according to DIN 51603-1 with a sulfur content of less than 50 ppm in addition to the advantage of reducing SO2 emissions one Combustion with in the exhaust condensation mode, the one ensures higher efficiency. When burning However, under certain circumstances, there is one unwanted attack of the metal in the combustion chamber by Deposition of unburned hydrocarbons (or Soot) and subsequent corrosion, the so-called metal dusting. This phenomenon occurs because otherwise the spontaneously forming sulfide protective layer during combustion at low sulfur content no more build fast enough. This will be an attack of metallic surfaces by unburned portions of the Fuel possible.

Es ist z. B. bei Neuanlagen versucht worden, Abhilfe durch eine Veränderung der Geometrie einerseits oder des Materials andererseits zu schaffen. Diese Maßnahmen können den Schutz bereits im Markt bestehender Anlagen allerdings nicht gewährleisten. Weiterhin ist es bekannt, ein die Verbrennungsreaktion beschleunigendes Additiv , 2-Ethyl-Hexyl-Nitrat (2-EHN), einzusetzen, das in der Mineralölindustrie zur Erhöhung der Zündwilligkeit von Kraftstoff verwendet wird. Trotz eines gewissen Erfolgs hat die Verwendung eines solchen Additivs den Nachteil, dass die für die Lagerung von Heizöl wichtige Langzeitstabilität stark beeinträchtigt wird.It is Z. B. has been tried in new plants, remedy by a change of the geometry on the one hand or the Materials on the other hand. These measures can protect already existing equipment in the market but not guarantee. Furthermore, it is known an additive that accelerates the combustion reaction, 2-ethyl-hexyl-nitrate (2-EHN), used in the Petroleum industry to increase the ignitability of Fuel is used. Despite a certain success the use of such an additive has the disadvantage that is important for the storage of fuel oil Long-term stability is severely impaired.

Trotz intensiver Forschungen konnte dem Markt bisher keine andere Lösung angeboten werden. ,Despite intensive research, the market has so far no other solution will be offered. .

Der Erfindung liegt daher die Aufgabe zugrunde, für Brenn- und Kraftstoffe mit reduziertem Schwefelgehalt, insbesondere schwefelarme Heizöle, ein Additiv zu schaffen, mit welchem das metal dusting verhindert oder zumindest wesentlich reduziert wird.The invention is therefore based on the object for Fuels and fuels with reduced sulfur content, especially low-sulfur heating oils, an additive to create, with which the metal dusting prevents or is at least significantly reduced.

Die Aufgabe wird gemäß der Erfindung dadurch gelöst, dass dem Kraft- oder Brennstoff vor der Verbrennung ein phosphorhaltiges Additiv zugegeben wird. Die Zugabe eines phosphorhaltigen Additivs behebt die Probleme der Korrosionsbildung, indem gleichzeitig mit der Verbrennung des Heizöls eine Verbindung in den Feuerraum eingebracht wird, die einen extrem schnellen Schutzschichtaufbau bei sehr geringen Einbringraten ermöglicht. Vorzugsweise ist das Additiv öllöslich.The object is achieved according to the invention in that the fuel before combustion phosphorus-containing additive is added. The addition of a phosphorus-containing additive solves the problems of Corrosion, by simultaneously with the combustion introduced a compound in the combustion chamber of the fuel oil which contributes to extremely fast protective layer buildup very low rates of introduction. Preferably the additive oil-soluble.

Gängige Phosphorverbindungen sind Phosphorsäuren oder deren Ester. Erstere werden unter anderem in der Metallverarbeitung zu Phosphatierzwecken und letztere insbesondere in der Waschmittel- bzw. Tensid-Industrie eingesetzt. Einerseits führen Phosphorsäuren jedoch aufgrund des Säurecharakters zum vorzeitigen Altern des Brennstoffes bei der Lagerung; außerdem sind sie in Mineralöl unlöslich. Die in der Tensidindustrie üblichen Phosphorsäure-(Teil-)Ester andererseits reagieren mit abgelagerten Sedimenten und führen dadurch in kurzer Zeit zu Störungen des Brennstoffversorgungsssystems.Common phosphorus compounds are phosphoric acids or their esters. The former are among others in the Metalworking for phosphating purposes and the latter especially in the detergent or surfactant industry used. On the one hand, however, lead phosphoric acids due to the acid character of the premature aging of the Fuel during storage; besides they are in Mineral oil insoluble. The usual in the surfactant industry On the other hand, phosphoric acid (partial) esters react with deposited sediments and thereby lead in a short time to disturbances of the fuel supply system.

