WO2003091361A2 - Method and apparatus for improving the oxidative thermal stability of distillate fuel - Google Patents
Method and apparatus for improving the oxidative thermal stability of distillate fuel Download PDFInfo
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- WO2003091361A2 WO2003091361A2 PCT/GB2003/001752 GB0301752W WO03091361A2 WO 2003091361 A2 WO2003091361 A2 WO 2003091361A2 GB 0301752 W GB0301752 W GB 0301752W WO 03091361 A2 WO03091361 A2 WO 03091361A2
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
- C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
- C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur compounds
Definitions
- the present invention relates to methods of improving the thermal oxidative stability of a distillate fuel, to methods of determining the thermal oxidative stability of a distillate fuel and to apparatus for performing said methods.
- thermal oxidation stability relates to the stability of the distillate jet fuel at elevated temperatures, such as in the aircraft fuel system and engine. Jet fuels need to meet certain thermal stability specifications to comply with international operational safety requirements .
- JFTOT Jet Fuel Thermal Oxidation Tester
- Oxidation Stability of Aviation Turbine Fuels American Society for Testing and Materials, 1991. Numerous chemical factors have been linked with the problems of thermal oxidative stability. Although forming only a minor proportion of the fuel, the majority of the deposits formed have been attributed to reactions of relatively minor components present. For example, auto-oxidation has been proposed to be a significant process for deposit formation, and compounds containing oxygen, sulphur, nitrogen and metals have all been linked to the extent of deposit formation.
- thermal oxidative stability has been shown to vary strongly between different fuels. Although individual components have been identified as contributing to problems of stability in certain fuels in certain situations the previous results have often been contradictory or have been performed under experimental conditions or at temperatures inconsistent with the standard JFTOT test.
- WO 91/05242 relates to a method of testing oil for unstable reactive compounds characterised by contacting at least one said reactive compound from a sample of oil with an acid catalyst to form a coloured reaction product, then relating the visible colour and/or colorimetric absorbance between 600-850 nm of this product to the presence and/or amount of unstable reactive compounds in the oil.
- the test relies upon the oxidation of phenalenes by the oxidising agent to phenalenones and the subsequent formation of coloured indolylphenalene salts in the presence of acid.
- Such salts are said to be generally blue to blue- violet in colour, but may vary between blue and green in the test.
- ASTM standard UOP 276-85 entitled Pyrrole Nitrogen in Petroleum Distillates by Visible Spectroscopy is said to be a method for determining the approximate concentration of pyrroles and indoles having at least one hydrogen per carbon atom in the heterocyclic ring by visible spectroscopy.
- the method is said to be applicable to gasolines, naphthas, kerosenes and distillate burner oils, but not applicable to crude and vacuum gas oils, which are not completely soluble in n-hexane.
- Olefins are said to interfere with the reaction and must be removed prior to analysis. It is said that aromatic amines or aliphatic mercaptans can also interfere with the reaction.
- the method is said to involve removal of olefins by column chromatography followed by addition of 85% phosphoric acid containing p-dimethylaminobenzaldehyde. Acetic acid is added and a deeply coloured red solution is formed. The absorbance of the coloured solution is determined spectroscopically at 540 nm and the result compared to a previously prepared calibration curve, prepared using 2-methylindole as a standard.
- This method involves the use of both phosphoric acid and acetic acid as well as chromatographic removal of olefins.
- a method for improving the thermal stability of a distillate fuel which comprises selectively reducing the active concentration in the fuel of N-H containing heterocychc aromatic compounds in which the nitrogen atom of the N-H group is part of the aromatic system and wherein said fuel also contains an active concentration of metal compounds or will be exposed to active metal compounds in storage or in use.
- a method for improving the thermal stability of a distillate fuel which comprises reducing the active concentration of metal compounds in the fuel, wherein the fuel also contains a deleterious level of N-H containing heterocychc aromatic compounds in which the nitrogen atom of the N-H group is part of the aromatic system.
- Deleterious level refers to a level which would have a significant effect on thermal stability as shown by deposit formation on a JFTOT test. Typically, this level will be greater than 20 mg/litre, such as greater than 50mg/litre.
- a method for improving the thermal stability of a distillate fuel which comprises selectively reducing the active concentration of N-H containing heterocychc aromatic compounds in which the nitrogen atom of the N-H group is part of the aromatic system and reducing the active concentration of metal compounds present in the fuel.
