EP0947577B1 - Verwendung von tertiäralkylprimären Aminen in Brennstoffzusammensetzungen, die als Wärmeträgerfluid verwendet werden - Google Patents
Verwendung von tertiäralkylprimären Aminen in Brennstoffzusammensetzungen, die als Wärmeträgerfluid verwendet werden Download PDFInfo
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- EP0947577B1 EP0947577B1 EP99302308A EP99302308A EP0947577B1 EP 0947577 B1 EP0947577 B1 EP 0947577B1 EP 99302308 A EP99302308 A EP 99302308A EP 99302308 A EP99302308 A EP 99302308A EP 0947577 B1 EP0947577 B1 EP 0947577B1
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- Prior art keywords
- fuel
- alkyl primary
- tertiary alkyl
- cetane
- primene
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Classifications
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- 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
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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- 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
- C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
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- 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
- C10L1/1811—Organic compounds containing oxygen peroxides; ozonides
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- 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
- C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
- C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
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- 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
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
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- 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
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2425—Thiocarbonic acids and derivatives thereof, e.g. xanthates; Thiocarbamic acids or derivatives thereof, e.g. dithio-carbamates; Thiurams
Definitions
- This invention relates to improved fuel oil compositions.
- fuel oil compositions containing cetane improvers having improved thermal stability The compositions further enjoy improved stabilization against: 1) sediment formation, and 2) color degradation during storage and distribution as well as improved cetane number, rust inhibition and demulsibility.
- the useful life of a fuel is a function of its quality and of storage conditions.
- middle distillate fuels such as diesel, jet fuels and heating fuels
- Fuel storage stability was a well-understood problem prior to the introduction of low-sulfur diesel fuel. It is well established that diesel fuels can exhibit instability when stored for extended periods of time (storage stability), or when brought into contact with high temperature engine parts (thermal stability). Hydrotreating to meet 1993 regulations reduced storage stability problems for highway fuels. However, low-sulfur fuels resulted in other issues, such as peroxide and thermal stability problems in distillate fuels. However, fuels are often stored for much longer periods because of logistical and economic necessities.
- oxidative degradation products formed under both prolonged storage and thermal stress, continue to be a problem in the utilization of, for example, diesel fuels.
- Fuel-instability reactions are defined in terms of the formation of deleterious products, such as filterable sediment, adherent gums, and peroxides. Sediments and gums which result from the oxidation reactions act to block filters and deposit on surfaces. Both the low-temperature storage and high-temperature thermal degradation, are of concern. Hydrotreating is generally considered the most effective means of improving stability. However, the cost of stability improvement by additives doping can often be less than the hydrotreatment costs.
- Diesel fuel performs multiple functions in a diesel engine and the associated fuel system. In addition to its primary role as an energy source, the fuel also serves as the sole lubricant of critical moving parts and as a heat-transfer fluid. Diesel fuel is increasingly used as a circulating coolant for high pressure fuel injections systems. This causes a problem in that as engine heat passes from injectors into the fuel, it can trigger a process that leads to particle formation, thus clogging filters and injectors. Fuels resistant to such thermal degradation must get a minimum 80% reflectance measurement using a green filter in the updated Octel F21-61 test (180 minutes, 150°C).
- thermal stability may become even more important in the future. Diesel engine manufacturers have indicated that engines under development to meet future exhaust emission standards will expose the fuel to more severe operating environments (stress), e.g., higher pressures and longer contact with high-temperature engine parts. In particular, thermal stability can be troublesome in some heavy-duty applications in some areas with widespread use of cetane improvers. Accordingly, cetane improvers will become increasingly important as engine makers promote and/or require higher cetane fuels, especially in premium diesel products.
- Additives can cause diesel fuel degradation if they are not oxidatively stable. Above 120°C, a cetane improver may oxidize and decompose, leading to particulate and sediment problems that can block filters. It is commonly accepted that 2-ethylhexyl nitrate functions as a diesel ignition improver because it is unstable, i.e., it thermally begins to decompose at about 155°C (311°F), i.e., just above the 300°F stability test temperature (Bacha, John; Lesnini, D. G., Proceedings of the 6 th International Conference on stability and Handling of Liquid Fuels, 1997, Eds., H. N.; US Dept. of Energy, Vol. 2, 671). This result suggests that the stability test temperature and test duration together are just sufficient for 2-ethylhexyl nitrate to contribute to the observed fuel thermal instability in the 300°F test.
