US20070044374A1 - Aviation fuel cold flow additives and compositions - Google Patents
Aviation fuel cold flow additives and compositions Download PDFInfo
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- US20070044374A1 US20070044374A1 US11/438,816 US43881606A US2007044374A1 US 20070044374 A1 US20070044374 A1 US 20070044374A1 US 43881606 A US43881606 A US 43881606A US 2007044374 A1 US2007044374 A1 US 2007044374A1
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- 0 [1*]N([2*])C(=O)CC(=O)[O-].[3*][NH3+] Chemical compound [1*]N([2*])C(=O)CC(=O)[O-].[3*][NH3+] 0.000 description 3
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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
- C10L1/224—Amides; Imides carboxylic acid amides, imides
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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
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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
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
Definitions
- the invention pertains to jet fuel blends and methods in which a cold flow enhancement agent is added to the jet fuel to improve fuel flow rates and flow characteristics at low fuel temperatures.
- polymeric pour point depressant additives For example, use of poly[(meth)acrylates] as a pour point depressant for hydrocarbon lubricating oil is taught by U.S. Pat. Nos. 5,312,884 and 5,368,761. Additionally, the use of poly[ ⁇ -olefins] to improve the cold flow properties of gas oil is taught by El-Gamal et al., J. of Polym. Sci. 61, pp. 1265-1272 (1966). The use of a low molecular weight highly branched polymer of normal ⁇ -olefin to improve the cold flow properties of residual fuel oil is taught in U.S. Pat. No. 4,022,590.
- nitrogen compounds such as amides, amine salts, and ammonium salts of carboxylic acids or anhydrides, or sulpho anhydrides
- These compounds act as wax crystal modifiers and/or anti-agglomeration agents to provide enhanced cold flow properties relative to the polymeric pour point additive as a stand-alone treatment.
- WO 01/62874 A2 teaches the use of various chemical additives, including certain copolymers of vinyl acetate and ethylene, to lower the freeze point of aviation fuels. It is further taught that certain classes of pour point additives known to those skilled in the art for treating middle distillates, such as heating oils and diesel fuels, are not necessarily effective in the treatment of aviation fuel and actually may be detrimental.
- the invention is directed to a method of improving the cold flow rate of jet fuel.
- the method includes adding to the jet fuel an effective amount of the purpose of a cold flow rate enhancement agent (CFREA) having an oil-soluble, polar, nitrogen-containing compound.
- CFREA cold flow rate enhancement agent
- from 1-7,500 mg of CFREA is added to 1 liter of the jet fuel.
- FIG. 1 is a viscosity curve illustrating the effect additives have upon the viscosity of the aviation fuel according to one embodiment of the invention.
- CFREA cold flow rate enhancement agent
- oil-soluble, polar nitrogen-containing compounds are set forth in U.S. Pat. No. 4,211,534 (Feldman) incorporated by reference herein. Basically, as stated in the '534 specification, these compounds are oil-soluble amine salts and/or amides that are generally formed by reaction of at least one molar proportion of hydrocarbyl acid having 1-4 carboxyl groups or their anhydrides, with a hydrocarbyl substituted primary, secondary, and/or tertiary amine.
- all of the acid groups may be converted to amine salts or amides, or part of the acid groups may be left unreacted.
- hydrocarbyl as defined in U.S. Pat. No. 4,211,534 includes groups that may be branched or straight chain, saturated or unsaturated, aliphatic, cycloaliphatic, aryl, alkaryl, substituted derivatives thereof and the like. Typically, these hydrocarbyl groups will consist from about 4-24 carbon atoms, more preferably 10-20 carbon atoms. In general, the resultant compound should contain sufficient hydrocarbyl content so as to be soluble in the fuel matrix.
- hydrocarbyl substituted acids and anhydrides include, but are not limited to, hexanoic acid, lauric acid, palmitic acid, steric acid, behenic acids, benzoic acids, 1,2,4,5-benzenetetracarboxylic dianhydride, 1,2-cyclohexanedicarboxylic anhydride, ethylenediaminetetraacetic dianhydride, salicylic acid, succinic acid, succinic anhydride, alkenyl succinic anhydrides, polyisobutenyl succinic anhydrides (PIBSA), phthalic acids, phthalic anhydride, naphthenic acids, naphthenic anhydrides, and the like. Particularly preferred is phthalic anhydride.
