Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
  • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 present invention is directed to cold flow improving fuel additive compound. More particularly, it is directed to an additive compound consisting of the reaction product of an amide or ester derivative of a branched-chain monocarboxylic acid having at least one tertiary-amine group, an epoxide and a carboxylic acid and to said additive compounds. It is further directed to hydrocarbyl fuel compositions containing such cold flow improving fueld additive compounds.
• distillate fuels such as diesel fuels are subject to poor flowability at low temperatures and have relatively high cold filter plugging points.
• Many expedients have been attempted in the prior art to overcome these adverse cold temperature properties.
• U.S. Patent 4,108,613 teaches the use of a mixture of (1) the reaction product of an epoxidized alpha-olefin with a nitrogen-­containing compound selected from ammonia, an amine, a polyamine or a hydroxyamine and (2) an ethylene-olefin copolymer as an additive to depress the pour point of hydrocarbonaceous fuels and oils.
• U.S. Patent 3,962,104 discloses lubricating oil compositions containing minor amounts of quaternary ammonium salts useful as oil improving additives.
• the quaternary ammonium salts utilize a cation derived from the reaction product of one molar proportion of a tertiary amine with one or more molar proportions of an olefin oxide and an amount of water in excess of stoichiometric.
• the anion is derived from an organic acid and the tertiary amine has substituents which are alkyl, alkenyl, substituted alkyl, substituted alkenyl, aromatic or substituted aromatic groups.
• the present invention provides novel fuel additive compounds useful in improving the low temperature characteristics of distillate fuel compositions comprising the reaction product of (1) an amide or ester derivative of a branched chain monocarboxylic acid having at least one tertiary amine group, (2) an epoxide and (3) additional carboxylic acid.
• This invention also provides liquid hydrocarbyl distillate fuels having improved low temperature characteristics comprising a major proportion of a liquid hydrocarbyl distillate fuel and a minor proportion, effective to improve low temperature characteristics of the fuel, of the reaction product of (1) an amide or ester derivative of a branched chain monocarboxylic acid having at least one tertiary amine group, (2) an epoxide and (3) additional carboxylic acid.
• This invention further provides a method of reducing the pour point and cold flow plugging point of liquid distillate fuels, which method comprises additin to the fuel an effective amount of the reaction product of (1) an amide or ester derivative of a branched chain monocarboxylic acid having at least one tertiary amine group, (2) an epoxide and (3) additional carboxylic acid.
• the low temperature distillate fuel additive product or compound when added to the fuel in cold flowability effective amounts significantly decreases the cold flow plugging point, cloud point, filterability as well as the pour point of the fuel to which it is added.
• Suitable fuels include, but are not limited to, diesel fuel, home heating oil, airplane jet fuel and the like.
• the additive providing these properties is a product of reaction formed by the reaction of (1) an amide or ester derivative of a branched chain monocarboxylic acid having at least one t -amine group, (2) an epoxide and (3) additional carboxylic acid.
• the additional carboxylic acid may be the same branched chain carboxylic acid or a different branched chain acid or a linear carboxylic acid.
• the preferred branched chain carboxylic acids are telomer acids which may be prepared by the free radical addition of one mole of acetic anhydride to at least 3 moles of hexene and/or a higher olefin having up to about 30 or more carbon atoms (C3 ) in the presence of a trivalent manganese compound.
• This invention is not, however, limited to any specific method of preparing the telomer acids. Any method known in the art may be used.
• Preferred telomer acids are those made from C10-C20 alpha olefins and manufactured under the trade name Kortacid through Akzo Chemie, Chicago, Illinois. Specific acids are identified for example as Kortacid T-1801, Kortacid T-1001 and the like.
• the first two digits give the number of carbon atoms in at least one side chain of the acid. More specifically it is noted that the monocarboxylic acid having the below structural formula is known and further identified as a telomer acid and may be formulated in accordance with a procedure provided in U.S. Patent 4,283,314 in which a compound having the same structural formula and meanings is disclosed. U.S. Patent 4,283,­314 is incorporated herein by reference.