- Tertiary alkyl amines are known as diesel fuel additives as antioxidants for storage improvement (see U.S. Patent 2,945,749 ); in combination with fatty amines to counteract tendency of fatty amines to emulsify (see U.S Patent 3,014,793 ); to minimize coking, especially throttling nozzed coking, in the prechambers or swirl chambers of injection compression ignition engines US-A-4,482,355; and as stabilizers in combination with detergent, rust preventors and demulsifier additives (see U.S. Patent 2 , 793 , 943 ).
- none of these references discusses the use of tertiary alkyl primary amines as thermal stabilizers and cetane improvers especially in the presence of conventional cetane improvers.
- the present inventors have now unexpectedly found that fuels are made thermally stable in the presence of cetane improvers, which are known to make fuels thermally unstable, by the addition of tertiary alkyl primary amines in the C 8 - C 24 range .
- the tertiary alkyl primary amines of the present invention also operate as cetane number improvers and the combination of cetane number improvers with the tertiary alkyl primary amines of the present invention provide a higher cetane number than that provided by the cetane improver alone.
- fuel oil compositions containing these amines are also characterized as having improved dispersability, improved rust inhibition and improved demulsibility.
- a fuel composition which is used as a heat-transfer fluid in a heavy duty diesel engine, said composition comprising: (A) a major amount of diesel fuel; (B) at least one cetane number improver; of from 1 to 1000 ppm of at least one tertiary (C 8 -C 24 ) alkyl primary amine of the formula: wherein: R 1 , R 2 , and R 3 are each independently (C 1 -C 21 ) alkyl, substituted (C 1 -C 21 ) alkyl, (C 1 -C 21 ) alkenyl or substituted (C 1 -C 21 ) alkenyl.
- (C 1 -C 21 ) means a straight chain or branched chain alkyl group having from 1 to 21 carbon atoms per group.
- major amount is understood to mean greater than 50 percent by weight and the term “minor amount” is understood to mean less than 50 percent by weight.
- the diesel fuel is present in a major amount in the fuel composition.
- the diesel fuel is present in an amount of at least 60% by weight, preferably at least 75% by weight, more preferably at least 90% by weight of the total fuel composition.
- the fuel compositions also include at least one cetane improver.
- Cetane improvers are compounds that readily decompose to form free radicals and then, in turn, promote the rate of chain initiation. The increased rate of chain initiation improves ignition characteristics for diesel fuel. Accordingly, cetane number (ignition quality) improvers are used to increase the cetane number when the base fuel cetane does not meet required specifications.
- Suitable cetane improvers include, without limitation, alkyl nitrates, such as 2-ethylhexyl nitrate (2-EHN); peroxides, such as di-t-butylperoxide; tetrazoles; thioaldehydes, tertiary alkyl primary amines, and mixtures thereof.
- the at least one cetane improver is an alkyl nitrate.
- the at least one cetane improver is 2-ethylhexyl nitrate (2-EHN).
- the at least one cetane improver is a tertiary alkyl primary amine.
- the at least one cetane improver is a tertiary alkyl primary amine and the fuel composition further includes a second cetane improver selected from alkyl nitrates, peroxides, tetrazoles; thioaldehydes, tertiary alkyl primary amines, and mixtures thereof.
- the at least one cetane improver is a tertiary alkyl primary amine and the fuel composition further includes a second cetane improver which is an alkyl nitrate, such as 2-EHN.
- the cetane improver is present in the fuel composition at a concentration of 50 to 7500, preferably 100 to 5000, more preferably 100 to 2000 ppm.
- the at least one tertiary alkyl primary amine is a tertiary (C 8 -C 24 ) alkyl primary amine according to the formula: wherein: R 1 , R 2 , and R 3 are each independently (C 1 -C 21 ) alkyl, substituted (C 1 -C 21 ) alkyl, (C 1 -C 21 ) alkenyl or substituted (C 1 -C 21 ) alkenyl.
- Suitable examples of (C 1 -C 21 ) alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-ethylhexyl, octyl, decyl, isodecyl, undecyl, dodecyl (also known as lauryl), tridecyl, tetradecyl (also known as myristyl), pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, cosyl, and eicosyl.