Es ist daher gemäß einer bevorzugten Ausführungsform der Erfindung vorgesehen, dass der phosphorhaltige Wirkstoff aus einer Stoffgruppe gewählt wird, die sich als neutralisierter Phosphorsäureester (Mono- oder Di-Ester) beschreiben lässt. Vorzugsweise erfolgt die Neutralisation durch eine Aminverbindung, kann aber auch über weitere Alkohole erfolgen. Die Ester-Reste liegen bevorzugt, nicht wie in der Tensidchemie üblich, in nicht-ethoxylierter Form vor.It is therefore according to a preferred embodiment of Invention provided that the phosphorus-containing active ingredient is chosen from a group of substances that is considered neutralized phosphoric acid ester (mono- or di-ester) can describe. Preferably, the Neutralization by an amine compound, but can also via further alcohols. The ester residues are preferably, not as customary in surfactant chemistry, in non-ethoxylated form.

Mit einer Phosphorsäure-Ester mit aliphatischen Mono- und Diestern mit einer Kettenlänge zwischen C4 und C20, welches mit einem sekundären Amin neutralisiert wurde, sind an einem Brenner mit einem zum metal dusting neigenden Heizöl Versuche durchgeführt worden. Die verwendeten Konzentrationen des Additivs betrugen 10 ppm, 100 ppm und 500 ppm. Während bei einer Konzentration von 10 ppm der Angriff auf den Brenneraufsatz vernachlässigbar klein war, trat bei einer Konzentration von 100 ppm kein metal dusting mehr auf. Bei 500 ppm war eine deutliche Verfärbung des Brenneraufsatzes zu erkennen, was auf eine starke Deckschichtbildung hinweist.With a phosphoric acid ester with aliphatic mono- and Diesters with a chain length between C4 and C20, which was neutralized with a secondary amine, are at a burner with a metal dusting Tending fuel oil tests have been carried out. The used concentrations of the additive were 10 ppm, 100 ppm and 500 ppm. While at a concentration of 10 ppm of attack on the burner attachment negligible, occurred at a concentration of 100 ppm no more metal dusting up. At 500 ppm was a significant discoloration of the burner attachment to realize what a strong topcoat formation points.

Claims (13)

