EP1854867A1 - New stabilized fuel composition - Google Patents
New stabilized fuel composition Download PDFInfo
- Publication number
- EP1854867A1 EP1854867A1 EP07108062A EP07108062A EP1854867A1 EP 1854867 A1 EP1854867 A1 EP 1854867A1 EP 07108062 A EP07108062 A EP 07108062A EP 07108062 A EP07108062 A EP 07108062A EP 1854867 A1 EP1854867 A1 EP 1854867A1
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- European Patent Office
- Prior art keywords
- fuel
- hereinabove
- dispersant
- gas
- oil
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- 0 *c(cc1*)cc(O*)c1O Chemical compound *c(cc1*)cc(O*)c1O 0.000 description 1
- YAAWNLZAQXIESP-UHFFFAOYSA-N OCC(C(C1O)O)OOC1C(O)=O Chemical compound OCC(C(C1O)O)OOC1C(O)=O YAAWNLZAQXIESP-UHFFFAOYSA-N 0.000 description 1
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
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
-
- 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
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
-
- 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
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
- C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
-
- 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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
-
- 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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
Definitions
- This invention is related to a new fuel composition which incorporates a chelating agent capable of stabilizing said fuel against the degradation thereof under working conditions and exposure to contamination by metals observed in the new combustion facilities and engines.
- Liquid fuels are used widely in industry for transport or furnaces. They are mostly obtained from oil refining, although they may incorporate components from other sources, for example biofuels.
- the stability of the oil fractions and the new fuel components is a property essential to ensuring their appropriate use. And guaranteeing this property is a highly difficult task, especially considering the wide variety of fuel compositions, depending upon their sources and the manner in which they are obtained.
- Metal deactivators are compounds complexing the metals dissolved in the hydrocarbons, preventing the metal ions from initiating or catalyzing the radicalary reactions responsible for said oxidation.
- the metal passivating compounds which laminate the metal surfaces for prevent their corrosion are also sometimes termed metal deactivators. These compounds, although having a secondary effect on the stability on reducing the solubility of the metals, do not inhibit the catalytic effect thereof for the degradation reactions.
- Fuel formulations are progressively more variable as a result of the new oil refining processes.
- the combined presence of direct distillation and conversion currents at different hydrotreatment levels is progressively more frequent and increases this variability to an even greater degree.
- the fuel compositions may therefore vary within broad ranges, having highly variable contents in critical compounds such as olefins, diolefins, sulfur and nitrogen heteroatoms, metals, etc.
- critical compounds such as olefins, diolefins, sulfur and nitrogen heteroatoms, metals, etc.
- Metals have recently been found to be present in fuels. In a sampling process conducted in 2003 on 78 commercial samples in Spain, the amount of said metals (Cu+Zn) was found to total up to 0.2 mg per kilo of fuel. In addition thereto, the high temperature of the new injection systems has been detected as capable of causing a high solution of Cu up to levels in excess of 1 ppm. These levels of high-temperature metal dissolution have been simulated in high-temperature laboratory tests, the concentrations determined in the field having been found to exist.
- antioxidants and metal deactivators are stated in resources in kerosene-type medium distillates with sulfur contents of over 350 mg/kg (up to 3000 mg/kg). Sulfur being present is essential, given that it is a natural antioxidant. However, the use thereof in diesel fuel is extremely rare, and the effectiveness of these components varies when the sulfur content is less than 350 mg/kg (European legislation since 1999). The response of gas-oil to these additives still differs even more as the sulfur is reduced, being totally different on completely eliminating this element (sulfur content below 10 mg/kg).
- the EN-590 specification requires content of less than 50 mg/kg in all automotive gas-oils as of 2005 and of less than 10 mg/kg as of 2009.
- the DEF-STAN 91-91 specification indicates that aviation kerosene may incorporate an antioxidant in a concentration within the 17-24 mg/l range and an N,N'-disalicylidene-1,2-propanediamine metal deactivator in a concentration of ⁇ 2 mg/l. This is the only metal deactivator permitted in kerosenes and the only one used in other medium distillates.
- N,N'-disalicylidene-1,2-propanediamine in kerosene is described in several publications ( Pande, S.G. et al. in 6th International Conference on Stability and Handling of Liquid Fuel, Canada, 211-230 (1997 ) and Cyrus, P.H.
- Triazoles and benzotriazoles are used in motor oils for the purpose of prevent corrosion related to the Pb in presence of metals (Cu, brass and bronze) as stated in US patent 0038835 A1 .
- the proportioning used is quite high (2000 ppm).
- Patent WO 03/004476 A1 also states these products in high proportions (200-1000ppm) as deactivators against Cu and Fe, preferably in lubricant bases for the manufacture of any type of fluid subject to coming into contact with metal surfaces.
- deactivators used in lubricants which are described in the Fuels and Lubricants Handbook (Totten, G.E., ASTM International, USA (2003) are lecithin, heterocyclic compound derivatives (thiadiazole, imidazole and pyrazole) and citric and gluconic acid derivatives.
- gluconic acid has been analyzed in depth given the interest in this patent. It is used as a metal and amine captor in refinery processes ( WO 2004020553 ) and as a raw material for lubricants ( US 5773391 , JP 61031213 ), for corrosion inhibitors ( US 4892671 ) and for sulfur recovery from natural gas ( US 2004192995 ). In no case has it been used as a metal deactivator for improving the stability of a medium distillate.
- N,N'-disalicylidene-1,2-propanediamine is also used in automotive gas-oil, as is stated in patent EP 0476197 A1 .
- This patent is related to a formulation comprised mainly of a deactivator and an agent for improving the low-temperature stability of the additive. The effectiveness of said additive in the presence of Cu has not been demonstrated.