- Suitable examples of (C 1 -C 21 ) alkenyl include, but are not limited to, ethenyl, n-propenyl, isopropenyl, 1-butenyl, cis-2-butenyl, isobutylene, trans-2-butenyl, 2-3, dimethyl-2-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butene, 1-pentenyl, cis-2-pentenyl, trans-2-pentenyl, 1-hexenyl, 1-heptenyl, 1-octentl, 1-nonenyl, and 1-decenyl.
- Suitable examples of (C 1 -C 21 ) substituted alkyl and alkenyl include, but are not limited to, the above recited alkyl and alkenyl groups substituted with hydroxy, halide such as fluorine, chlorine or bromine; cyano; alkoxy; haloalkyl; carbalkoxy; carboxy; amino; alkylamino derivatives and the like; or nitro groups.
- the at least one tertiary alkyl primary amine may be a single amine or a mixture of amines, for instance as described following.
- the at least one tertiary alkyl amine is 1,1,3,3-tetramethylbutylamine available from Rohm and Haas Co of Philadelphia, PA as PRIMENE TOA®.
- the at least one tertiary alkyl amine is an isomeric mixture of C 16 to C 22 tertiary alkyl primary amines available from Rohm and Haas Co of Philadelphia, PA as PRIMENE JM-T®.
- the at least one tertiary alkyl amine is an isomeric mixture of C 8 to C 10 tertiary alkyl primary amines available from Rohm and Haas Co of Philadelphia, PA as PRIMENE BC-9® or an isomeric mixture of C 12 to C 14 tertiary alkyl primary amines available from Rohm and Haas Co of Philadelphia, PA as PRIMENE 81-R® or a mixture of PRIMENE BC-9® and PRIMENE 81-R®.
- the at least one tertiary alkyl amine is an isomeric mixture of C 12 to C 14 tertiary alkyl primary amines available from Rohm and Haas Co of Philadelphia, PA as PRIMENE 81-R®.
- the at least one tertiary alkyl primary amine is present in the fuel composition at a concentration of 1 to 1000, preferably 5 to 500, more preferably 10 to 200 ppm, most preferably 10 to 100 ppm. In another embodiment, the at least one tertiary alkyl primary amine is present in the fuel composition at a concentration of 50 to 100, or 1 to 10 ppm.
- the tertiary alkyl primary amines used in the fuel compositions are prepared using substrate compounds known as substrates for the Ritter reaction and include, for example, alcohols, alkenes, aldehydes, ketones, and ethers, ( see, generally, L. I. Krimen and D. J. Cota, "The Ritter Reaction", Organic Reactions, Vol. 17, 1969, pp. 213-325).
- substrate compounds known as substrates for the Ritter reaction and include, for example, alcohols, alkenes, aldehydes, ketones, and ethers, ( see, generally, L. I. Krimen and D. J. Cota, "The Ritter Reaction", Organic Reactions, Vol. 17, 1969, pp. 213-325).
- Processes for preparing tertiary alkyl primary amines are known in the art and are described for instance in U.S Patent 5,527,949 and in co-pending provisional application 60/051,867.
- the fuel compositions may also include other additives well known in the art such as, without limitation, anti-oxidants, dispersants, anti-foaming agents and the like.
- Fuel samples #A- # I were fresh test fuels without any additives and were obtained from commercial sources. The fuel samples were analyzed to ensure conformance with specifications and stored under ambient temperature, in dark, and under nitrogen atmosphere. All of the C 8 , C 9 , C 12 , and C 18 tertiary alkyl primary amines samples were commercial products sold under the trademark Primene® by Rohm and Haas Company of Philadelphia, Pa. The results are shown in Table 1.
- Fuel #A was evaluated for thermal stability and cetane number improvement.
- a sample of Fuel #A containing 100 ppm Primene® 81-R and a sample without were prepared. The fuel samples were stored in an air atmosphere at room temperature during the test period.
- the fuel samples were tested for a prolonged period of storage stability. Periodically, as indicated in Table 2, the fuels were sampled and tested for oxidative stability according to ASTM D 2274 Diesel Oxidation Stability test method as follows. A 350 mL sample of fuel was heated at 95°C for 40 hr. while oxygen is bubbled through at the rate of 3 liters per hour. After aging, the sample is cooled to room temperature and filtered to obtain the filterable insoluble quantity. Adherent insolubles are then removed from the associated glassware with trisolvent (TAM). The TAM is then evaporated to obtain the adherent insolubles. The sum of filterable and adherent insolubles, expressed as milligrams per 100 mL, is reported as total insolubles.