• the branched chain monocarboxylic acid have the structural formula where Z is -(CH2) n CH3 where n is an integer of from about 3 to about 42; x and y are different and are either 0 or 2; a is 0 or 1, if a is 0, R is hydrogen but if a is 1, R is -CH2; and b is 0 or 1, if b is 0, R1 is hydrogen but if b is 1, R1 is -CH2.
• the amide or ester derivative of a branched chain monocarboxylic acid having at least one tertiary amine group has the general formula: R2COXR4N(R5)(R6) where R2 is a branched chain monocarboxylic acid radical having a molecular weight of between 300 and 1,000; X is O or NR3 in which R3 is hydrogen or C1-C25 alkyl; R4 is a hydrocarbyl group of 1 to 25 carbon atoms; and R5 and R6 are the same or different and are C1-C25 alkyl.
• the amide derivative reaction product may be classified by the general formula: R2CON(R3)R4N(R5)(R6) wherein R2, R3, R4, R5, and R6 have the definitions given above.
• the branched chain monocarboxylic acid having a molecular weight of about 300 to 1,000 may be reacted as disclosed below with a suitable diamine to produce the above described amide derivative.
• the branched chain monocarboxylic acid has a molecular weight of 400 to 900. Still more preferably, the molecular weight of the branched chain monocarboxylic acid is in the range of between 500 and 800.
• the amide derivatives may be formed by a simple reaction between the acid and a suitable diamine such as RCO2H + H2N-CH2CH2CH2N(CH3)2 ⁇ RCO-NH2-CH2CH2CH2N(CH3)2 where R is a telomer acid radical.
• a suitable diamine such as RCO2H + H2N-CH2CH2CH2N(CH3)2 ⁇ RCO-NH2-CH2CH2CH2N(CH3)2 where R is a telomer acid radical.
• Any suitable diamine may be used and any conventional process known to the art may be used to provide the amide derivative.
• the amide derivative is thereafter reacted with an epoxide and additional carboxylic acid and is further defined by the branched chain hydrocarbyl having a molecular weight of between about 300 and 1,000.
• R2 in a preferred embodiment for both amide and ester derivatives, has the structural formula where Z, R, R1, n, a, b, x and
• Some of the useful diamines include but are not limited to N-­(3-aminopropyl) morpholine, N-(2-aminoethyl) morpholine, N-(2-­aminopropyl) morpholine, N,N′-bis(3-aminopropyl) piperazine, N,N-­diethylethylenediamine, 3-dimethylaminopropylamine, unsymmetrical (unsym.) dimethylethylenediamine, N,N-dimethyl-N′-­ethylethylenediamine and the like and mixtures of two or more of these. Especially preferred is 3-dimethylaminopropylamine.
• R groups mentioned are alkyl, nevertheless, others can be alkenyl, aryl, alkaryl, aralkyl or cycloalkyl. If aryl the group will contain 6 to 14 carbon atoms.
• the amines may be obtained as articles of commerce or prepared in any convenient manner.
• the epoxides useful herein generally contain from 2 to about 18 carbon atoms.
• the epoxides may be substituted with an aromatic or a saturated or unsaturated aliphatic group.
• preferred epoxides that may be used in the present invention are ethylene oxide, propylene oxide, styrene oxide, 1,2-epoxybutane, decene epoxide, tetradecene epoxide and octadecene epoxide and the like. It is emphasized that the above list is non-limiting. Any other epoxides, within the preferred group of epoxides having 2 to 18 carbon atoms may be advantageously used.
• the ester derivatives may be formed by a simple reaction between the branched chain monocarboxylic acid (preferably telomer) and a suitable hydroxy amine such as RCO2H + HO-CH2CH2CH2N(CH3)2 ⁇ RCO-O-CH2CH2CH2N(CH3)2 where R is a telomer acid radical.
• a suitable hydroxy amine such as RCO2H + HO-CH2CH2CH2N(CH3)2 ⁇ RCO-O-CH2CH2CH2N(CH3)2 where R is a telomer acid radical.
• Any suitable amino alcohol or hydroxy compound may be used and any conventional process known to the art may be used to provide the ester derivative.
• the ester derivative is thereafter reacted with an epoxide and additional carboxylic acid.
• the ester derivative reaction product may be classified by the general formula R2COO(R3)N(R5)(R6) (II) where R2, R3, R5 and R6 have the meanings given above.