- US patent 2813080 a formulation comprised of an N,N'-disalicylidene-1,2-propanediamine deactivator in combination with a dispersant and a combustion enhancer is described. The effectiveness of said formulation in the presence of metals is demonstrated only in the ASTM D-665 test (corrosion related to steel) where the function of the metal deactivator is as a filming agent and not a metal complexing agent.
- the inventors of the present invention have developed an alternative composition capable of stabilizing fuels by adding a certain amount of a chelating agent which is capable of forming complexes with the metal ions, inhibiting the catalytic effect thereof and checking the formation of insoluble substances which could have an effect on the proper working order of the engines and boilers (clogging, corrosion, build-up).
- a new fuel composition in which the chelating agent is the compound in Formula I: or any of the salts thereof.
- Gluconic acid is included in Formula I.
- the fuel is automotive, agricultural or heating gas-oil.
- the composition described comprises 2-50 mg of Formula 1 compound per kilogram of fuel.
- a dispersant is used for improving the stability of the fuel by preventing the agglomeration of insolubles and the depositing thereof.
- composition described in the following invention may also comprise a dispersant such as, for example but without being limited to, a Mannich base or the derivatives thereof, represented by the following Formula IIa: where n ranges from 1 to 10, both included and n' ranges from 10 to 100, both included. or a poly-isobutenesuccinimide or the derivatives thereof represented by the following formula IIb: where n ranges from 1 to 10 and n' ranges from 10 to 100, or any mixture of these two dispersants or the derivatives thereof.
- a dispersant such as, for example but without being limited to, a Mannich base or the derivatives thereof, represented by the following Formula IIa: where n ranges from 1 to 10, both included and n' ranges from 10 to 100, both included. or a poly-isobutenesuccinimide or the derivatives thereof represented by the following formula IIb: where n ranges from 1 to 10 and n' ranges from 10 to 100, or any mixture of these two dispersants or the derivative
- the dispersant added to the composition described in the present invention is used in a proportion ranging from 10 to 1000 mg per kilogram of fuel, more preferably from 50 to 300 mg per kilogram of fuel.
- An antioxidant may also be added to the composition described in the following invention for the purpose of enhancing the stability of the fuel, particularly of low-sulfur gas-oils or in absence of this natural antioxidant.
- composition described in the following invention may also comprise an antioxidant such as, for example but without being limited to the compounds in formula III: where n ranges from 1 to 5, all inclusive.
- a polyisobutenesuccinimide type dispersant according to Formula IIb described hereinabove and preferably proportioned at 10 to 1000 mg per kilogram of fuel and more preferably, 50 to 300 mg per kilogram of fuel is included.
- One final aspect of the present invention provides the use of the Formula I compound described hereinabove for the stabilization of a fuel.
- fuel includes the liquid fuels intended for producing heat energy or for being used in internal combustion engines for producing mechanical energy.
- multifunctional package refers to a composition which comprises but is not limited to one or more dispersing, deemulsifying or antifoaming components. This composition may likewise include other components such as stabilizers, anti-rust additives or cetane improvers.
- the best performance is achieved with gluconic acid.
- the other chelating agents show a worse performance, even going as far as promoting degradation in some of the gas-oil samples evaluated.
- gluconic acid has been evaluated by comparing it to the metal deactivator authorized for aviation kerosenes (NNDDP: N,N'-disalicylidene-1,2-propanediamine), at different proportions (2-50 mg/kg), in low-sulfur gas-oils (50 and 10 mg/kg), in presence or absence of metal (Cu 2+ ) and in presence or absence of a dispersant (DISP).
- NNDDP N,N'-disalicylidene-1,2-propanediamine
- gluconic acid on different properties, such as filterability (internal method), compatibility with additives (proprietary method), antifoaming capacity (dry and wet manual tests, as well as test tube injection, NF-M-07-075), anti-rust properties (ASTM D-665-B; seawater) and emulsion with water (internal method) were also tested.
- a 50 ml sample of gas-oil doped with 1 ppm Cu 2+ was aged for 90 minutes at 150°C in absence of light. Afterward, the increase in color in the gas-oil was evaluated as a measurement of the absorbance of the sample diluted in a zero-absorbance solvent.
- the effectiveness of the metal deactivators on three types of gas-oil of different sulfur contents: automotive gas-oil (GDM1005), agricultural gas-oil (GDM1006) and heating gas-oil (GDM239) were evaluated.
- HLPS detergency A 250 ml sample of gas-oil was aged at 280°C, 38 bars, in a system similar to that used for determining the kerosene stability (ASTM-D-3241), recirculating the sample for a maximum of 4 hours. Afterward, the load loss through a filter located downstream from the maximum temperature area was evaluated. The Tendency to Deposits Formation (TDF) was determined in terms of the load loss and the time lapsed up to said loss.
- TDF Tendency to Deposits Formation
- UOP-835 thermal stability A 50 ml sample of gas-oil was aged for 90 minutes at 150°C in absence of light. Afterward, the sample was filtered and the increase in color of the gas-oil evaluated as a measurement of the absorbance of the diluted sample and the filter opacity.
- Oxidation stability A 350 ml sample of gas-oil was aged under the conditions stipulated in standard ISO12205 (16 hours, 95°C, with 3L/h oxygen bubbling) in presence of 1 mg/kg Cu 2+ . Afterward, the insolubles produced were determined as the sum of filterable (0.8 microns) and adherent forms (washed with trisolvent and evaporation at 160°C), measured in g/m3. The Cu 2+ was added as a reagent in acetate form.
- the gluconic acid showed the best results at 20 ppm (8-11 g/m 3 ), being effective from 2 ppm and achieving less from 21 g/m3 at 10 ppm. In other words, in this case, no benefit was found from increasing the proportion. Tests were conducted up to 50 ppm.