- the hydrocarbyl substituted amines may be primary, secondary, or tertiary; preferably primary or secondary.
- hydrocarbyl substituted primary amines include, but are not limited to, coco amine, tallow amine, hydrogenated fatty primary amine, 2-ethylhexylamine, n-dodecyl amine, C 12-14 or C 16-22 tertiary alkyl primary amines from Rohm and Haas Company marketed under the trade name Primene®, mixtures thereof and the like. Particularly preferred is the C 16-22 tertiary alkyl primary amine marketed by Rohm and Haas Company under the trade name Primene® JM-T.
- hydrocarbyl substituted secondary amines include, but are not limited to, dicocoalkylamine, didecylamine, dioctadecylamine, ditallowamine, dihydrogenated tallowalkylamine, mixtures thereof and the like. Particularly preferred is dihydrogenated tallowalkylamine which is commercially available from Akzo Nobel Corporation under the trade name Armeen® 2HT.
- ester analogs derived from a hydrocarbyl alcohol and hydrocarbyl sulfo acid analogs such as those derived from o-sulphobenzoic acid or its anhydride, are also within the purview of the present invention.
- An especially preferred group of polar nitrogen-containing compounds are mixed amine salt/amides derived from reaction of hydrocarbyl acid (having two or more carboxyl groups) or its anhydrides as set forth above with a hydrocarbyl secondary amine.
- the resulting intermediate amide acid is then neutralized with a primary amine.
- the preferred group of polar nitrogen containing compounds can be represented by the formula wherein Z is a divalent organic radical, and R 1 , R 2 and R 3 are independently chosen from C 10 -C 40 hydrocarbyl groups.
- the hydrocarbyl groups include straight or branched chain, saturated or unsaturated aliphatic, cycloaliphatic, aryl or alkylaryl moieties. These hydrocarbyl groups may contain other groups or atoms such as hydroxy groups, carbonyl groups, ester groups, oxygen, sulfur, or chlorine groups. As stated above, the hydrocarbyl groups may be on the order of C 10 -C 40 with the range of C 14 -C 24 even more preferred.
- the R 1 , R 2 , and R 3 groupings can also represent mixtures of different hydrocarbyl groups. Preferably, R 3 ⁇ R 1 or R 2 .
- the resulting compound should contain sufficient hydrocarbon content to be oil-soluble.
- the preferred oil-soluble, polar nitrogen-containing compound is prepared by initial reaction of a hydrocarbyl acid or its anhydride and a secondary amine, such as the Armeen® 2HT. Then, the resulting mixed amine salt/amide is neutralized with a primary amine such as the commercially available Primene® JM-T product. Approximately equimolar amounts of the reactants are used, resulting in a mixed substituted amide/amine salt.
- the most preferred polar nitrogen containing compound is an oil-soluble mixed amide/amine salt formed via reaction of equimolar amounts of phthalic anhydride with the secondary amine, Armeen® 2HT. The product of this reaction is then further reacted with an equimolar amount of the primary amine, Primene® JM-T to form benzoic acid, 2-[(bis(hydrogenated tallow alkyl)amino)carbonyl]-C 16 -C 22 tert-alkyl amine salt having the structural formula: wherein R 1 and R 2 are mixtures of C 16 and C 18 hydrocarbons from the commercially available tallowamine product, and R 3 is a mixture of C 18-22 hydrocarbons from the commercially available Primene® JM-T product.
- the CFREAs of the present invention should be added to an aviation fuel, for which improved cold flow performance is desired, in an amount effective for the purpose.
- the aviation fuel is selected from Jet Fuel A, Jet Fuel A-1, Jet Fuel B, JP-4, JP-8, and JP-8+100.
- the jet fuel is a JP-8 based fuel such as neat JP-8 or the formulated JP-8+100.
- Jet Fuel A and Jet Fuel A-1 are kerosene-type fuels with Jet Fuel B being a “wide cut” fuel. Jet A is used for many domestic commercial flights in the U.S. Most preferably, the CFREAs of the invention are used to increase the cold flow characteristics of military jet fuels such as JP-5, JPTS, JP-7, JP-8, and JP-8+100. JP-5 is currently used by the U.S. Navy with JP-8 and JP-8+100 used by the Air Force.
- the CFREA is preferably added to the jet fuel in an amount of about 1-7,500 mg/L of the jet fuel. More preferably, the CFREA is added in an amount of between about 200-5,000 mg/L, most preferably about 4,000 mg/L.