- the thermal stability of the fuel can be significantly improved by reducing the active concentration of the metal compounds, or alternatively by reducing the active concentration of the N-H containing heterocyclic aromatic compounds, or alternatively by reducing both components.
- the thermal stability of the fuel is improved by selectively reducing the active concentration in the fuel of N-H containing heterocychc aromatic compounds in which the nitrogen atom of the N-H group is part of the aromatic system.
- selectively reducing as used herein is meant to reduce the active concentration of one or more of the N-H containing species in preference to reducing the concentration of other nitrogen-containing species, and, most preferably, without deliberate reduction of said other species.
- selectively reducing pyrroles and indoles means to reduce the levels of pyrroles and indoles in preference to other N-containing species, such as pyridines, for example.
- non-selective methods of reduction of N-containing compounds, such as hydrotreating are excluded from the method of the present invention.
- Hydrotreating for example, reduces large numbers of N-containing and other polar compounds in a non-selective manner which can have significant effects on other properties of the fuel, such as the lubricity of the fuel.
- Selective reduction has the advantage that the overall composition of the fuel is less significantly changed, and hence the other properties of the fuel, such as lubricity are less significantly affected by the method of the present invention.
- hydrotreating uses a large amount of hydrogen, which has a significant cost.
- a large amount of this hydrogen is thus utilized removing N-containing species which have relatively insignificant effects in the thermal stability of a fuel.
- selectively reducing the species which have been found to be most deleterious according to the method of the present invention is a more efficient treatment method and avoids or at least mitigates problems with non-selective reduction methods which lead to more significant changes in the composition of the fuel.
- the distillate fuel maybe a jet fuel, avgas, diesel or gasoline.
- the distillate fuel is a jet fuel, such as Jet- A, Jet A-l, JP-8 or F-35.
- the deleterious N-H containing heterocyclic aromatic compounds are those in which the electrons of the nitrogen atom of the N-H group can interact with the aromatic system.
- examples of such compounds include pyrrole, indole, pyrazole, carbazole, substituted pyrroles, indoles, pyrazoles and carbazoles, and related compounds, preferably pyrrole, indole, substituted pyrroles and substituted indoles.
- Such nitrogen atoms, as part of the aromatic system have a significantly reduced basicity compared to conventional amines. Without wishing to be bound by theory it is believed that this property makes the ring more reactive to coupling and polymerisation type reactions, and hence makes these compounds susceptible to reactions leading to deposit formation.
- metals or metal compounds have now been found to contribute to the deposition process. Again without wishing to be bound by theory it is also believed that these metals and metal compounds may catalyse at least a part of the deposition process.
- Metals typically present in a distillate fuel may include copper, iron, lead and zinc. Typically these are present at low levels, such as in the parts per billion range (ppb).
- the active metal compounds which it may be desirable to remove or reduce preferably comprise transition metals and, most preferably, comprise copper and/or iron compounds present in the fuel. Most preferably, the active metal compounds which it maybe desirable to remove or reduce comprise copper compounds.
- the fuel may be exposed to active metals in storage and in use.
- the US Navy has encountered problems with copper contamination of JP-5 fuels on aircraft carriers.
- the fuel may be exposed to any of the transition metals present in the steel and/or these metals may potentially leach in to the fuel.
- any method for the reduction of active metal components at source may not have a significant effect after storage or in use. Methods that reduce the amount of active metals, such as copper, to which the fuel is exposed or otherwise prevent the formation of active metal species, are hence preferred.
- problems of deposit formation are particularly an issue when the fuel is at temperature, such as just prior to combustion, for example, in nozzles.
- the fuel can also be circulated as a coolant prior to use which may increase the extent of degradation before use.
- the methods of the present invention comprise selectively reducing the active concentration of deleterious N-H containing heterocyclic aromatic compounds and/or the active concentration of metal compounds present in the fuel.
- the active concentration of the deleterious N-H containing heterocyclic aromatic compounds may be selectively reduced by any known method, h one embodiment this may include physical removal of at least a portion of said compounds from the fuel, for example by treatment with a suitable adsorbent material.
- the suitable adsorbent material is rendered selectively active towards said compounds. Selective adsorption, as distinct from general removal of polar species, will prolong the lifetime of the adsorption unit by increasing the time for saturation to occur.