• Structural formula II is limited to those derivatives having only one ester group and only one tertiary amine group. However, the invention is also directed to derivatives having more than one (multiple) ester groups and more than one (multiple) tertiary amine groups.
• An example is: with 4 ester groups and 2 tertiary amine groups where at least one R′ is a telomer acid radical and the remaining R′ groups may be the same or different or may be linear or branched and are from C1 to about C25 hydrocarbyl or hydrogen.
• the branched chain monocarboxylic acid having a molecular weight of about 300 to 1,000 may be reacted as disclosed above with a suitable hydroxy amine or amino alcohol to produce the described ester derivative.
• the branched chain monocarboxylic acid has a molecular weight of 400 to 900. Still more preferably, the molecular weight of the branched chain monocarboxylic acid is in the range of between 500 and 800.
• Some of the useful amines include but are not limited to N,N′N′-tris-(2-hydroxypropyl)N-tallowalkyl-1,3- diaminopropane, N,N,N′,N′-tetrakis(2-hydroxypropyl) ethylenediamine, N,N,N′,N′-tetrakis (2-hydroxymethyl) ethylenediamine, 3-dimethylaminopropanol, N-methyldiethanolamine and the like and mixtures of two or more of these. Especially preferred is N,N,N′,N′ tetrakis (2-hydroxypropyl) ethylenediamine.
• R groups mentioned are alkyl, nevertheless, other useful groups can be alkenyl, aryl, alkaryl, aralkyl or cycloalkyl. If aryl, the group will contain 6 to 14 carbon atoms.
• the amines may be obtained as articles of commerce or prepared in any convenient manner.
• the various reactants are usually reacted in substantially stoichiometric amounts or equimolar amounts, however, a slight molar excess of telomer acid to other reactants may be used if desired at temperatures ranging from about 50-175°C at pressures determined by the specific reaction, i.e., autogenous in 0.5 to about 3 hours or more.
• the additional carboxylic acid may also be a branched chain acid which may be a telomer acid that is different or the same as the acid from which the amide derivative is prepared or a linear monocarboxylic acid.
• the additional carboxylic acid has up to 20 or more carbon atoms, preferably 10-20.
• the improved cold flow effect manifested by the additives of the present invention to distillate fuels is accomplished by providing an effective cold flow improving amount of the additive compound of the present invention to a distillate fuel. More preferably, the amount added to the distillate fuel is in the range of between about 0.01 and 3-5 percent by weight, based on the total weight of the fuel composition. Still more preferably, the concentration of the flow improving product of reaction of the present invention to the distillate fuel is in the range of between 0.02 and 2 percent by weight. In certain cases, depending, inter alia, on the particular fuel and/or weather conditions, up to about 10 wt.% may be used. Up to about 10-20 wt.% of other additives for their known purposes may also be used.
• Kortacid (trademark) T-1801 a branched chain monocarboxylic telomeric acid (obtained from AKZO Chemie) was reacted with 3-­dimethylaminopropylamine) as follows to produce the 3-dimethyl­aminopropylamide of Kortacid T-1801.
• Example 2 30.5g. of the amide derivative formed in Example 1 was charged into a pressure vessel with 2.3g. of propylene oxide and 27.­0g of Kortacid T-1801, representing equimolar amounts of the three reactants, and heated at 70-100°C until all the propylene oxide was reacted. Completion of the reaction was evidenced by loss of pressure.
• the pressure is autogenous, from unreacted propylene oxide, and depends on the temperature, amounts of materials present and vessel size.
• the Rx reaction
• pressure drops to 0 if all the propylene oxide is consumed (actually, the Rx is run under N2 for safety, 2-5 psi of N2 is left in the vessel at all times).
• Example 3 23.9g of the compound of Example 1 was reacted with 4.9g of 1,2-epoxydecane and 21.3g of Kortacid T-1801.
• Example 4 24.4g of the compound of Example 1, 3.8g of styrene oxide and 21.7g of Kortacid T-1801 were reacted in a pressure vessel at a temperature of 90-100°C.
• Example 5 25.2g of the compound of Example 1, 2.4g of 1,2-epoxybutane and 22.4g of Kortacid T-1801 were reacted at a temperature of 70-­100°C.