- Test 5-1 Light stability .
- a 50 mL sample of gas-oil was aged at 40°C subjected to constant UV radiation for 48 hours, the resulting insolubles having been evaluated in a manner similar to Test 2, adapting the filter, the filtering equipment and the evaporation to the amount of sample employed.
- Table 5-1 Gas-oil Sulfur content mg/kg DISP, m/m3 MD1, mg/kg MD2, mg/kg Cu 2+ content mg/kg Total insolubles, g/m3 Increase in absorbance G235 50 0 0 0 0 27.1 0.031 G235 50 0 0 0 1 32.2 0.065 G235 50 600 0 0 1 38.0 0.051 G235 50 600 5 0 1 13.2 0.033 G235 50 600 0 10 1 23.0 0.022 G235 50 600 0 20 1 29.9 0.043 MD.
- Metal deactivator Metal deactivator
- the GA at 10 ppm was found to reduce the insolubles to 23 g/m3.
- Test 5-2 DUPONT stability (6 weeks, 43°C). A 350 ml volume of sample was stored at 43°C for 42 days, both the insoluble and the adherent forms and the increase in absorbance having then been quantified.
- Table 5-2 Gas-oil Sulfur content mg/kg DISP, ml/m3 MD1, mg/kg MD2, mg/kg Cu 2+ content mg/kg Total insolubles g/m3 Increase in absorbance G235 50 0 0 0 0 1.7 0.031 G235 50 0 0 0 1 6.6 0.182 G235 50 600 0 0 1 19.5 0.214 G235 50 600 5 0 1 7.5 0.373 G235 50 600 0 10 1 5.9 0.277 G235 50 600 0 20 1 7.4 0.353 MD.
- Metal deactivator Metal deactivator
- Test 5-3 Rancimat stability. Air was made to flow through a sample of gas-oil at 110°C. The fumes given off in the oxidation process, along with the air, were routed through a vessel containing distilled water, where the conductivity was measured, which increases by way of the acids formed during the aging process. The end of the induction period was indicated when the conductivity began to rapidly increase. For the purpose of identifying the progressive destabilization (without any abrupt increase in the production of acids), the length of time having lapsed up to a certain conductivity was also recorded.
- Table 5-3 Gas-oil Sulfur content mg/kg DISP, ml/m3 MD1, mg/kg MD2; mg/kg Cu2+ content mg/kg Induction period, h Time for delta kappa 40 microsiemens G235 50 0 0 0 0 20.7//17.1 21.1//20.8 G235 50 0 0 0 1 6//6.5 3.8//0.6 G235 50 600 0 0 1 15//17.3 8.3//8.1 G235 50 600 5 0 1 17.3//19.3// 19.5 7.3//7.3//7.1 G235 50 600 0 10 1 14.9//17.5 10.3//9.5 G235 50 600 0 20 1 20//14.9 8.7//8.2 MD.
- Metal deactivator Metal deactivator
Abstract
Description
- This invention is related to a new fuel composition which incorporates a chelating agent capable of stabilizing said fuel against the degradation thereof under working conditions and exposure to contamination by metals observed in the new combustion facilities and engines.
- Liquid fuels are used widely in industry for transport or furnaces. They are mostly obtained from oil refining, although they may incorporate components from other sources, for example biofuels.
- The stability of the oil fractions and the new fuel components is a property essential to ensuring their appropriate use. And guaranteeing this property is a highly difficult task, especially considering the wide variety of fuel compositions, depending upon their sources and the manner in which they are obtained.
- Numerous additives designed to solve the problems related to hydrocarbon instability currently exist on the market, with different formulations incorporating a complex balance of antioxidants, metal deactivators, neutralizers, detergents and dispersants. Most degradation routes lead to insoluble products, dispersants therefore usually being effective for alleviating this problem. However, there are rubber-forming routes which require an antioxidant to be avoided. In this regard, stabilizing additives exert an influence by neutralizing the acids resulting from oxidation. Other factors causing the speed-up of the oxidation mechanisms are metals (ex. Zn or Cu), such that metal deactivators are also a major factor controlling the degradation mechanisms.
- Metal deactivators are compounds complexing the metals dissolved in the hydrocarbons, preventing the metal ions from initiating or catalyzing the radicalary reactions responsible for said oxidation. The metal passivating compounds which laminate the metal surfaces for prevent their corrosion are also sometimes termed metal deactivators. These compounds, although having a secondary effect on the stability on reducing the solubility of the metals, do not inhibit the catalytic effect thereof for the degradation reactions.
- The use of metal deactivators and antioxidants in gasoline, kerosene and lubricants is mentioned in resources as detailed hereinabove. This is not the case of gas-oils, because the customary consequences of the degradation thereof has been sufficiently remedied to date with the use of dispersants, avoiding the complex use of other products. The use of this type of compounds in gas-oils has always been highly limited, given the complex nature of this fraction.
- The conventional scenario of medium distillates, the stability of which had been reasonably remedied with dispersants, is changing fast. Refineries now need to achieve progressively higher conversion ratios by incorporating currents which have undergone thermal or catalytic stress, their stability differing from the direct distillation currents. The environmental requirements are progressively greater; the permitted maximum sulfur contents are being drastically reduced, increasing the harshness of the hydrotreatment. This process eliminates natural antioxidants in the fuel, where sulphur is also included. Lastly, the modifications in the new combustion facilities and engines favor the presence of metal contaminants, with higher working temperatures and pressures.