- Selective adsorption may also increase the ease by which regeneration can be achieved, owing to the specific nature of the adsorbed species.
- Selective adsorption may be obtained by surface modification of common adsorbents to tailor the adsorbent for the specific chemical species, as is known for a range of different applications.
- selective adsorption techniques are well known from developments in chromatographic stationary phase technology and could be readily applied to removal of species according to the present invention.
- the relatively low basicity of the deleterious N-H containing heterocyclic aromatic compounds, such as pyrroles the active concentration of which are to be reduced in the present invention, distinguish them from the more basic compounds also present in the fuel that have found to be less important in the deposit forming process.
- Suitable adsorbent material examples include compounds having a benzaldehyde functionality supported on a suitable support.
- the compound having a benzaldehyde functionality (hereinafter referred to as "benzaldehyde”) is a 4- aminobenzaldehyde. It has been found that such compounds will react with pyrroles and indoles to form a complex, thus removing the pyrroles and indoles from the fuel.
- the 4-aminobenzaldehyde is a 4-dialkylaminobenzaldehyde.
- the alkyl groups of the 4-dialkylaminobenzaldehyde may be the same or may be different.
- the alkyl groups are independently selected from methyl, ethyl, propyl and butyl groups.
- the 4-dialkylaminobenzaldehyde may be, for example, 4-methylethylaminobenzaldehyde, but preferably the alkyl groups are the same, and most preferably the 4-dialkylaminobenzaldehyde is 4- dimethylaminobenzaldehyde.
- the suitable support is preferably selected from the group consisting of clays, carbons, aluminas, silicas and zeolites.
- the benzaldehyde may be a 4-aminobenzaldehyde functionality which is chemically part of the suitable support, for example, is an end group or pendant group on a polymer backbone that forms the support material.
- the support is a clay.
- the suitable adsorbent material is thus, preferably, a surface-modified clay, which clay has been modified by addition of a benzaldehyde.
- the surface-modified clay is prepared by adsorption on to the surface of the clay of the benzaldehyde, more preferably by adsorption of 4- dimethylaminobenzaldehyde.
- the clay should exhibit high affinity characteristics for the benzaldehyde, such that the benzaldehyde is strongly, preferably irreversibly, adsorbed.
- Clays with suitably high affinity for benzaldehydes may be found in a suitable handbook of clay properties, such as the "Data Handbook for Clay Minerals and Other Non-metallic Minerals", edited by H. Van Olphen and J. J. Fripiat, and published by Pergamon Press.
- the clay is a kaolinite, more preferably a low defect kaolinite, such as Kaolin KGa-1, available from the Clay Repository of the Clay Minerals Society.
- the adsorbent is preferably a low defect kaolinite on which has been adsorbed 4- dimethylaminobenzaldehyde.
- Benzaldehydes in particular 4-dialkylaminobenzaldehydes, have been found to strongly adsorb on the surfaces of kaolinite materials.
- the benzaldehyde is preferably adsorbed to a level of at least 0.5 of a monolayer coverage, most preferably to a level of approximately 1 monolayer coverage, such as a coverage equivalent to 0.8 to 1.2 monolayers.
- the active concentration of N-H containing heterocyclic aromatic compounds in a fuel may be reduced by contacting said fuel with the suitable adsorbent material in any known manner. This may be done, for example, by mixing the fuel and adsorbent material and subsequently separating the fuel, for example, by filtration. Alternatively, and preferably, the contacting may be achieved by passing the fuel through a suitable column containing the adsorbent material. Any suitable temperature may be used, such as 5 to 100°C, preferably ambient temperature.
- the method of the present invention may be performed on the fuel at any suitable stage from, and including at, the refinery, during transportation or in storage of the fuel and up to, including in, the fuel system of the appropriate vehicle.
- the method of the present invention may be performed before the fuel is hydrotreated.
- specific absorbents derived from size- or shape-selective materials may be used to reduce the active concentration of the deleterious N-H containing heterocyclic aromatic compounds.
- the reduction of the active concentration of the deleterious N-H containing heterocyclic aromatic compounds may be achieved by reacting the compounds to form species that are inactive or less active in the deposition reaction, for example by complexing the compound (including its participation as a "guest” in a molecular "host-guest” relationship), by addition of a protecting group to the N-H functionality, or by reduction of the reactivity of the compound by substitution of a substituent that makes the aromatic heterocycle less susceptible to deposit forming reactions.