- the jet fuel/CFREA blend is capable of improving the cold flow rate of jet fuel, specifically, JP-8 based jet fuel, at fuel temperatures on the order of about ⁇ 53° C. and below.
- the CFREAs of the invention can be employed in combination with conventional fuel additives such as dispersants, antioxidants, and metal deactivators.
- fuel additives such as dispersants, antioxidants, and metal deactivators.
- Such additives are known to those skilled in the art, for example see U.S. Pat. Nos. 5,596,130 and 5,614,081.
- This preparation was a scaleup of Example 1 (basis: phthalic anhydride, 99%, 344.74 g, 2.30 mole) except the hold times after the Armeen® 2HT and Primene® JM-T additions were decreased to one-hour each.
- JP-8 jet fuel was then treated with a known amount of additive solution and subjected to cold flow testing.
- Cold flow tests were conducted utilizing a Cold Additive Screening Test (CAST) and low temperature viscometer apparatus.
- CAST Cold Additive Screening Test
- the CAST apparatus consists of two 500 ml flasks, one at atmospheric pressure and one sealed, connected via a 1 ⁇ 4′′ Teflon tube.
- a known amount of fuel is charged to the flask at atmospheric pressure, and the apparatus is cooled to the desired test temperature in an environmental chamber. Once cooled to the desired temperature vacuum (2′′ Hg) is applied to the sealed flask.
- the effectiveness of an additive is determine by measuring the time it takes for the fuel to flow to the sealed flask, and the amount of fuel remaining in the atmospheric flask after the fuel flow ceases.
- Example 1 Fuel Temp Holdup Flow Rate Additive 1 (mg/L)* (° C.) (%) (g/s) None N/A ⁇ 53.5 100 N/A Example 1 8000 ⁇ 52.7 10 1.34 Example 1 16000 ⁇ 53.3 9 0.93 Example 2 12000 ⁇ 57.8 25 0.47 Example 2 12000 ⁇ 55.1 7 0.85 Example 2 14000 ⁇ 57.0 13 0.83 Example 2 14000 ⁇ 55.2 10 1.06 Example 2 16000 ⁇ 57.1 8 0.82 Example 2 16000 ⁇ 55.2 8 0.93
- the knee temperature is defined as the temperature at which a rapid viscosity increase occurs due to crystal formation. It is desirable to have the “knee temperature” for a treated fuel to be shifted to a lower temperature relative to the neat fuel. It is also highly desirable to minimize the rate of viscosity increase as the fuel is cooled below the knee temperature.
- Table 3 summarizes the results for the low temperature viscosity studies.
- the letter designation corresponds to the viscosity curve for that treatment in the companion graph presented in FIG. 1 . It can be seen from the data presented that the additives of the present invention lower the knee temperature of the fuel. Additionally, as shown in FIG. 1 , addition of the additives of the invention significantly reduces the rate of viscosity increase. The effect is pronounced to the extent that at higher additive levels there was no obvious knee temperature (curve “C” of FIG. 1 ).
Abstract
Aviation fuel, such as jet fuel, blends and methods for improving cold flow properties of such fuels at extremely low temperatures are disclosed. Cold flow properties of, for example, JP-8 jet fuel are improved by addition to the fuel of an oil-soluble, polar nitrogen-containing compound. Demonstratable cold flow improvement of such fuels at temperatures of about −53° C. and lower is shown.
Description
- This application is a continuation of U.S. patent application Ser. No. 10/459,842 filed Jun. 12, 2003 and claims the benefit of the filing date of the aforesaid application under 35 USC §120.
- The invention pertains to jet fuel blends and methods in which a cold flow enhancement agent is added to the jet fuel to improve fuel flow rates and flow characteristics at low fuel temperatures.
- It is important that aviation fuel exhibits a freeze point that is sufficiently low to allow adequate fuel flow through fuel system lines and filters to the engine. It is known that fuel temperature decreases as flight time increases and that longer duration flights typically require lower freezing point fuels than do shorter duration flights.
- Additionally, high altitude flights, such as those conducted under military operational conditions, also require lower freezing point fuels than do lower altitude conventional flights. Quite obviously then, there is a need to provide freeze point depressant/cold flow enhancement aids for aviation fuels, particularly for jet fuels, which will allow for sufficient fuel flow to desired combustion locations at the extremely low fuel temperatures encountered at high altitude and long duration flights. Publications WO 01/32811 A1 and WO 01/62874 A2 discuss details of aviation fuels and the need for lowered freeze point fuel blends.