- Fuel formulations are progressively more variable as a result of the new oil refining processes. The combined presence of direct distillation and conversion currents at different hydrotreatment levels is progressively more frequent and increases this variability to an even greater degree. The fuel compositions may therefore vary within broad ranges, having highly variable contents in critical compounds such as olefins, diolefins, sulfur and nitrogen heteroatoms, metals, etc. As a result of all of the above, the response of the stabilizers in medium distillates, especially in gas-oils, is highly complex and hardly foreseeable.
- Metals have recently been found to be present in fuels. In a sampling process conducted in 2003 on 78 commercial samples in Spain, the amount of said metals (Cu+Zn) was found to total up to 0.2 mg per kilo of fuel. In addition thereto, the high temperature of the new injection systems has been detected as capable of causing a high solution of Cu up to levels in excess of 1 ppm. These levels of high-temperature metal dissolution have been simulated in high-temperature laboratory tests, the concentrations determined in the field having been found to exist.
- The use of antioxidants and metal deactivators is stated in resources in kerosene-type medium distillates with sulfur contents of over 350 mg/kg (up to 3000 mg/kg). Sulfur being present is essential, given that it is a natural antioxidant. However, the use thereof in diesel fuel is extremely rare, and the effectiveness of these components varies when the sulfur content is less than 350 mg/kg (European legislation since 1999). The response of gas-oil to these additives still differs even more as the sulfur is reduced, being totally different on completely eliminating this element (sulfur content below 10 mg/kg). The EN-590 specification requires content of less than 50 mg/kg in all automotive gas-oils as of 2005 and of less than 10 mg/kg as of 2009.
- The way in which fuels are used is critical, given that the presence of certain factors such as light, dissolved metals, oxygen or the temperature accelerates the destabilizing of the fuel, which entails the forming of insoluble substances which could have a bearing on proper working order (clogging, corrosion, build-up). The evolution of the uses of this fuel requires improving the resistance thereof to the degradation processes.
- In the case of heating fuels, the evolution of their formulations has also been in conjunction with the evolution of the facilities where it is burned. The choice taken was that of a massive incorporation of copper pipes in the facilities, which facilitates the incorporation of copper into the fuel, to which a high recirculation rate to the fuel tank is also added. Additionally, the use of translucent materials for the storage tanks has likewise become widespread, which allows sunlight to act on the fuels. All of the above could help to increase the inestability of the fuels. Lastly, the injection systems have become progressively more complex, thus making fuel stability a critical property for the proper functioning thereof.
- In the case of diesel fuels, another important factor is the evolution of the new engines, with injection systems based on a pump injector and common rail. These systems are highly critical to insolubles and run at high temperatures. The study of the fuels on the market and of the dissolution of metals at high temperatures reveals the presence of metals which catalyze the degradation reactions. The presence of these catalysts and the high working temperatures degrade the fuel and give rise to the formation of insoluble residue which causes the fuel injection to malfunction.
- It is advisable to provide a solution to this type of contaminations and to protect the fuel. To this end, advantage can be taken of the experience acquired in other hydrocarbons and other uses different from combustion.
- Numerous sources make reference to the use of metal deactivators in naphthas. For example, di-(2-hydroxybenzal)-ethylendiamine (
US 2284267 ,US 2181121 andUS 2181122 ) and derivatives of N,N'-di-(3-alkenyl-salicylidene)-diaminoalkane (US 3071451 ) as a Cu deactivator in gasoline. Products of this type have a marked filming nature, their effectiveness on reducing the catalytic activity of metals is limited. - The DEF-STAN 91-91 specification indicates that aviation kerosene may incorporate an antioxidant in a concentration within the 17-24 mg/l range and an N,N'-disalicylidene-1,2-propanediamine metal deactivator in a concentration of < 2 mg/l. This is the only metal deactivator permitted in kerosenes and the only one used in other medium distillates. The use of N,N'-disalicylidene-1,2-propanediamine in kerosene is described in several publications (Pande, S.G. et al. in 6th International Conference on Stability and Handling of Liquid Fuel, Canada, 211-230 (1997) and Cyrus, P.H. in 6th International Conference on Stability and Handling of Liquid Fuel, Canada, 51-59 (1997)). In the article published by Chusei, C.C. et al. in Applied Surface Science, USA, 153 23-24 (1999), it is proven how the breakdown thereof may take place at temperatures in excess of 350°C.
- Triazoles and benzotriazoles are used in motor oils for the purpose of prevent corrosion related to the Pb in presence of metals (Cu, brass and bronze) as stated in
US patent 0038835 A1 . The proportioning used is quite high (2000 ppm). PatentWO 03/004476 A1 - The use of gluconic acid has been analyzed in depth given the interest in this patent. It is used as a metal and amine captor in refinery processes (
WO 2004020553 ) and as a raw material for lubricants (US 5773391 ,JP 61031213 US 4892671 ) and for sulfur recovery from natural gas (US 2004192995 ). In no case has it been used as a metal deactivator for improving the stability of a medium distillate. - The use of other Cu, Fe, Co and Cr deactivators, such as 1,1,1-tris-(salicylidenaminomethyl)-alkanes, are described in
US patent 3843536 . The effectiveness of these deactivators is solely demonstrated in gasoline and in lubricant oils in the presence of high concentrations of metals (respectively 8 and 18 ppm) and at high treatment proportioning with deactivator (100-1000 ppm). Nevertheless, these compounds function in a markedly filming manner, as revealed by the high proportions in which they are used. - N,N'-disalicylidene-1,2-propanediamine is also used in automotive gas-oil, as is stated in patent
EP 0476197 A1 . This patent is related to a formulation comprised mainly of a deactivator and an agent for improving the low-temperature stability of the additive. The effectiveness of said additive in the presence of Cu has not been demonstrated. InUS patent 2813080 , a formulation comprised of an N,N'-disalicylidene-1,2-propanediamine deactivator in combination with a dispersant and a combustion enhancer is described. The effectiveness of said formulation in the presence of metals is demonstrated only in the ASTM D-665 test (corrosion related to steel) where the function of the metal deactivator is as a filming agent and not a metal complexing agent. - It is highly advisable to broaden the application of the metal deactivators to the field of fuels and, more specifically, to the field of gas-oils. It is necessary in low-sulfur automotive gas-oils, which require a greater stability capable of withstanding the high temperatures reached in the new-generation combustion engines and the metal contamination detected in these systems. It is also necessary for the heating gas-oils, due to the progressive incorporation of conversion fractions and the impact which copper and sunlight have on the boiler facilities, the mechanisms (filters and pumps) of which are capable of tolerating a lesser degree of contamination and build-up.
