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

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Citations (18)

• 2006
  • 2006-05-12 ES ES200601236A patent/ES2301358B1/es active Active
• 2007
  • 2007-05-11 EP EP07108062A patent/EP1854867A1/fr not_active Withdrawn

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