- One such means of enhancing the cold flow properties of wax containing hydrocarbon fluids is via use of polymeric pour point depressant additives. For example, use of poly[(meth)acrylates] as a pour point depressant for hydrocarbon lubricating oil is taught by U.S. Pat. Nos. 5,312,884 and 5,368,761. Additionally, the use of poly[α-olefins] to improve the cold flow properties of gas oil is taught by El-Gamal et al., J. of Polym. Sci. 61, pp. 1265-1272 (1966). The use of a low molecular weight highly branched polymer of normal α-olefin to improve the cold flow properties of residual fuel oil is taught in U.S. Pat. No. 4,022,590.
- The use of nitrogen compounds, such as amides, amine salts, and ammonium salts of carboxylic acids or anhydrides, or sulpho anhydrides, as an adjuvant to polymeric pour point additives in middle distillate fuels is also known to those skilled in the art. These compounds act as wax crystal modifiers and/or anti-agglomeration agents to provide enhanced cold flow properties relative to the polymeric pour point additive as a stand-alone treatment. For example, see U.S. Pat. Nos. 3,982,909; 4,211,534; and 5,516,443; and EP Application Nos. 0 261 959 A2; 0 261 957 A2; and 0 272 889 A2.
- WO 01/62874 A2 teaches the use of various chemical additives, including certain copolymers of vinyl acetate and ethylene, to lower the freeze point of aviation fuels. It is further taught that certain classes of pour point additives known to those skilled in the art for treating middle distillates, such as heating oils and diesel fuels, are not necessarily effective in the treatment of aviation fuel and actually may be detrimental.
- The invention is directed to a method of improving the cold flow rate of jet fuel. The method includes adding to the jet fuel an effective amount of the purpose of a cold flow rate enhancement agent (CFREA) having an oil-soluble, polar, nitrogen-containing compound. In one aspect, from 1-7,500 mg of CFREA is added to 1 liter of the jet fuel.
- The present invention and its advantages over the prior art will become apparent upon reading the following detailed description and the appended claims with reference to the accompanying drawings.
- The above mentioned and other features of this invention will become more apparent and the invention itself will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein:
-
FIG. 1 is a viscosity curve illustrating the effect additives have upon the viscosity of the aviation fuel according to one embodiment of the invention. - Corresponding reference characters indicate corresponding parts throughout the views of the drawings.
- Methods for improving the cold flow rate of aviation fuels, and jet fuels in particular are provided wherein the jet fuel is blended with a cold flow rate enhancement agent (CFREA). The CFREA is an oil-soluble, polar, nitrogen-containing compound.
- The oil-soluble, polar nitrogen-containing compounds are set forth in U.S. Pat. No. 4,211,534 (Feldman) incorporated by reference herein. Basically, as stated in the '534 specification, these compounds are oil-soluble amine salts and/or amides that are generally formed by reaction of at least one molar proportion of hydrocarbyl acid having 1-4 carboxyl groups or their anhydrides, with a hydrocarbyl substituted primary, secondary, and/or tertiary amine.
- In the case of the polycarboxylic acids, or anhydrides, all of the acid groups may be converted to amine salts or amides, or part of the acid groups may be left unreacted.
- The term “hydrocarbyl” as defined in U.S. Pat. No. 4,211,534 includes groups that may be branched or straight chain, saturated or unsaturated, aliphatic, cycloaliphatic, aryl, alkaryl, substituted derivatives thereof and the like. Typically, these hydrocarbyl groups will consist from about 4-24 carbon atoms, more preferably 10-20 carbon atoms. In general, the resultant compound should contain sufficient hydrocarbyl content so as to be soluble in the fuel matrix.
- Exemplary hydrocarbyl substituted acids and anhydrides include, but are not limited to, hexanoic acid, lauric acid, palmitic acid, steric acid, behenic acids, benzoic acids, 1,2,4,5-benzenetetracarboxylic dianhydride, 1,2-cyclohexanedicarboxylic anhydride, ethylenediaminetetraacetic dianhydride, salicylic acid, succinic acid, succinic anhydride, alkenyl succinic anhydrides, polyisobutenyl succinic anhydrides (PIBSA), phthalic acids, phthalic anhydride, naphthenic acids, naphthenic anhydrides, and the like. Particularly preferred is phthalic anhydride.