- The limited availability of N,N'-disalicylidene-1,2-propanediamine has given rise to the need of seeking alternative products affording the possibility of diversifying the source of this component. In addition thereto, an opportunity has been found of enhancing the stabilizing effectiveness on certain low-sulfur gas-oil formulations.
- As a result of all of the above, an alternative metal deactivator to N,N'-disalicylidene-1,2-propanediamine has been found for gas-oils and fuels in general which also improves upon some deficiencies thereof.
- The inventors of the present invention have developed an alternative composition capable of stabilizing fuels by adding a certain amount of a chelating agent which is capable of forming complexes with the metal ions, inhibiting the catalytic effect thereof and checking the formation of insoluble substances which could have an effect on the proper working order of the engines and boilers (clogging, corrosion, build-up).
-
- In this invention, an assessment has been made of the effectiveness of gluconic acid in different proportions, ranging from 1 to 100 mg per kilogram of fuel.
- In one preferred embodiment of the following invention, the fuel is automotive, agricultural or heating gas-oil.
- In another preferred embodiment of the following invention, the composition described comprises 2-50 mg of Formula 1 compound per kilogram of fuel.
- In some cases, a dispersant (DISP) is used for improving the stability of the fuel by preventing the agglomeration of insolubles and the depositing thereof.
- Therefore, the composition described in the following invention may also comprise a dispersant such as, for example but without being limited to, a Mannich base or the derivatives thereof, represented by the following Formula IIa:
or a poly-isobutenesuccinimide or the derivatives thereof represented by the following formula IIb: - The dispersant added to the composition described in the present invention is used in a proportion ranging from 10 to 1000 mg per kilogram of fuel, more preferably from 50 to 300 mg per kilogram of fuel.
- An antioxidant may also be added to the composition described in the following invention for the purpose of enhancing the stability of the fuel, particularly of low-sulfur gas-oils or in absence of this natural antioxidant.
-
- In a second aspect of the present invention, a method for obtaining the fuel composition described hereinabove is provided, consisting of the following stages:
- a) formulating a fuel, preferably an automotive, agricultural or heating gas-oil, and
- b) Adding a quantity of the compound of Formula I, previously disclosed, to the fuel prepared in a)
- In a preferred embodiment of the method of the present invention, the addition of a polyisobutenesuccinimide type dispersant according to Formula IIb described hereinabove and preferably proportioned at 10 to 1000 mg per kilogram of fuel and more preferably, 50 to 300 mg per kilogram of fuel is included.
- One final aspect of the present invention provides the use of the Formula I compound described hereinabove for the stabilization of a fuel.
- More preferably, the use of the Formula I compound described in the present invention for the stabilization of a fuel, in which said fuel is preferably automotive, agricultural or heating gas-oil.
- In the present invention, the term "fuel" includes the liquid fuels intended for producing heat energy or for being used in internal combustion engines for producing mechanical energy.
- The term "multifunctional package" refers to a composition which comprises but is not limited to one or more dispersing, deemulsifying or antifoaming components. This composition may likewise include other components such as stabilizers, anti-rust additives or cetane improvers.
- In the present invention, all of the technical and scientific terms are of the same meaning as that commonly understood by an expert in the field to which the invention pertains. Throughout the description and the claims, the word "comprises" and the variations thereon are not intended to exclude other technical features, components or steps. For the person skilled in the art, other objects, advantages and characteristics of the invention will be implied in part from the description and in part from the practice of the invention. The following examples and drawings are provided for illustrative purposes and are not intended to be limiting of the present invention.
- The invention will be illustrated in following by means of some tests conducted by the inventors revealing the stability of the new composition described as an alternative to other compositions currently existing in the state-of-the-art.
- In example 1, a comparison is drawn between gluconic acid (Formula I) and different products having a chelating capacity, at 5 mg of product per kilogram of gas-oil. The different compounds compared are detailed in following:
- Ethylendiaminotetracetic acid
- Citric acid
- Pyrazole
- Imidazole
- Monoalkyl thiadazoles
- Dialkyl thiadazoles
- Benzoltriazol
- Tolyltriazol
- The best performance is achieved with gluconic acid. The other chelating agents show a worse performance, even going as far as promoting degradation in some of the gas-oil samples evaluated.
- In the following examples, the effectiveness of gluconic acid has been evaluated by comparing it to the metal deactivator authorized for aviation kerosenes (NNDDP: N,N'-disalicylidene-1,2-propanediamine), at different proportions (2-50 mg/kg), in low-sulfur gas-oils (50 and 10 mg/kg), in presence or absence of metal (Cu2+) and in presence or absence of a dispersant (DISP).
- The possible side-effects of the gluconic acid on different properties, such as filterability (internal method), compatibility with additives (proprietary method), antifoaming capacity (dry and wet manual tests, as well as test tube injection, NF-M-07-075), anti-rust properties (ASTM D-665-B; seawater) and emulsion with water (internal method) were also tested.