- the active concentration of the metal compounds present in the fuel may also be reduced by any known method. Suitable methods may or may not be molecularly specific in their action. In one embodiment this may include physical removal of at least a portion of said compounds from the fuel, for example by treatment such as ion exchange or by filtration through a suitable adsorbent, such as clay filtration.
- the reduction of the active concentration of metal compounds may be achieved by reacting the compounds to form insoluble species that may be removed from the fuel or by reacting the metal compounds to form species that are inactive or less active for the deposition reaction, for example by complexing the metal compound or by adding a metal deactivator (MDA) such as a chelating agent, for example disalicylidene-l,2-propandiamine.
- MDA metal deactivator
- solid-supported metal chelators can be used whereby selective adsorption of metal species can occur.
- complexing agents or metal deactivators should be compatible with the intended use of the fuel.
- both deleterious N-H containing heterocyclic aromatic compounds and active metal complexes may be selectively adsorbed by one supported adsorbent system comprising two specific adsorption sites. Where it is desired to reduce the active concentrations of both species this allows effectively simultaneous reduction.
- thermal oxidative stability has previously been shown to vary strongly between different fuels and results have often been contradictory.
- the deposit formation is strongly influenced by the co-presence of both certain active metal compounds and certain N-H containing heterocyclic aromatic compounds, and that, relative to these components, certain other compounds, including other nitrogen compounds, sulphur compounds and oxygen compounds have been found to have a relatively smaller effect on deposit formation, it is possible to explain at least some of the previous variation in thermal oxidative stability results between different fuels and by different groups.
- test method for determining the thermal stability of a distillate fuel comprises (a) contacting the distillate fuel with a solvent being at least partially immiscible with said fuel and comprising 4-aminobenzaldehyde in formic acid, to form an oil-immiscible layer and (b) relating the visible colour and or colorimetric absorbance between 400 and 700 nm of said oil-immiscible layer to the thermal stability of the fuel.
- the 4-aminobenzaldehyde is a 4-dialkylaminobenzaldehyde.
- the alkyl groups of the 4-dialkylaminobenzaldehyde may be the same or may be different.
- the alkyl groups are independently selected from methyl, ethyl, propyl and butyl groups.
- the 4-dialkylaminobenzaldehyde maybe, for example, 4-methylethylaminobenzaldehyde. More preferably the alkyl groups are the same, and most preferably the 4-dialkylaminobenzaldehyde is 4-dimethylaminobenzaldehyde.
- test method of the present invention solves the technical problem identified with prior art testing methods above, not least by providing a test which does not require the prior removal of olefins.
- test method takes advantage of the immiscibility of formic acid with the fuel, its ability to partition the active pyrrolic and indolic compounds from the fuel, and its relatively weak acidity, such that the procedure uses fewer reagents and operations, and avoids the necessity of separating the indoles by column chromatography.
- the colour and or colorimetric absorbance may be related to thermal stability of the fuel by a suitable comparison.
- the visible colour of the oil immiscible layer may be compared, by eye, with a suitable reference colour chart.
- the colorimetric absorbance between 400 and 700nm may be measured using a suitable spectrometer to give measured absorption values at one or more values or over one or more ranges within the range 400 to 700 nm, and this value may then be compared with suitable reference data, such as absorbance values for suitable reference fuels.
- suitable reference data may be in the form of a graph of absorbance versus concentration of particular components or may relate the absorbance directly to the thermal stability of the distillate fuel.
- the reference fuels may be solutions comprising known concentrations of model compounds, such as indole or 2-methylindole, in hydrocarbon model fuels, such as, for example, dodecane.
- the test method of the present invention may be applied to jet fuel, avgas, diesel or gasoline distillate fuels.
- the solvent is preferably a solution of the 4-aminobenzaldehyde in formic acid but may also comprise water, for example, a solution of 4-aminobenzaldehyde in aqueous formic acid, or mixtures with other oil-immiscible liquids.
- the concentration of formic acid in the solvent may be at least 20% by weight, preferably at least 50% by weight.
- the concentration of 4-aminobenzaldehyde in the solvent may be in the range
- the 4-aminobenzaldehyde is 4-dimethylaminobenzaldehyde, which is a commercially available compound sometimes referred to as Ehrlich's reagent.
- test method of the present invention can be preformed using on relatively small amounts of fuel, and using relatively small amount of solvent.