- The hydrocarbyl substituted amines may be primary, secondary, or tertiary; preferably primary or secondary.
- Exemplary hydrocarbyl substituted primary amines include, but are not limited to, coco amine, tallow amine, hydrogenated fatty primary amine, 2-ethylhexylamine, n-dodecyl amine, C12-14 or C16-22 tertiary alkyl primary amines from Rohm and Haas Company marketed under the trade name Primene®, mixtures thereof and the like. Particularly preferred is the C16-22 tertiary alkyl primary amine marketed by Rohm and Haas Company under the trade name Primene® JM-T.
- Exemplary hydrocarbyl substituted secondary amines include, but are not limited to, dicocoalkylamine, didecylamine, dioctadecylamine, ditallowamine, dihydrogenated tallowalkylamine, mixtures thereof and the like. Particularly preferred is dihydrogenated tallowalkylamine which is commercially available from Akzo Nobel Corporation under the trade name Armeen® 2HT.
- As would be understood by one skilled in the art in view of the present disclosure, it is intended that the aforementioned examples do not in any way limit the description of the nitrogen-containing compounds. Furthermore, it is to be understood that ester analogs derived from a hydrocarbyl alcohol, and hydrocarbyl sulfo acid analogs such as those derived from o-sulphobenzoic acid or its anhydride, are also within the purview of the present invention.
- An especially preferred group of polar nitrogen-containing compounds are mixed amine salt/amides derived from reaction of hydrocarbyl acid (having two or more carboxyl groups) or its anhydrides as set forth above with a hydrocarbyl secondary amine. The resulting intermediate amide acid is then neutralized with a primary amine.
- Generally, the preferred group of polar nitrogen containing compounds can be represented by the formula
wherein Z is a divalent organic radical, and R1, R2 and R3 are independently chosen from C10-C40 hydrocarbyl groups. The hydrocarbyl groups include straight or branched chain, saturated or unsaturated aliphatic, cycloaliphatic, aryl or alkylaryl moieties. These hydrocarbyl groups may contain other groups or atoms such as hydroxy groups, carbonyl groups, ester groups, oxygen, sulfur, or chlorine groups. As stated above, the hydrocarbyl groups may be on the order of C10-C40 with the range of C14-C24 even more preferred. The R1, R2, and R3 groupings can also represent mixtures of different hydrocarbyl groups. Preferably, R3≠R1 or R2. - The resulting compound should contain sufficient hydrocarbon content to be oil-soluble.
- The preferred oil-soluble, polar nitrogen-containing compound is prepared by initial reaction of a hydrocarbyl acid or its anhydride and a secondary amine, such as the Armeen® 2HT. Then, the resulting mixed amine salt/amide is neutralized with a primary amine such as the commercially available Primene® JM-T product. Approximately equimolar amounts of the reactants are used, resulting in a mixed substituted amide/amine salt.
- The most preferred polar nitrogen containing compound is an oil-soluble mixed amide/amine salt formed via reaction of equimolar amounts of phthalic anhydride with the secondary amine, Armeen® 2HT. The product of this reaction is then further reacted with an equimolar amount of the primary amine, Primene® JM-T to form benzoic acid, 2-[(bis(hydrogenated tallow alkyl)amino)carbonyl]-C16-C22 tert-alkyl amine salt having the structural formula:
wherein R1 and R2 are mixtures of C16 and C18 hydrocarbons from the commercially available tallowamine product, and R3 is a mixture of C18-22 hydrocarbons from the commercially available Primene® JM-T product. - The CFREAs of the present invention should be added to an aviation fuel, for which improved cold flow performance is desired, in an amount effective for the purpose. In the preferred embodiment of the invention, the aviation fuel is selected from Jet Fuel A, Jet Fuel A-1, Jet Fuel B, JP-4, JP-8, and JP-8+100. Most preferably the jet fuel is a JP-8 based fuel such as neat JP-8 or the formulated JP-8+100.
- Jet Fuel A and Jet Fuel A-1 are kerosene-type fuels with Jet Fuel B being a “wide cut” fuel. Jet A is used for many domestic commercial flights in the U.S. Most preferably, the CFREAs of the invention are used to increase the cold flow characteristics of military jet fuels such as JP-5, JPTS, JP-7, JP-8, and JP-8+100. JP-5 is currently used by the U.S. Navy with JP-8 and JP-8+100 used by the Air Force.