- A 50 ml sample of gas-oil doped with 1 ppm Cu2+ was aged for 90 minutes at 150°C in absence of light. Afterward, the increase in color in the gas-oil was evaluated as a measurement of the absorbance of the sample diluted in a zero-absorbance solvent. The effectiveness of the metal deactivators on three types of gas-oil of different sulfur contents: automotive gas-oil (GDM1005), agricultural gas-oil (GDM1006) and heating gas-oil (GDM239) were evaluated.
Table 1 Gas-oil MD used Increase in absorbance GDM239 None 0.2068 GDM239 B 0.3076 GDM239 C 0.2426 GDM239 Gluconic acid 0.1368 GDM239 E 0.2136 GDM239 F 0.2142 GDM239 G 0.2649 GDM239 H 0.2704 GDM239 I 0.2789 GDM239 J 0.3286 GDM239 K 0.3700 GDM1006 None 0.0741 GDM1006 B 0.0595 GDM1006 C 0.0386 GDM1006 Gluconic acid 0.0269 GDM1006 E 0.0584 GDM1006 F 0.0485 GDM1006 G 0.0652 GDM1006 H 0.0661 GDM1006 I 0.0512 GDM1006 J 0.0427 GDM1006 K 0.0538 GDM1005 None 0.0699 GDM1005 B 0.0462 GDM1005 C 0.0654 GDM1005 Gluconic acid 0.0445 GDM1005 E 0.0421 GDM1005 F 0.0536 GDM1005 G 0.0534 GDM1005 H 0.0599 GDM1005 I 0.0555 GDM1005 J 0.0805 GDM1005 K 0.0672 MD. Metal deactivator - HLPS detergency. A 250 ml sample of gas-oil was aged at 280°C, 38 bars, in a system similar to that used for determining the kerosene stability (ASTM-D-3241), recirculating the sample for a maximum of 4 hours. Afterward, the load loss through a filter located downstream from the maximum temperature area was evaluated. The Tendency to Deposits Formation (TDF) was determined in terms of the load loss and the time lapsed up to said loss.
- Gas-oils with 50 and 10 ppm sulfur were used and the effectiveness of the GA in presence of dispersant at 10 ppm was found to be better than that of the NNDDP at 5 ppm (gluconic TDF: 1.1-0.2; NNDDP TDF: 2.4-1.1), see Table 2.
- However, when the proportion of GA was increased up to 20 ppm, the results were worse (TDF: 1.3-3.6).
In this test, it was found, in turn, that neither of the two metal deactivators used are effective on their own, in other words, without a dispersant. - UOP-835 thermal stability. A 50 ml sample of gas-oil was aged for 90 minutes at 150°C in absence of light. Afterward, the sample was filtered and the increase in color of the gas-oil evaluated as a measurement of the absorbance of the diluted sample and the filter opacity.
Table 3 Gas-oil Sulfur content, mg/kg DISP, ml/m3 MD1, mg/kg MD2, mg/kg CU2+ content mg/kg Increase in absorbance Opacity G388 10 0 0 0 0 0.035 0.00 G388 10 0 0 0 1 0.059 0.06 G388 10 0 0 2 1 0.052 0.02 G388 10 0 0 5 1 0.050 0.04 G388 10 0 0 10 1 0.044 0.02 G388 10 600 0 2 1 0.048 0.03 G388 10 600 0 5 1 0.062 0.02 G388 10 600 0 10 1 0.048 0.02 G388 10 0 2 0 1 0.051 0.04 G388 10 0 5 0 1 0.039 0.03 G388 10 0 10 0 1 0.032 0.03 G388 10 600 2 0 1 0.060 0.02 G388 10 600 5 0 1 0.058 0.03 G388 10 600 10 0 1 0.044 0.03 G235 50 0 0 0 0 0.031 0.01 G235 50 0 0 0 1 0.072 0.04 G235 50 0 0 2 1 0.087 0.03 G235 50 0 0 5 1 0.084 0.02 G235 50 0 0 10 1 0.087 0.02 G235 50 0 0 20 1 0.096 0.01 G235 50 0 0 50 1 0.064 0.00 G235 50 600 0 2 1 0.073 0.01 G235 50 600 0 5 1 0.072 0.02 G235 50 600 0 10 1 0.092 0.01 G235 50 600 0 20 1 0.080 0.01 G235 50 600 0 50 1 0.096 0.01 G235 50 0 2 0 1 0.056 0.01 G235 50 0 5 0 1 0.051 0.01 G235 50 0 10 0 1 0.027 0.02 G235 50 600 2 0 1 0.054 0.02 G235 50 600 5 0 1 0.049 0.01 G235 50 600 10 0 1 0.02 0.01 G682 10 0 0 0 0 0.017 0.01 G682 10 0 0 0 1 0.045 0.01 G682 10 0 0 2 1 0.040 0.02 G682 10 0 0 5 1 0.040 0.01 G682 10 0 0 10 1 0.041 0.03 G682 10 0 0 20 1 0.045 0.01 G682 10 0 0 50 1 0.044 0.00 G682 10 600 0 2 1 0.028 0.01 G682 10 600 0 5 1 0.035 0.02 G682 10 600 0 10 1 0.035 0.02 G682 10 600 0 20 1 0.036 0.01 G682 10 600 0 50 1 0.035 0.03 G682 10 0 2 0 1 0.036 0.01 G682 10 0 5 0 1 0.027 0.00 G682 10 0 10 0 1 0.009 0.02 G682 10 600 2 0 1 0.030 0.01 G682 10 600 5 0 1 0.029 0.01 G682 10 600 10 0 1 0.025 0.01 G306 50 0 0 0 0 0.016 0.04 G306 50 0 0 0 1 0.118 0.07 G306 50 0 0 2 1 0.096 0.04 G306 50 0 0 5 1 0.112 0.03 G306 50 0 0 10 1 0.132 0.04 G306 50 600 0 2 1 0.090 0.03 G306 50 600 0 5 1 0.102 0.04 G306 50 600 0 10 1 0.093 0.04 G306 50 0 2 0 1 0.086 0.03 G306 50 0 5 0 1 0.015 0.04 G306 50 0 10 0 1 0.020 0.01 G306 50 600 2 0 1 0.077 0.03 G306 50 600 5 0 1 0.065 0.02 G306 50 600 10 0 1 0.064 0.02 MD. Metal deactivator - MD1
- N,N'-disalicylidene-propanediamine (NNDDAP)
- MD2
- gluconic acid (GA)
-
- Four 50 and 10 ppm gas-oil samples were used, it was found that, in presence of the dispersant (added as multifunctional package) on the gas-oils with 10 ppm sulfur, the GA at 10 ppm showed better results than the NNDDAP at 5 ppm.