- the amount of distillate fuel used in the test method of the present invention may be in the range 2 to 25 ml, preferably in the range 5 to 10 ml.
- the amount of solvent should be sufficient for the colour and/or colorimetric comparison, for example for colorimetric analysis, typically at least 5ml, preferably in the range 5 to 25 ml, more preferably in the range 5 to 10 ml
- the fuel may be contacted with the solvent, preferably by mixing under agitation, such as stirring or shaking, and suitably at ambient temperature. Suitable mixing may be achieved in 5 seconds or less, but preferably mixing may be for at least 10 seconds, such as 10 to 30 seconds. Generally, shaking for 10 to 20 seconds is sufficient to achieve mixing.
- agitation such as stirring or shaking
- the fuel and solvent are then allowed to separate, typically for a period of at least 5 minutes, such as 5 to 30 minutes, preferably 10 to 20 minutes.
- an apparatus comprising a kit of parts suitable for use in the test method of the present invention.
- said apparatus comprises a first vessel containing a determined amount of solvent comprising a determined amount of 4- aminobenzaldehyde in formic acid, a measuring container suitable for measuring a determined amount of the distillate fuel, a second vessel suitable for mixing the determined amount of solvent with the determined amount of distillate fuel, and a third vessel suitable for optical analysis of the solvent phase.
- the 4-aminobenzaldehyde is a 4-dialkylaminobenzaldehyde.
- the alkyl groups of the 4-dialkylaminobenzaldehyde may be the same or may be different.
- the alkyl groups are independently selected from methyl, ethyl, propyl and butyl groups.
- the 4-dialkylaminobenzaldehyde may be, for example, 4-methylethylaminobenzaldehyde.
- the alkyl groups are the same, and most preferably the 4-dialkylaminobenzaldehyde is 4-dimethylaminobenzaldehyde.
- first to third vessels described in the first embodiment of the apparatus may be replaced by a single vessel.
- first vessel containing a determined amount of solvent may also be suitable for mixing of the determined amount of solvent with the determined amount of distillate fuel, and/or may also be suitable for optical analysis of the solvent phase.
- the vessel suitable for mixing the determined amount of solvent with the determined amount of distillate fuel is also suitable for the subsequent optical analysis of the solvent phase.
- the first vessel preferably comprises a vial containing a specific volume of the solvent comprising a determined concentration of 4-aminobenzaldehyde in formic acid- for example 5ml of solvent containing 3mg of 4-dimethylaminobenzaldehyde per ml of formic acid.
- the preferred apparatus also comprises a measuring container, such as a measuring cylinder or a suitable pipette for measuring the required amount of distillate fuel, and a stoppered container for mixing the fuel and solvent, said container also being suitable for subsequent optical analysis.
- the stoppered container may be a stoppered cuvette suitable for mixing the fuel and solvent, which cuvette, after allowing the phases to separate and being placed in a suitable measurement device, allows the solvent phase to be directly analysed.
- the suitable measurement device may be a colour comparator or may comprise a more sophisticated spectrophotometer which may measure absorbance at one or more specific wavelengths and/or over a given wavelength range (for example, by integration), such as, especially where the 4- aminobenzaldhyde is 4-dimethylaminobenzaldehyde, the range 530 to 570nm.
- the present invention also allows improvements to be made in the JFTOT test.
- JFTOT or other thermal oxidative stability testing apparatus using one or more calibration fluids (standards) comprising the active metal compounds and/or active N-H containing heterocyclic aromatic compounds, said compounds being as defined above.
- This calibration allows the user of the apparatus to plot the response of the JFTOT or other thermal oxidative stability apparatus to said compounds, and hence to identify the contribution of said compounds to the deposits formed in JFTOT or thermal oxidative stability tests.
- the present invention also provides one or more calibration fluids comprising a known concentration of active N-H containing heterocyclic aromatic compounds and/or a known concentration of active metal compounds, and a hydrocarbon phase.
- the present invention also provides a method of calibration of a thermal oxidative stability apparatus using one or more calibration fluids comprising a known concentration of active N-H containing heterocyclic aromatic compounds and/or a known concentration of active metal compounds, and a hydrocarbon phase.
- the active N-H containing heterocyclic aromatic compounds and/or active metal compounds are as described above.
- the thermal oxidative stability apparatus is preferably a JFTOT apparatus.