- TAM trisolvent
- a total sediment of 1 mg/100 mL or less is generally acceptable to pass the test, anything above 1 mg/100 mL sediment results in failing the test.
- the results are shown in Table 2 following. Comparison of the Results from Oxidation Stability of diesel Fuel #A @ No. of Weeks by ASTM D 2274 No. of Weeks of Storage Total Sediments (mg/100ml) Diesel Fuel #A Diesel Fuel #A + 100 ppm Primene® 81-R 2 1.0 0.2 5 2.2 0.5 7 2.8 0.6 10 19 1.0 15 27 2.2 The highest sediment reported in the Table 2 is 27mg for diesel Fuel #A, which is an indication of instability of the fuel at the prolonged period of time.
- the Fuel #A samples were also tested for cetane number with and without additives.
- the method used for cetane number determination was ASTM D 613 as well as tested for oxidation stability using ASTM D 2274.
- the results are shown in Table 3.
- Addition of 2-ethylhexylnitrate (2-EHN) improves the cetane number, but lowers the oxidative storage stability of the fuel #A as seen in Table 3.
- Addition of 100 ppm of Primene® 81-R to the fuel #A with 1000 ppm 2-EHN increases the storage stability without sacrificing the effect of 2-EHN as seen in the results in Table 3.
- Primene® 81-R is not only a stabilizer additive for the diesel fuel by itself, but, also is thermal stabilizer and synergistic cetane improver. Additionally, the tertiary alkyl primary amine (Primene®) enhances the cetane number both with and without the presence of conventional cetane improvers.
- Samples of fuel #C, #D, and #E having a sulfur concentration of 0.047%, 0.035%, and 0.035%, respectively were also evaluated for thermal stability and cetane number improvement.
- the cetane numbers of these fuels are listed in Table 5, and found to be 44.1, 45.5, and 45.4 respectively for the fuel # C, #D, and #E.
- the fuels were tested for oxidation/thermal stability with and without 2-EHN and combined with Primene amines.
- 2-EHN is used as a cetane number improver additive, and the addition of 2-EHN does increase the cetane number.
- it has an adverse effect on the thermal stability of the fuel when subjected to the Octel/DuPont F21-61 test at 150°C for 90 minutes.
- the Octel/DuPont F21-61 test also evaluates the filter pad by comparing with a standard filter color chart provided by Octel/DuPont. A rating of up to 7 is generally considered as a pass, and anything above 7 is considered a fail.
- the data presented in the Table 5 show that the addition of 2-EHN in all three fuel samples increased the filter pad rating to failure, 16, 10, and 9 for the fuels # C, #D, and #E respectively.
- the addition of Primene 81-R in the presence of 2-EHN increased the thermal stability in terms of pad rating and color and increased the cetane number as well.
- Table 8 The results shown in Table 8 were from continued testing of diesel Fuel #F to improve thermal stability in the presence of 2-EHN.
- the results showed that Primene® 81-R, and Primene® BC-9 and a combination of both at 100 ppm concentration with 2000 ppm of 2-EHN is effective in improving the thermal stability of the fuel.
- the combination of 2-ethylhexylnitrate and Primenes® improves the cetane number of the base fuel more than 2-EHN alone.
- Table 7 represents the relationship between the concentration of the additives, cetane number, and the filter pad rating of the DuPont F-21 test.
- Fuel oil samples of 500 mL were stored in 600 mL beakers covered with watch glasses in oven at 40°C. At arbitrary intervals, optical density measurements were made on samples before and after filtering a small portion of vigorously shaken sample through a CORNING 30 F fritted glass crucible. The unused portion was immediately returned to the oven for further aging. The failure time was determined by three methods: 1) the number of days to a stated level of optical density difference ( ⁇ OD) of 0.12 between unfiltered portions, 2) days to reach an OD value of 1.00 for the unfiltered sample, and 3) days to reach a residue level of 2.0 mg/100 mL as determined by filtration.
- ⁇ OD optical density difference
- Oxidative and thermal stability of diesel fuels was studied on fuel samples (a) collected from major regions around the world; (b) containing both high and low levels of sulfur and (c) containing both straight run and cracked components.
- the results of the various stability tests as measured by color, sediments and gum formation show clearly that addition of tertiary alkyl primary amines, at few ppm levels, significantly improves the stability of fuels.