The equivalency ratio, with dispersant, between the NNDDAP and GA would be 5:10 ppm, the GA being more effective on the bases of 10 ppm and the NNDDAP on those of 50 ppm. - Oxidation stability A 350 ml sample of gas-oil was aged under the conditions stipulated in standard ISO12205 (16 hours, 95°C, with 3L/h oxygen bubbling) in presence of 1 mg/kg Cu2+. Afterward, the insolubles produced were determined as the sum of filterable (0.8 microns) and adherent forms (washed with trisolvent and evaporation at 160°C), measured in g/m3. The Cu2+ was added as a reagent in acetate form.
Table 4 Gas-oil Sulfur content mg/kg DISP, ml/m3 MD1, mg/kg MD2, mg/kg Cu2+ content mg/kg Total insolubles, g/m3 Increase in absorbance G235 50 0 0 0 0 1.7 0.020 G235 50 0 0 0 1 Blocks filter Not measured G235 50 0 0 2 1 Blocks filter 0.625 G235 50 0 0 5 1 Blocks filter 0.562 G235 50 0 0 10 1 Blocks filter 0.635 G235 50 0 0 20 1 Blocks filter 0.604 G235 50 0 0 50 1 Blocks filter 0.620 G235 50 600 0 2 1 16.3 0.311 G235 50 600 0 5 1 26.0 0.284 G235 50 600 0 10 1 20.0 0.319 G235 50 600 0 20 1 8.0 0.145 G235 50 600 0 50 1 61.0 0.329 G235 50 0 2 0 1 Blocks filter 0.505 G235 50 0 5 0 1 11.7 0.149 G235 50 0 10 0 1 6.8 0.045 G235 50 600 2 0 1 11.4 0.344 G235 50 600 5 0 1 4.8 0.038 G235 50 600 10 0 1 2.9 0.041 G682 10 0 0 0 0 6.0 0.011 G682 10 0 0 0 1 448.8 0.344 G682 10 0 0 2 1 249.1 0.349 G682 10 0 0 5 1 286.9 0.387 G682 10 0 0 10 1 250.6 0.367 G682 10 0 0 20 1 176.5 0.369 G682 10 0 0 50 1 187.4 0.395 G682 10 600 0 2 1 33.2 0.241 G682 10 600 0 5 1 20.8 0.224 G682 10 600 0 10 1 15.4 0.153 G682 10 600 0 20 1 10.6 0.089 G682 10 600 0 50 1 32.3 0.317 G682 10 0 2 0 1 260.5 0.425 G682 10 0 5 0 1 354.3 0.391 G682 10 0 10 0 1 4.8 0.029 G682 10 0 20 0 1 6.3 0.025 G682 10 0 50 0 1 5.7 0.036 G682 10 600 2 0 1 9.7 0.216 G682 10 600 5 0 1 9.2 0.240 G682 10 600 10 0 1 12.0 0.031 G682 10 600 20 0 1 6.9 0.028 G682 10 600 50 0 1 6.9 0.046 MD Metal deactivator - MD1
- N,N'-disalicylidene-propanediamine (NNDDAP)
- MD2
- gluconic acid (GA)
-
- It was found that, on adding GA without a dispersant, to a 10 ppm sulphur content base fuel, the insolubles in the base were reduced to the half (from 448.8 to 187-250 g/m3) at any additioning proportion (2-50 mg/kg).
- In the cases in which dispersant was added, the gluconic acid showed the best results at 20 ppm (8-11 g/m3), being effective from 2 ppm and achieving less from 21 g/m3 at 10 ppm. In other words, in this case, no benefit was found from increasing the proportion. Tests were conducted up to 50 ppm.
- Test 5-1. Light stability. A 50 mL sample of gas-oil was aged at 40°C subjected to constant UV radiation for 48 hours, the resulting insolubles having been evaluated in a manner similar to Test 2, adapting the filter, the filtering equipment and the evaporation to the amount of sample employed.
Table 5-1 Gas-oil Sulfur content mg/kg DISP, m/m3 MD1, mg/kg MD2, mg/kg Cu2+ content mg/kg Total insolubles, g/m3 Increase in absorbance G235 50 0 0 0 0 27.1 0.031 G235 50 0 0 0 1 32.2 0.065 G235 50 600 0 0 1 38.0 0.051 G235 50 600 5 0 1 13.2 0.033 G235 50 600 0 10 1 23.0 0.022 G235 50 600 0 20 1 29.9 0.043 MD. Metal deactivator - MD1
- N,N'-disalicylidene-propanediamine (NNDDAP)
- MD2
- gluconic acid (GA)
-
- The GA at 10 ppm was found to reduce the insolubles to 23 g/m3.