- the hydrocarbon phase may be any suitable hydrocarbon or mixture of hydrocarbons of known composition.
- the hydrocarbon phase is a saturated aliphatic hydrocarbon of 8 to 15 carbons atoms, for example, n-dodecane.
- the one or more calibration fluids preferably comprise one or more fluids containing both active N-H containing heterocyclic aromatic compounds and active metal compounds, but may also comprise one or more fluids containing active N-H containing heterocyclic aromatic compounds but not containing active metal compounds and/or one or more fluids containing active metal compounds but not containing active N-H containing heterocyclic aromatic compounds.
- a single calibration fluid may be used to produce a deposit in the thermal oxidative stability apparatus, such as in a JFTOT tube.
- more than one calibration fluid is used, and the calibration fluids may be used to produce more than one deposit, such as a series of deposits, in the thermal oxidative stability apparatus, for example a series of deposits in JFTOT tubes with varying deposit colouration.
- Such deposits may be used as standard responses (standards) and allow the results from unknown fuels to be compared. Where enough standards are known a calibration curve may be derived. In addition to measuring unknown fuels on an apparatus, results on fuels from different thermal oxidative stability equipment can be readily compared using the results from equivalent standards run on the respective pieces of equipment.
- the deposits formed from a calibration fluid according to the present invention may also be used to verify the performance of a thermal oxidative stability apparatus, for example, to check that the apparatus is performing within acceptable ranges and/or with required reproducibility/accuracy.
- calibration fluids as used herein includes verification fluids comprising the active metal compounds and/or active N-H containing heterocyclic aromatic compounds
- the method of calibration according to the present invention includes verification of the performance of the thermal oxidative stability apparatus using one or more verification fluids.
- the calibration fluids may be run individually to create such standards and/or may be mixed with other such calibration fluids and/or with fuels.
- the mixture of two calibration fluids in a known combination will give a third calibration fluid of known composition.
- an unknown fuel may be combined (or doped) with a known quantity of a calibration fluid, and the results from the doped fuel compared to the undoped fuel (and, optionally, with standards).
- the calibration fluids preferably have an active N-H containing heterocyclic aromatic compound content, for example 2-methylindole, pyrrole arid/or 2,5- dimethylpyrrole content, of from 0 to 250mg/l.
- the calibration fluids preferably have an active metal compounds content, for example a copper(II) ion content, of from 0 to lOOppb.
- the calibration fluids may also be used as calibration fluids for other types of thermal oxidative stability tests, such as the test method of the fourth aspect of the present invention.
- Figure 1 shows results from JFTOT screening of different compounds in Jet A-l (Jl) at 270 and 280°C on aluminium JFTOT tubes.
- Figure 2 shows a comparison between deposition tendencies for Jl jet fuel and dodecane containing 250 mg l "1 2-methylindole as a function of JFTOT test temperature.
- Figure 3 shows JFTOT tube profiles showing the effect of different copper (II) concentrations in dodecane on deposit formation in the presence of 250 mg I "1 2- methylindole at 260°C.
- Figure 4 shows aluminium JFTOT tube profiles showing the deposition occurring in dodecane containing 100 ppb Cu 11 and 250 mg l '1 thianaphthene at 260 and 340°C.
- Figure 5 shows aluminium JFTOT tube profiles showing the deposition occurring in dodecane containing different concentrations (indicated) of collidine and copper(II) at 260°C.
- Figure 6 shows the dependence of JFTOT deposit volume on copper(II) concentration in the presence of pyrrole and 2,5-dimethylpyrrole using aluminium tubes at 260°C.
- Figure 7 shows the effect of a metal deactivator (6 mg l "1 ) on deposition produced from dodecane in the 2-methylindole (250 mg l "1 ) / 100 ppb copper(II) system (aluminium tubes).
- Figure 8 shows stainless steel JFTOT tube deposit profiles showing the deposition occurring in dodecane containing 2-methylindole (250 mgl "1 ) and different copper(II) concentrations at 260°C.
- Figure 9 shows the effect of a metal deactivator on deposition produced from dodecane in the 2-methylindole (250 mg l "1 ) / 100 ppb copper(II) system (stainless steel tubes).
- Figure 10 shows a calibration plot showing absorbance at 545 nm of formic acid/DMAB solutions as a function of 2-methylindole concentration in dodecane.
- Figure 11 shows the UN- Visible spectra for formic acid/DMAB solutions of extracts from three jet fuels.
