WO2005033253A1 - Schwefelarmes öl, verfahren zur senkung der aggressivität eines solchen öls - Google Patents
Schwefelarmes öl, verfahren zur senkung der aggressivität eines solchen öls Download PDFInfo
- Publication number
- WO2005033253A1 WO2005033253A1 PCT/CH2004/000615 CH2004000615W WO2005033253A1 WO 2005033253 A1 WO2005033253 A1 WO 2005033253A1 CH 2004000615 W CH2004000615 W CH 2004000615W WO 2005033253 A1 WO2005033253 A1 WO 2005033253A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oil
- additive
- substance
- heating
- derivative
- Prior art date
Links
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, 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
- C10L1/2608—Organic compounds containing phosphorus containing a phosphorus-carbon bond
- C10L1/2616—Organic compounds containing phosphorus containing a phosphorus-carbon bond sulfur containing
-
- 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
-
- 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
- C10L1/2608—Organic compounds containing phosphorus containing a phosphorus-carbon 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
- C10L1/2608—Organic compounds containing phosphorus containing a phosphorus-carbon bond
- C10L1/2625—Organic compounds containing phosphorus containing a phosphorus-carbon 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
- 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)
- C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
-
- 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)
- C10L1/265—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen and/or sulfur bonds
-
- 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
Definitions
- the invention relates to the use of a substance for lowering a property of diesel oil or heating oil that causes metal dusting during combustion, and to the use of an additive for reducing a property of metal oil or heating oil that causes combustion during combustion to be particularly easy (Heating oil EL), a process to reduce or prevent erosion damage in the combustion chamber of a boiler or engine, as well as a low-sulfur heating oil extra light and a low-sulfur diesel.
- Heating oil EL Heating oil EL
- This additive was used in aviation fuel to increase the conductivity of aviation fuel.
- Such a “static dissipator additive” ensures that the electrostatic charges remain low during combustion, since electrical charges that occur are immediately reduced thanks to the increased conductivity.
- diesel and heating oil EL can and must be differentiated, even if it is technically possible to use diesel as fuel and heating oil as fuel for older diesel engines.
- Diesel has a cetane number of at least 51 (EU standard) and thanks to cetane number improvers up to 58 or more and its flowability is less temperature-dependent than that of heating oil. With heating oil, however, the cetane number is not determined at all (it is usually less than 50), and heating oil does not contain any cetane number improvers. Diesel also contains other additives such as pour point improvers etc.
- an organic phosphorus substance can therefore be used as an additive in low-sulfur oil in order to reduce the newly discovered property of the oil which causes metal dusting during combustion.
- An additive advantageously has no sulfur content. Substances without nitrogen content are also preferred. This prevents sulfur oxide and nitrogen oxide emissions. Sulfur oxide emissions are unsuitable for condensing technology. Nitrogen oxide emissions must be avoided due to the strict emission regulations. There are basically two alternative ways to ensure that the added quantity of the additive is sufficient to eliminate the metal dusting effect of the oil. An equal amount of additive can be added to many batches, or a minimal amount of additive can be added. The former option has the disadvantage that the amount of additive is too high for most batches. On the other hand, it has the advantage that the batches do not have to be checked individually.
- the second alternative has the advantage of the economy of the additive added, but requires a batch-specific determination of the aggressiveness of the oil, as well as for each batch a calculation of the required additive quantity and the corresponding individual addition of the additive and a control of the product to be delivered.
- the erosive properties of a batch of oil must be determined and the additive must be added to this batch in a minimal amount.
- the amount added should just be sufficient to reduce the erosive property of this batch to such an extent that erosion caused by metal dusting is unlikely to occur when the oil burns.
- Esters of phosphoric acid and their derivatives For example, the following mono-, di- and tri-aryl esters: trixylyl phosphate, tricresyl phosphate, triphenyl phosphate, dibenzyl phosphate and its derivatives neutralized with amine, monobenzyl phosphate and derivatives neutralized with its amine; or for example the following mono-, di- and tri-alkyl esters: Tris (2-ethylhexyl) phosphate, tri-butyl phosphate, distearyl phosphate and its amine neutralized derivatives, monocetyl phosphate and its amine neutralized derivatives.
- Phosphorous acid esters and their derivatives e.g. the following aryl esters: triphenyl phosphite, dibenzyl phosphite and its amine neutralized derivatives, monobenzyl phosphite and its amine neutralized derivatives; or the following alkyl esters: tricetyl phosphite, trinonyl phosphite, triethyl phosphite, dicetyl phosphite and its amine neutralized derivatives, monocetyl phosphite and its amine neutralized derivatives
- Esters of phosphonic acid and its derivatives e.g .: octanephosphonic acid and its amine neutralized derivatives; but also derivatives of various phosphonocarboxylic acids such as: triethyl phosphonoacetate, trimethyl phosphonoformate, triethyl phosphonoformate, phenyl methyl phosphonoacetate, phenylethyl phosphonoformate; trimethyl phosphonoformate is particularly preferred; and further derivatives of various phosphonoamides.