- Results show that the thermal stability of both low and high sulfur fuels can be improved by tertiary alkyl primary amines doping at 8-40 ppm range. Furthermore, thermal stability is achieved without negatively effecting the cetane number. In fact, the cetane number is improved.
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
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- Solid Fuels And Fuel-Associated Substances (AREA)
Claims (9)
- Verwendung einer Treibstoffzusammensetzung die als Wärmeübertragungsflüssigkeit in einem Hochleistungsdieselmotor verwendet wird, wobei die Zusammensetzung umfasst: worin R1, R2 und R3 unabhängig voneinander (C1-C4) Alkyl, substituiertes (C1-C21)Alkyl, (C1-C21)Alkenyl oder substituiertes (C1-C21)Alkenyl sind, um die thermische Stabilität der Zusammensetzung zu verbessern.
- Verwendung nach Anspruch 1, wobei der mindestens eine Cetanverbesserer in einer Konzentration von 50 bis 7500 ppm vorliegt.
- Verwendung nach Anspruch 1, wobei der mindestens eine Cetanverbesserer 2-Ethylhexylnitrat ist.
- Verwendung nach Anspruch 1, wobei das mindestens eine primäre Tertiäralkylamin ein C9-Tertiäralkylamin ist.
- Verwendung nach Anspruch 1, wobei das mindestens eine primäre Tertiäralkylamin ein primäres C12-Tertiäralkylamin ist.
- Verwendung nach Anspruch 1, wobei das mindestens eine primäre Tertiäralkylamin ein primäres C18-Tertiäralkylamin ist.
- Verwendung nach Anspruch 4, wobei die Treibstoffzusammensetzung ferner ein primäres C12-Tertiäralkylamin umfasst.
- Verwendung nach Anspruch 1, wobei der mindestens eine Cetanverbesserer ein primäres Tertiäralkylamin ist.
- Verwendung nach Anspruch 8, ferner umfassend einen zweiten Cetanverbesserer ausgewählt aus Alkylnitraten, Peroxiden, Tetrazolen, Thioaldehyden, primären Tertiäralkylaminen, sowie Mischungen davon.
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DE69922566T DE69922566T2 (de) | 1999-03-25 | 1999-03-25 | Verwendung von tertiäralkylprimären Aminen in Brennstoffzusammensetzungen, die als Wärmeträgerfluid verwendet werden |
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US7725098P | 1998-03-09 | 1998-03-09 | |
US77250P | 1998-04-03 |
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EP0947577A1 EP0947577A1 (de) | 1999-10-06 |
EP0947577B1 true EP0947577B1 (de) | 2004-12-15 |
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Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1054051A1 (de) * | 1999-05-19 | 2000-11-22 | Rohm And Haas Company | Primäre Tertiäralkylamine enthaltende Dieselbrennstoffzusammensetzungen |
US7615085B2 (en) | 2003-11-04 | 2009-11-10 | Afton Chemical Corporation | Composition and method to reduce peroxides in middle distillate fuels containing oxygenates |
CN102093917B (zh) * | 2009-12-09 | 2013-11-13 | 济南开发区星火科学技术研究院 | 一种可替代柴油的调和燃料油及其制备方法 |
ES2809826T3 (es) | 2010-02-12 | 2021-03-05 | Donaldson Co Inc | Filtros de líquido |
CN104245900A (zh) * | 2012-04-24 | 2014-12-24 | 巴斯夫欧洲公司 | 具有清净作用的添加剂用于进一步增加燃料油的十六烷值的用途 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2456569A (en) * | 1944-12-18 | 1948-12-14 | Union Oil Co | Motor fuel |
US3014793A (en) * | 1956-02-28 | 1961-12-26 | Exxon Research Engineering Co | Distillate fuel oil compositions |
US2945749A (en) * | 1956-04-18 | 1960-07-19 | Socony Mobil Oil Co Inc | Stabilized fuel oil containing tertiary alkyl primary amines |
US4482355A (en) * | 1983-12-30 | 1984-11-13 | Ethyl Corporation | Diesel fuel compositions |
TW388752B (en) * | 1997-07-07 | 2000-05-01 | Rohm & Haas | Tertiary-alkyl primary amines and process for preparing the same |
-
1999
- 1999-03-25 EP EP99302308A patent/EP0947577B1/de not_active Expired - Lifetime
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EP0947577A1 (de) | 1999-10-06 |
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