- Materials n-Dodecane (ex Aldrich) was used as the model hydrocarbon phase for the JFTOT studies.
- Samples of a jet fuel (Jet A-l, ex Coryton Refinery) with a breakpoint of 270°C were also used in several of the tests.
- Thianaphthene, benzofuran and indene were also tested in an identical manner. However these substrates all showed low deposit volumes with no significant change in the deposition tendencies for these substrates in the presence of copper, compared with its absence. These results show that these non-N-H containing aromatic compounds do not give significant deposit formation.
- Figure 4 shows this for dodecane containing 100 ppb copper(II) and 250 mg l "1 of thianaphthene at two temperatures.
- Figure 8 contains deposit profiles for JFTOT tests carried out on 2-methylindole
- active metal compounds are present when using a stainless steel JFTOT tube.
- Figure 9 shows the effect of addition of a metal deactivator (disalicylidene-1,2- propanediamine), in the case of the 2-methylindole system on stainless steel. Again the use of a metal deactivator reduces the formation of deposits. These results illustrate that the use of a metal deactivator will still reduce the active concentration of metal compounds when these are due to the metallurgy with which the fuel is in contact.
- a metal deactivator diisalicylidene-1,2- propanediamine
- the following examples illustrates the production of a calibration fluid comprising active N-H containing heterocyclic aromatic compounds and/or active metal compounds, and the use of such a fluid to calibrate a thermal oxidative stability apparatus.
- the method of preparation of the calibration fluid is similar to that used to prepare the solutions described in the Examples above.
- the resultant mixture was then be subjected to testing in a JFTOT under ASTM D3241 conditions at 260°C.
- the deposit thus formed may be used as a standard and compared to deposits obtained from jet fuels in the same apparatus or may be used to verify the performance of the apparatus.
- the volume of deposit resulting from this test using the calibration fluid as described above should be in the range 1 to 2 x 10 "5 cm 3 , corresponding approximately to a "3" visual colour rating on the ASTM D3241 scale.
- Figure 3 shows a series of deposits formed at varying concentrations of copper (II) compounds in a model fuel with 250mg/l of 2-methyindole. These could form a series of standard deposits, as described above, for the particular JFTOT apparatus and conditions. An unknown fuel could be tested on the same apparatus and under the same conditions and compared to these deposit profiles. The calibration data could be used to derive the level of deposit forming compounds in the fuel.
- II copper
- one or more calibration fluids equivalent to the calibration fluids used to generate the standard deposits could be run in the JFTOT to form further deposits, which can be compared to the standard deposits expected to verify the performance of the JFTOT apparatus is as expected.
- Figure 8 shows a similar series of deposits formed under different conditions (in this case with a different JFTOT tube), which could be used to compare an unknown fuel tested under these different conditions.
- JFTOT Jet Fuel Thermal Oxidation Tester
- an integrated abso ⁇ tion intensity is selected as a criterion, opening up the possibility that substituent effect in the indole structure may change the position of maximum abso ⁇ tion.
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JP2003587900A JP2005529197A (en) | 2002-04-26 | 2003-04-24 | Method and apparatus for improving oxidation heat stability of distilled fuel |
AU2003227877A AU2003227877A1 (en) | 2002-04-26 | 2003-04-24 | Method and apparatus for improving the oxidative thermal stability of distillate fuel |
EP03725337A EP1499698A2 (en) | 2002-04-26 | 2003-04-24 | Method and apparatus for improving the oxidative thermal stability of distillate fuel |
CA002483300A CA2483300A1 (en) | 2002-04-26 | 2003-04-24 | Method and apparatus for improving the oxidative thermal stability of distillate fuel |
US10/510,604 US20050103686A1 (en) | 2002-04-26 | 2003-04-24 | Method and apparatus for improving the oxidative thermal stability of distillate fuel |