Verfahren zur Vermeidung von Korrosionsschäden bei der Verbrennung von Brenn- und Kraftstoffen, deren Schwefelgehalt reduziert wurde, oder von schwefelarmem Heizöl, dadurch gekennzeichnet, dass dem Brenn- oder Kraftstoff oder dem Heizöl vor der Verbrennung ein phosphorhaltiges Additiv zugegeben wird.A method for preventing corrosion damage in the combustion of fuels and fuels whose sulfur content has been reduced, or of low-sulfur fuel oil, characterized in that the fuel or fuel or fuel oil is added prior to combustion, a phosphorus-containing additive. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Additiv in Mineralöl löslich ist.A method according to claim 1, characterized in that the additive is soluble in mineral oil. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass das Additiv eine neutrale oder basische Reaktion zeigt.Method according to one of claims 1 or 2, characterized in that the additive shows a neutral or basic reaction. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Struktur des Additivs von einem Phosphorsäure-Ester abgeleitet ist.Method according to one of claims 1 to 3, characterized in that the structure of the additive is derived from a phosphoric acid ester. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Additiv in nicht-ethoxilierter Form vorliegt und/oder keine ethoxylierten Seitenketten besitzt.Method according to one of claims 1 to 4, characterized in that the additive is present in non-ethoxylated form and / or has no ethoxylated side chains. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Additiv in einer Konzentration zwischen 1 ppm und 500 ppm zugesetzt wird. Method according to one of claims 1 to 5, characterized in that the additive is added in a concentration between 1 ppm and 500 ppm. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass das Additiv in einer Konzentration zwischen 5 ppm und 250 ppm zugesetzt wird.A method according to claim 6, characterized in that the additive is added in a concentration between 5 ppm and 250 ppm. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass das Additiv in einer Konzentration zwischen 10 ppm und 150 ppm zugesetzt wird.A method according to claim 6, characterized in that the additive is added in a concentration between 10 ppm and 150 ppm. Additiv für Heizöl zur Vermeidung von Korrosionsschäden bei der Verbrennung von Brenn- und Kraftstoffen, deren Schwefelgehalt reduziert wurde, oder bei der Verbrennung von schwefelarmem Heizöl, dadurch gekennzeichnet, dass es eine phosphorhaltige Verbindung, als Wirkstoff enthält.Additive for fuel oil to prevent corrosion damage in the combustion of fuels and fuels whose sulfur content has been reduced, or in the combustion of low-sulfur fuel oil, characterized in that it contains a phosphorus-containing compound, as an active ingredient. Additiv nach Anspruch 9, dadurch gekennzeichnet, dass es in Mineralöl löslich ist.Additive according to claim 9, characterized in that it is soluble in mineral oil. Additiv nach einem der Ansprüche' 9 oder 10, dadurch gekennzeichnet, dass es eine neutrale oder basische Reaktion zeigt.Additive according to one of claims 9 or 10, characterized in that it shows a neutral or basic reaction. Additiv nach einem der Ansprüche 9 bis 11, dadurch gekennzeichnet, dass dessen Struktur von einem Phosphorsäure-Ester abgeleitet ist.Additive according to one of claims 9 to 11, characterized in that its structure is derived from a phosphoric acid ester. Additiv nach einem der Ansprüche 9 bis 12, dadurch gekennzeichnet, dass es in nicht-ethoxilierter Form vorliegt und/oder keine ethoxylierten Seitenketten besitzt.An additive according to any one of claims 9 to 12, characterized in that it is in non-ethoxylated form and / or has no ethoxylated side chains.
EP04011844A 2004-05-19 2004-05-19 Process and means for avoiding damage by corrosion during the combustion of low sulfur fuels Withdrawn EP1600492A1 (en)

Priority Applications (1)

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EP04011844A EP1600492A1 (en) 2004-05-19 2004-05-19 Process and means for avoiding damage by corrosion during the combustion of low sulfur fuels

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EP04011844A EP1600492A1 (en) 2004-05-19 2004-05-19 Process and means for avoiding damage by corrosion during the combustion of low sulfur fuels

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EP1600492A1 true EP1600492A1 (en) 2005-11-30

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2387537A (en) * 1945-03-19 1945-10-23 Gulf Oil Corp Fatty amine salts of alkyl phosphoric acids
GB789778A (en) * 1955-05-09 1958-01-29 Gulf Oil Corp Jet engine fuel
US3384466A (en) * 1967-02-21 1968-05-21 Esso Res And Engienering Compa Amine-phosphates as multi-functional fuel additives
US5630852A (en) * 1994-11-23 1997-05-20 Fmc Corporation Organophosphorus additives for improved fuel lubricity
EP0811676A1 (en) * 1995-02-24 1997-12-10 Better Mask Co., Ltd. Composition for cleaning and coating the interior of an internal combustion engine and method for cleaning and coating the interior of an internal combustion engine therewith

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2387537A (en) * 1945-03-19 1945-10-23 Gulf Oil Corp Fatty amine salts of alkyl phosphoric acids
GB789778A (en) * 1955-05-09 1958-01-29 Gulf Oil Corp Jet engine fuel
US3384466A (en) * 1967-02-21 1968-05-21 Esso Res And Engienering Compa Amine-phosphates as multi-functional fuel additives
US5630852A (en) * 1994-11-23 1997-05-20 Fmc Corporation Organophosphorus additives for improved fuel lubricity
EP0811676A1 (en) * 1995-02-24 1997-12-10 Better Mask Co., Ltd. Composition for cleaning and coating the interior of an internal combustion engine and method for cleaning and coating the interior of an internal combustion engine therewith

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