- various phosphonocarboxylic acids such as: triethyl phosphonoacetate, trimethyl phosphonoformate, triethyl phosphonoformate, phenyl methyl phosphonoacetate, phenylethyl phosphonoformate; trimethyl phosphonoformate is particularly preferred; and further derivatives of various phosphonoamides.
- Esters of diphosphoric acid and its derivatives such as e.g. Tetrabenzylpyrophospreheat.
- Phosphines and their derivatives e.g. following aryl and alkylphosphines: trioctylphosphine, tri-tolylphosphine, tri-phenylphosphine, 1,2-bis (diphenylphosphino) ethane and their oxides such as e.g. Trioctylphosphine oxide.
- Phosphoranes and their derivatives such as e.g. Methylentriphenyrphosphoran
- Phosphorus-containing heterocyclic compounds such as the phosphines and phospholes and their derivatives
- An additive alone can be added to the oil.
- two or more additives can also be added to the oil.
- the above examples of additives have the additional advantage that they improve the lubricity of the oil.
- the addition of such an additive according to the invention not only eliminates the aggressiveness of the oil with regard to metal dusting during its combustion, but also creates a desirable lubricity of the diesel and the heating oil.
- Figures 1 to 5 show damage patterns on burners of five test specimens of an extremely risky first fuel (CH-B) with different admixtures of arnine phosphate.
- CH-B extremely risky first fuel
- Figures 6 to 9 show damage patterns to burners after 32.9 hours of test operation, caused by a second fuel (CH-
- the risk of the fuel in the tested composition is divided into four levels: high risk, level 4; risky, level 3; not very dangerous, level 2; no risk, level 1.
- a first test specimen 119 of the CH-B fuel is tested without the addition of additives. It is classified as very risky.
- the erosion of the burner caused by metal dusting after approx. 60 minutes of test operation is shown in FIG. 1.
- the area under attack covers a few square centimeters. So far, no other fuels have been found that are as aggressive as the CH-B fuel, even if many other fuels from other batches have to be classified as highly risky.
- test specimen 136 the additive to the CH-B fuel is added in an amount of 0.5 percent by volume.
- the result shows a still risky fuel, level 3.
- the erosion caused by metal dusting takes up a small area and is significantly less violent than in test piece 135 (FIG. 4).
- the test specimen 137 produces a fuel that is not very hazardous, but which contains 0.8% additive CH-B. Erosion caused by metal dusting is visible, but very small (Fig. 4).
- this extremely aggressive fuel is often used for research purposes, since it quickly leads to clear results. Accordingly, this fuel CH-B is also used in the second series of tests. This time triphenyl phosphorothionate is used as an additive.
- a first test item is the CH-B fuel with 0.1 percent by volume of this triphenylphosphorothionate. In this composition, too, the fuel can still be classified as highly risky.
- Figure 9 shows a
- the substances listed above are added as additives to heating oils which cause metal dusting without an additive. Positive results are achieved with each of the substances listed above. However, the differences in their effectiveness are considerable.
- the amount of additive required depends on the substance used. The amount required for the same oil varies in the order of 1 to 10 depending on the substance. The most effective substances or substance mixtures have to be added at most in an amount of 500 to 1000 mg per kilogram of heating oil.
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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)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH16992003 | 2003-10-07 | ||
CH1699/03 | 2003-10-07 |
Publications (1)
Publication Number | Publication Date |
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WO2005033253A1 true WO2005033253A1 (de) | 2005-04-14 |
Family
ID=34398339
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CH2004/000615 WO2005033253A1 (de) | 2003-10-07 | 2004-10-07 | Schwefelarmes öl, verfahren zur senkung der aggressivität eines solchen öls |
Country Status (1)
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WO (1) | WO2005033253A1 (de) |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR859846A (fr) * | 1938-12-22 | 1940-12-30 | Standard Oil Dev Co | Combustibles pour moteurs |
DE1199251B (de) * | 1958-10-28 | 1965-08-26 | Dr Friedrich Cramer | Verfahren zur Herstellung von Saeureanhydriden und Phenylestern saurer Phosphorsaeureester |