NZ535892A NZ535892A (en) | 2002-04-26 | 2003-04-24 | Method and apparatus for improving the oxidative thermal stability of jet fuel |
US11/898,716 US20080067110A1 (en) | 2002-04-26 | 2007-09-14 | Method and apparatus for improving the oxidative thermal stability of distillate fuel |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0209624.6 | 2002-04-26 | ||
GB0209624A GB0209624D0 (en) | 2002-04-26 | 2002-04-26 | Method |
GB0218871.2 | 2002-08-13 | ||
GB0218871A GB0218871D0 (en) | 2002-08-13 | 2002-08-13 | Method |
GB0305551A GB0305551D0 (en) | 2003-03-11 | 2003-03-11 | Method and apparatus |
GB0305551.4 | 2003-03-11 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US11/898,716 Continuation US20080067110A1 (en) | 2002-04-26 | 2007-09-14 | Method and apparatus for improving the oxidative thermal stability of distillate fuel |
Publications (2)
Publication Number | Publication Date |
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WO2003091361A2 true WO2003091361A2 (en) | 2003-11-06 |
WO2003091361A3 WO2003091361A3 (en) | 2004-03-04 |
Family
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Application Number | Title | Priority Date | Filing Date |
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PCT/GB2003/001752 WO2003091361A2 (en) | 2002-04-26 | 2003-04-24 | Method and apparatus for improving the oxidative thermal stability of distillate fuel |
Country Status (8)
Country | Link |
---|---|
US (2) | US20050103686A1 (en) |
EP (1) | EP1499698A2 (en) |
JP (1) | JP2005529197A (en) |
CN (1) | CN1329485C (en) |
AU (1) | AU2003227877A1 (en) |
CA (1) | CA2483300A1 (en) |
NZ (1) | NZ535892A (en) |
WO (1) | WO2003091361A2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2006199783A (en) * | 2005-01-19 | 2006-08-03 | Japan Energy Corp | Fuel composition |
JP2007526938A (en) * | 2004-02-13 | 2007-09-20 | シェブロン・オロナイト・カンパニー・エルエルシー | High-speed mass processing examination method for fuel compositions |
WO2013006527A1 (en) | 2011-07-07 | 2013-01-10 | Exxonmobil Research And Engineering Company | Method for increasing thermal stability of a fuel composition using a solid phosphoric acid catalyst |
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RU2644444C2 (en) * | 2012-04-03 | 2018-02-12 | Тайко Электроникс Райхем Бвба | Body and organizer for telecommunications |
US9394497B2 (en) * | 2012-09-17 | 2016-07-19 | Exxonmobil Research And Engineering Company | Characterization of pre-refined crude distillate fractions |
WO2018204256A1 (en) * | 2017-05-01 | 2018-11-08 | Exxonmobil Research And Engineering Company | Jet fuel treating for blending compatibility |
US10808194B2 (en) * | 2018-12-07 | 2020-10-20 | Exxonmobil Research And Engineering Company | Fuel high temperature antioxidant additive |
US11136516B2 (en) | 2018-12-07 | 2021-10-05 | Exxonmobil Research And Engineering Company | Motor gasoline with improved octane and method of use |
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- 2003-04-24 JP JP2003587900A patent/JP2005529197A/en not_active Withdrawn
- 2003-04-24 AU AU2003227877A patent/AU2003227877A1/en not_active Abandoned
- 2003-04-24 CA CA002483300A patent/CA2483300A1/en not_active Abandoned
- 2003-04-24 CN CNB038093596A patent/CN1329485C/en not_active Expired - Fee Related
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JP2007526938A (en) * | 2004-02-13 | 2007-09-20 | シェブロン・オロナイト・カンパニー・エルエルシー | High-speed mass processing examination method for fuel compositions |
JP2006199783A (en) * | 2005-01-19 | 2006-08-03 | Japan Energy Corp | Fuel composition |
WO2013006527A1 (en) | 2011-07-07 | 2013-01-10 | Exxonmobil Research And Engineering Company | Method for increasing thermal stability of a fuel composition using a solid phosphoric acid catalyst |
US9028675B2 (en) | 2011-07-07 | 2015-05-12 | Exxonmobil Research And Engineering Company | Method for increasing thermal stability of a fuel composition using a solid phosphoric acid catalyst |
Also Published As
Publication number | Publication date |
---|---|
JP2005529197A (en) | 2005-09-29 |
CN1649985A (en) | 2005-08-03 |
US20050103686A1 (en) | 2005-05-19 |
CA2483300A1 (en) | 2003-11-06 |
NZ535892A (en) | 2006-11-30 |
WO2003091361A3 (en) | 2004-03-04 |
EP1499698A2 (en) | 2005-01-26 |
CN1329485C (en) | 2007-08-01 |
US20080067110A1 (en) | 2008-03-20 |
AU2003227877A1 (en) | 2003-11-10 |
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