- These fuel types are described in the following Table 1.
TABLE 1 U.S. Military Jet Fuel Year Freeze Intro- Point Flash Fuel duced Type ° C. Max Point Comments JP-5 1952 kerosene −46 60 JPTS 1956 kerosene −53 43 High thermal stability JP-7 1960 kerosene −43 60 JP-8 1979 kerosene −47 38 U.S. Air Force JP-8 + 1998 kerosene −47 38 U.S. Air Force 100 contains additives for improved thermal stability
JP = jet propulsion
Source: Chevron “Aviation Fuels” Technical Review.
- On a 100% actives basis, the CFREA is preferably added to the jet fuel in an amount of about 1-7,500 mg/L of the jet fuel. More preferably, the CFREA is added in an amount of between about 200-5,000 mg/L, most preferably about 4,000 mg/L. The jet fuel/CFREA blend is capable of improving the cold flow rate of jet fuel, specifically, JP-8 based jet fuel, at fuel temperatures on the order of about −53° C. and below. Experimental results have indicated that the CFREAs when blended with JP-8 based jet fuel in accordance with the invention improve cold flow rates of the fuel so that they are, as measured in accordance with Table 2 and the test system described, on the order of about 0.60 (g/s) and greater at fuel temperatures of about −53° C. and lower.
- The CFREAs of the invention can be employed in combination with conventional fuel additives such as dispersants, antioxidants, and metal deactivators. Such additives are known to those skilled in the art, for example see U.S. Pat. Nos. 5,596,130 and 5,614,081.
- The invention will be described further in conjunction with the following examples that are included for illustrative purposes only and should not be construed to limit the invention.
- To a four-necked reaction flask equipped with a mechanical overhead stirrer, thermocouple, reflux condenser, nitrogen sparge tube, addition port with septum and a heating mantle was added phthalic anhydride (99%, 5.0 g, 0.03342 mole) and Armeen® 2HT (17.0 g, 0.03342 mole amine). The resulting wax mixture was then heated to 90° C. under nitrogen with mixing and held for four hours. Primene® JM-T (10.9 g, 0.03342 mole amine) was then added to the reactor at 90° C. over an eight-minute period, after which the batch was maintained at 90° C. for an additional four hours before cooling to room temperature to yield a wax like material. This was then diluted in Aromatic 100 to yield a 25 wt % solution of the nitrogen-containing compound.
- This preparation was a scaleup of Example 1 (basis: phthalic anhydride, 99%, 344.74 g, 2.30 mole) except the hold times after the Armeen® 2HT and Primene® JM-T additions were decreased to one-hour each.
- JP-8 jet fuel was then treated with a known amount of additive solution and subjected to cold flow testing. Cold flow tests were conducted utilizing a Cold Additive Screening Test (CAST) and low temperature viscometer apparatus.
- In general, the CAST apparatus consists of two 500 ml flasks, one at atmospheric pressure and one sealed, connected via a ¼″ Teflon tube. A known amount of fuel is charged to the flask at atmospheric pressure, and the apparatus is cooled to the desired test temperature in an environmental chamber. Once cooled to the desired temperature vacuum (2″ Hg) is applied to the sealed flask. The effectiveness of an additive is determine by measuring the time it takes for the fuel to flow to the sealed flask, and the amount of fuel remaining in the atmospheric flask after the fuel flow ceases.
- Screening results of the additives of the present invention in the CAST apparatus are provided in Table 2 below. At approximately −53° C. the untreated fuel has solidified and exhibited 100% holdup and essentially no fuel flow. Addition of the additives of the present invention to the fuel dramatically improved the cold flow properties at approximately −53° C. as evidenced by a substantial decrease in hold up and increase in fuel flow.
TABLE 2 CAST Testing Results Conc. Fuel Temp Holdup Flow Rate Additive 1 (mg/L)* (° C.) (%) (g/s) None N/A −53.5 100 N/A Example 1 8000 −52.7 10 1.34 Example 1 16000 −53.3 9 0.93 Example 2 12000 −57.8 25 0.47 Example 2 12000 −55.1 7 0.85 Example 2 14000 −57.0 13 0.83 Example 2 14000 −55.2 10 1.06 Example 2 16000 −57.1 8 0.82 Example 2 16000 −55.2 8 0.93 - Low temperature viscosity studies of the treated fuel were carried out using a scanning Brookfield Viscometer in the temperature range of −5° C. to −60° C. as described by S. Zabarnick and M. Vangsness, Petroleum Chemistry Preprints 2002, 47(3), pp. 243-246 (2002). The results of this testing are given in Table 2. The knee temperature is defined as the temperature at which a rapid viscosity increase occurs due to crystal formation. It is desirable to have the “knee temperature” for a treated fuel to be shifted to a lower temperature relative to the neat fuel. It is also highly desirable to minimize the rate of viscosity increase as the fuel is cooled below the knee temperature.