- Test 5-2. DUPONT stability (6 weeks, 43°C). A 350 ml volume of sample was stored at 43°C for 42 days, both the insoluble and the adherent forms and the increase in absorbance having then been quantified.
Table 5-2 Gas-oil Sulfur content mg/kg DISP, ml/m3 MD1, mg/kg MD2, mg/kg Cu2+ content mg/kg Total insolubles g/m3 Increase in absorbance G235 50 0 0 0 0 1.7 0.031 G235 50 0 0 0 1 6.6 0.182 G235 50 600 0 0 1 19.5 0.214 G235 50 600 5 0 1 7.5 0.373 G235 50 600 0 10 1 5.9 0.277 G235 50 600 0 20 1 7.4 0.353 MD. Metal deactivator - MD1
- N,N'-disalicylidene-propanediamine (NNDDAP)
- MD2
- gluconic acid (GA)
-
- Both metal deactivators were found to be effective at the proportions tested (NNDDP at 5 ppm and GA at 10 and 20 ppm), having managed to reduce the insolubles formed by the base in presence of copper and dispersant to less than half (from 19.5 g/m3 to < 5.9 g/m3). See Table 5-2.
- Test 5-3: Rancimat stability. Air was made to flow through a sample of gas-oil at 110°C. The fumes given off in the oxidation process, along with the air, were routed through a vessel containing distilled water, where the conductivity was measured, which increases by way of the acids formed during the aging process. The end of the induction period was indicated when the conductivity began to rapidly increase. For the purpose of identifying the progressive destabilization (without any abrupt increase in the production of acids), the length of time having lapsed up to a certain conductivity was also recorded.
- The results of the aforementioned test are provided in the second table (Table 5-3).
Table 5-3 Gas-oil Sulfur content mg/kg DISP, ml/m3 MD1, mg/kg MD2; mg/kg Cu2+ content mg/kg Induction period, h Time for delta kappa 40 microsiemens G235 50 0 0 0 0 20.7//17.1 21.1//20.8 G235 50 0 0 0 1 6//6.5 3.8//0.6 G235 50 600 0 0 1 15//17.3 8.3//8.1 G235 50 600 5 0 1 17.3//19.3// 19.5 7.3//7.3//7.1 G235 50 600 0 10 1 14.9//17.5 10.3//9.5 G235 50 600 0 20 1 20//14.9 8.7//8.2 MD. Metal deactivator - MD1
- N,N'-disalicylidene-propanediamine (NNDDAP)
- MD2
- gluconic acid (GA)
-
- As shown in the Table, there were no differences in effectiveness between the NNDDP at 5 ppm and the GA at 10 and 20 ppm. The two metal deactivators, in the stated proportions, enhanced the result in presence of copper and dispersant up to values nearing those of the base gas-oil. The gluconic acid shows a better performance than the NNDDP is the progressive destabilization is taken into account.
Claims (14)
- Composition according to Claim 1 hereinabove where the fuel is automotive, agricultural or heating gas-oil.
- Composition according to any of the preceding Claims hereinabove which comprises from 1 to 100 mg of Formula I compound per kilogram of fuel.
- Composition according to any of the preceding Claims hereinabove which comprises from 2 to 50 mg of Formula I compound per kilogram of fuel.
- Composition according to any of the preceding Claims hereinabove which also comprises a dispersant selected from among the following:a. a Mannich base or derivatives thereofb. a polyisobutenesuccinimide or the derivatives thereof, orc. a combination of both.
- Composition according to Claims 5 or 6 hereinabove in which the dispersant is used in a proportion of 10 to 1000 mg per kilogram of fuel.
- Composition according to Claims 5 or 6 hereinabove in which the dispersant is used in a proportion of 50 to 300 mg per kilogram of fuel.
- Composition according to any of Claims 5 to 8 hereinabove in which the dispersant is incorporated in conjunction with all of the components of a multifunctional package.
- Method for obtaining a fuel composition in accordance with Claim 1 hereinabove which comprises the following stages:a. formulating a fuel, andb. Adding a Formula I compound to the fuel prepared in a)
- Method according to Claim 11 hereinabove in which the fuel composition is any of the compositions described in Claims 2 to 10.
- Use of a Formula I compound for the stabilization of a fuel.
- Use according to Claim 13 hereinabove in which the fuel is automotive, agricultural or heating gas-oil.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009040584A1 (en) * | 2007-09-27 | 2009-04-02 | Innospec Limited | Fuel compositions |
WO2009040583A1 (en) * | 2007-09-27 | 2009-04-02 | Innospec Limited | Fuel compositions |
GB2453248B (en) * | 2007-09-27 | 2011-11-23 | Innospec Ltd | Fuel compositions |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2009040584A1 (en) * | 2007-09-27 | 2009-04-02 | Innospec Limited | Fuel compositions |
WO2009040583A1 (en) * | 2007-09-27 | 2009-04-02 | Innospec Limited | Fuel compositions |
CN102037104A (en) * | 2007-09-27 | 2011-04-27 | 因诺斯佩克有限公司 | Fuel compositions |
GB2453248B (en) * | 2007-09-27 | 2011-11-23 | Innospec Ltd | Fuel compositions |
CN102037104B (en) * | 2007-09-27 | 2014-12-31 | 因诺斯佩克有限公司 | Fuel compositions |
US9157041B2 (en) | 2007-09-27 | 2015-10-13 | Innospec Limited | Fuel compositions |
US9163190B2 (en) | 2007-09-27 | 2015-10-20 | Innospec Limited | Fuel compositions |
US9243199B2 (en) | 2007-09-27 | 2016-01-26 | Innospec Limited | Fuel compositions |
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ES2301358A1 (en) | 2008-06-16 |
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