US3262971A (en) * | 1962-10-12 | 1966-07-26 | Monsanto Res Corp | Phosphorus compounds |
GB1040896A (en) * | 1963-09-17 | 1966-09-01 | Chevron Res | Dithiophosphates |
US3374256A (en) * | 1963-08-16 | 1968-03-19 | Monsanto Res Corp | Complex phosphorus salts |
US3531394A (en) * | 1968-04-25 | 1970-09-29 | Exxon Research Engineering Co | Antifoulant additive for steam-cracking process |
CH498925A (de) * | 1965-05-07 | 1970-11-15 | Universal Oil Prod Co | Verfahren zur Verbesserung der die Vereisung verhindernden Eigenschaften eines Motortreibstoffs, nach dem Verfahren erhaltener Motortreibstoff und Motortreibstoffzusatz zur Durchführung dieses Verfahrens |
US3704107A (en) * | 1970-12-07 | 1972-11-28 | Texaco Inc | Fuel composition |
US4177768A (en) * | 1979-01-19 | 1979-12-11 | Ethyl Corporation | Fuel compositions |
EP0083124A1 (de) * | 1981-12-29 | 1983-07-06 | The Procter & Gamble Company | Alphaphosphonamide, und sie enthaltende Schmiermittel und Kohlenwasserstoff-Öl-Zusammensetzungen |
EP0083123A1 (de) * | 1981-12-29 | 1983-07-06 | The Procter & Gamble Company | Alphaphosphato-Amide-Verbindungen und sie enthaltende Schmiermittel und Kohlenwasserstoff-Öl-Zusammensetzungen |
US4532057A (en) * | 1983-08-31 | 1985-07-30 | Mobil Oil Corporation | Lubricant composition comprising the reaction product of a vicinal diol and a dihydrocarbyl phosphite |
US5382266A (en) * | 1992-11-25 | 1995-01-17 | Phillips Petroleum Company | Fuel with stability additive and process for stabilizing fuel using an additive |
US5490864A (en) * | 1991-08-02 | 1996-02-13 | Texaco Inc. | Anti-wear lubricity additive for low-sulfur content diesel fuels |
WO1996016143A1 (en) * | 1994-11-23 | 1996-05-30 | Fmc Corporation | Organophosphorus additives for improved fuel lubricity |
US5681798A (en) * | 1996-08-01 | 1997-10-28 | Farng; Liehpao O. | Load-carrying additives based on organo-phosphites and amine phosphates |
WO2003027668A1 (de) * | 2001-09-21 | 2003-04-03 | Swiss E-Technic Ag | Verfahren zur verminderung von schäden an heizungsanlagen und vorrichtung zur durchführung des verfahrens |
-
2004
- 2004-10-07 WO PCT/CH2004/000615 patent/WO2005033253A1/de active Application Filing
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR859846A (fr) * | 1938-12-22 | 1940-12-30 | Standard Oil Dev Co | Combustibles pour moteurs |
DE1199251B (de) * | 1958-10-28 | 1965-08-26 | Dr Friedrich Cramer | Verfahren zur Herstellung von Saeureanhydriden und Phenylestern saurer Phosphorsaeureester |
US3262971A (en) * | 1962-10-12 | 1966-07-26 | Monsanto Res Corp | Phosphorus compounds |
US3374256A (en) * | 1963-08-16 | 1968-03-19 | Monsanto Res Corp | Complex phosphorus salts |
GB1040896A (en) * | 1963-09-17 | 1966-09-01 | Chevron Res | Dithiophosphates |
CH498925A (de) * | 1965-05-07 | 1970-11-15 | Universal Oil Prod Co | Verfahren zur Verbesserung der die Vereisung verhindernden Eigenschaften eines Motortreibstoffs, nach dem Verfahren erhaltener Motortreibstoff und Motortreibstoffzusatz zur Durchführung dieses Verfahrens |
US3531394A (en) * | 1968-04-25 | 1970-09-29 | Exxon Research Engineering Co | Antifoulant additive for steam-cracking process |
US3704107A (en) * | 1970-12-07 | 1972-11-28 | Texaco Inc | Fuel composition |
US4177768A (en) * | 1979-01-19 | 1979-12-11 | Ethyl Corporation | Fuel compositions |
EP0083124A1 (de) * | 1981-12-29 | 1983-07-06 | The Procter & Gamble Company | Alphaphosphonamide, und sie enthaltende Schmiermittel und Kohlenwasserstoff-Öl-Zusammensetzungen |
EP0083123A1 (de) * | 1981-12-29 | 1983-07-06 | The Procter & Gamble Company | Alphaphosphato-Amide-Verbindungen und sie enthaltende Schmiermittel und Kohlenwasserstoff-Öl-Zusammensetzungen |
US4532057A (en) * | 1983-08-31 | 1985-07-30 | Mobil Oil Corporation | Lubricant composition comprising the reaction product of a vicinal diol and a dihydrocarbyl phosphite |
US5490864A (en) * | 1991-08-02 | 1996-02-13 | Texaco Inc. | Anti-wear lubricity additive for low-sulfur content diesel fuels |
US5382266A (en) * | 1992-11-25 | 1995-01-17 | Phillips Petroleum Company | Fuel with stability additive and process for stabilizing fuel using an additive |
WO1996016143A1 (en) * | 1994-11-23 | 1996-05-30 | Fmc Corporation | Organophosphorus additives for improved fuel lubricity |
US5681798A (en) * | 1996-08-01 | 1997-10-28 | Farng; Liehpao O. | Load-carrying additives based on organo-phosphites and amine phosphates |
WO2003027668A1 (de) * | 2001-09-21 | 2003-04-03 | Swiss E-Technic Ag | Verfahren zur verminderung von schäden an heizungsanlagen und vorrichtung zur durchführung des verfahrens |
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