- Table 3 summarizes the results for the low temperature viscosity studies. The letter designation corresponds to the viscosity curve for that treatment in the companion graph presented in
FIG. 1 . It can be seen from the data presented that the additives of the present invention lower the knee temperature of the fuel. Additionally, as shown inFIG. 1 , addition of the additives of the invention significantly reduces the rate of viscosity increase. The effect is pronounced to the extent that at higher additive levels there was no obvious knee temperature (curve “C” ofFIG. 1 ).TABLE 3 Low Temperature Viscosity Results-Knee Temperature in JP-8 Fuel Letter Additive 1 Conc. (mg/L)* Knee Temp (° C.) A None N/A −52.0 B Example 2 12000 −55.2 C Example 2 16000 None Observed - While the specification above has been drafted to include the best mode of practicing the invention as required by the patent statutes, the invention is not to be limited to that best mode or to other specific embodiments set forth in the specification. The breadth of the invention is to be measured only by the literal and equivalents constructions applied to the appended claims.
Claims (11)
1. Method of improving the cold flow rate of jet fuel comprising adding to said jet fuel an effective amount of the purpose of a cold flow rate enhancement agent (CFREA) comprising an oil-soluble, polar, nitrogen-containing compound.
2. Method as recited in claim 1 comprising adding from a 1-7,500 mg of said CFREA to said jet fuel, based upon 1 liter of said jet fuel.
3. Method as recited in claim 1 wherein said jet fuel is a JP-8 based jet fuel.
4. Method as recited in claim 1 wherein said oil-soluble, polar nitrogen compound comprises an amine salt or amide.
5. Method as recited in claim 4 , wherein said oil-soluble, polar nitrogen compound comprises a reaction product formed from reaction of a hydrocarbyl acid having two or more carboxyl groups or anhydride thereof, and a hydrocarbyl secondary amine followed by neutralization of the resulting product with a hydrocarbyl primary amine.
6. Method as recited in claim 1 wherein said oil-soluble, polar nitrogen compound is benzoic acid, 2-[(bis(hydrogenated tallow alkyl)amino)carbonyl]-C16-C22 tert-alkyl amine salt.
8. Method as recited in claim 2 wherein said oil-soluble, polar, nitrogen-containing compound is formed from a reaction of a hydrocarbyl acid having from about 1 to about 4 carboxyl groups or anhydrides thereof with a hydrocarbyl substituted primary, secondary, or tertiary amine.
9. Method as recited in claim 8 wherein said hydrocarbyl acid or anhydride and hydrocarbyl substituted primary, secondary, and tertiary amines each have from about 4 to about 24 carbon atoms.
10. Method as recited in claim 9 wherein said hydrocarbyl acid or anhydride and hydrocarbyl substituted primary, secondary, and tertiary amines each have from about 10-24 carbon atoms.
11. Method as recited in claim 3 wherein said JP-8 jet fuel is subjected to temperatures of −53.0° C. and lower.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/438,816 US20070044374A1 (en) | 2003-06-12 | 2006-05-23 | Aviation fuel cold flow additives and compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/459,842 US20040250468A1 (en) | 2003-06-12 | 2003-06-12 | Aviation fuel cold flow additives and compositions |
US11/438,816 US20070044374A1 (en) | 2003-06-12 | 2006-05-23 | Aviation fuel cold flow additives and compositions |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/459,842 Continuation US20040250468A1 (en) | 2003-06-12 | 2003-06-12 | Aviation fuel cold flow additives and compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
US20070044374A1 true US20070044374A1 (en) | 2007-03-01 |
Family
ID=33510883
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/459,842 Abandoned US20040250468A1 (en) | 2003-06-12 | 2003-06-12 | Aviation fuel cold flow additives and compositions |
US11/438,816 Abandoned US20070044374A1 (en) | 2003-06-12 | 2006-05-23 | Aviation fuel cold flow additives and compositions |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/459,842 Abandoned US20040250468A1 (en) | 2003-06-12 | 2003-06-12 | Aviation fuel cold flow additives and compositions |
Country Status (4)
Country | Link |
---|---|
US (2) | US20040250468A1 (en) |
AR (1) | AR044683A1 (en) |
TW (1) | TW200516137A (en) |
WO (1) | WO2005001005A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060236597A1 (en) * | 2003-06-12 | 2006-10-26 | General Electric Company | Aviation fuel cold flow additives and compositions |
US20070044375A1 (en) * | 2003-06-12 | 2007-03-01 | General Electric Company | Aviation fuel cold flow additives and compositions |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9989280B2 (en) | 2008-05-02 | 2018-06-05 | Heatcraft Refrigeration Products Llc | Cascade cooling system with intercycle cooling or additional vapor condensation cycle |
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US4211534A (en) * | 1978-05-25 | 1980-07-08 | Exxon Research & Engineering Co. | Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils |
US20060236597A1 (en) * | 2003-06-12 | 2006-10-26 | General Electric Company | Aviation fuel cold flow additives and compositions |
US20070044375A1 (en) * | 2003-06-12 | 2007-03-01 | General Electric Company | Aviation fuel cold flow additives and compositions |
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US3982909A (en) * | 1975-02-13 | 1976-09-28 | Exxon Research And Engineering Company | Nitrogen-containing cold flow improvers for middle distillates |
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US4898751A (en) * | 1982-04-26 | 1990-02-06 | Petrolite Corporation | Composition and method for prevention of adhesion of particulate matter to containers |
GB8510719D0 (en) * | 1985-04-26 | 1985-06-05 | Exxon Chemical Patents Inc | Fuel compositions |
GB9118105D0 (en) * | 1991-08-22 | 1991-10-09 | Exxon Chemical Patents Inc | Compounds and fuel compositions |
US5312884A (en) * | 1993-04-30 | 1994-05-17 | Rohm And Haas Company | Copolymer useful as a pour point depressant for a lubricating oil |
US5596130A (en) * | 1994-04-19 | 1997-01-21 | Betz Laboratories, Inc. | Methods and compositions for reducing fouling deposit formation in jet engines |
US5614081A (en) * | 1995-06-12 | 1997-03-25 | Betzdearborn Inc. | Methods for inhibiting fouling in hydrocarbons |
USH1768H (en) * | 1997-05-09 | 1999-01-05 | The United States Of America As Represented By The Secretary Of The Navy | Oxidizing agent |
US6610110B1 (en) * | 2000-02-11 | 2003-08-26 | The Lubrizol Corporation | Aviation fuels having improved freeze point |
EP1357168A1 (en) * | 2002-04-16 | 2003-10-29 | Infineum International Limited | Jet fuel compositions |
-
2003
- 2003-06-12 US US10/459,842 patent/US20040250468A1/en not_active Abandoned
-
2004
- 2004-06-11 WO PCT/US2004/018662 patent/WO2005001005A1/en active Application Filing
- 2004-06-11 TW TW093116977A patent/TW200516137A/en unknown
- 2004-06-11 AR ARP040102036A patent/AR044683A1/en unknown
-
2006
- 2006-05-23 US US11/438,816 patent/US20070044374A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4211534A (en) * | 1978-05-25 | 1980-07-08 | Exxon Research & Engineering Co. | Combination of ethylene polymer, polymer having alkyl side chains, and nitrogen containing compound to improve cold flow properties of distillate fuel oils |
US20060236597A1 (en) * | 2003-06-12 | 2006-10-26 | General Electric Company | Aviation fuel cold flow additives and compositions |
US20070044375A1 (en) * | 2003-06-12 | 2007-03-01 | General Electric Company | Aviation fuel cold flow additives and compositions |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060236597A1 (en) * | 2003-06-12 | 2006-10-26 | General Electric Company | Aviation fuel cold flow additives and compositions |
US20070044375A1 (en) * | 2003-06-12 | 2007-03-01 | General Electric Company | Aviation fuel cold flow additives and compositions |
Also Published As
Publication number | Publication date |
---|---|
AR044683A1 (en) | 2005-09-21 |
TW200516137A (en) | 2005-05-16 |
WO2005001005A1 (en) | 2005-01-06 |
US20040250468A1 (en) | 2004-12-16 |
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