• Example 6 23.1g of the compound of Example 1, 6.4g of commercial grade tetradecene epoxide and 20.5g of Kortacid T-1801 were reacted at a temperature of 70-100°C.
• Example 7 22.3g of the compound of Example 1, 7.8g of commercial grade octadecene epoxide and 19.9g of Kortacid T-1801, were reacted at a temperature of 70-100°C.
• Example 5 was otherwise run as Ex. 2. All the rest (Examples 3, 4, 6 and 7) have boiling points of about 125°C and were run in an open flask at 125°C until the reaction was complete (disappearance of epoxide band in infrared). This usually took from about 0.5-1.5 hours, depending on the reactivity of the epoxide.
• the fuel sample is cooled under prescribed conditions and, at intervals of 1°C, a vacuum of 200 mm water gauge is applied to draw the fuel through a fine wire mesh filter. As the fuel cools below its cloud point, increasing amounts of wax crystals will be formed. These will cause the flow rate to decrease and eventually complete plugging of the filter will occur.
• the Cold Filter Plugging Point is defined as the highest temperature (expressed as a multiple of 1°C) at which the fuel, when cooled under the prescribed conditions, either will not flow through the filter or requires more than 60 seconds for 20 ml to pass through.
• compositions (additives) in accordance with the invention is readily apparent from Table 2.
• telomer acids A tetraester of telomer acids was prepared from 66g Kortacid (Trade name) T-1801 (Akzo Chemie, Chicago, Illinois, and 5.7g Quadrol (BASF Wyandotte: N,N,N′,N′-tetrakis [2-hydroxypropyl] ethylenediamine) at 175°C with azeotropic removal of water. The material had an acid value of 10.1.
• a triester of telomer acids and Propoduomeen T/13 (Armak: N,N′,N′-(2-hydroxypropyl)-N-tallowalkyl-1,3- diaminopropane) was prepared in a similar manner from 168.2g Kortacid T-1801 and 36.3g of the aminoalcohol.
• a monoester of the telomer acids was prepared from 174.5g Kortacid T-1801 and 37.6g DMAMP (Angus Chemical: an 80% aqueous solution of 3-dimethylaminopropanol) using toluene for azeotropic removal of water at 150°C.
• DMAMP Angus Chemical: an 80% aqueous solution of 3-dimethylaminopropanol
• a diester was prepared from 188.5g Kortacid T-1801 and 16.5 N-­methyldiethanolamine under similar conditions.
• Texaco M-302 A diester of Kortacid T-1801 and Texaco M-302 was prepared in a similar manner. Texaco M-302 is described as having the approximate composition:
• Example 8 to 12 were blended percent by weight) into a typical diesel fuel (Table 1) and tested for pour point (ASTM D-97), cloud point (ASTM D-2500) and filterability by the LTFT procedure described below with the results shown in Table 3.
• the mole ratio of tertiary amine/epoxide/acid is 1/1/1 except as otherwise noted.
• LTFT testing starts at -21°C (-6°F). A failure at this point indicates essentially no significant reduction from the control base oil test at 1°.
• LTFT Low Temperature Flow Test for Diesel Fuels, a filtration test under consideration by CRC (Coordination Research Council).
• LTFT Procedure The test sample (200 ml) is gradually lowered to the desired testing temperature at a controlled cooling rate. After reaching that temperature the sample is removed from its cold box and filtered under vacuum through a 17 micrometer screen. If the entire sample can be filtered in less than 60 seconds it shall be considered as having passed the test. An F in this test indicates failure at the maximum acceptable temperature -21°C (-6°F). All test results are shown in Table 3.
• distillate fuel oil or diesel fuel oil may be used in accordance herewith.
• fuels having an initial boiling point of about 350°F and an end point of about 675°F are preferred.
• the base diesel fuel used in these tests was a blend of 15% kerosene with 85% of a straight distillate having the following characteristics shown in Table 1.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1986
  • 1986-10-14 AU AU63879/86A patent/AU6387986A/en not_active Abandoned
  • 1986-10-14 NZ NZ217912A patent/NZ217912A/xx unknown
  • 1986-10-17 EP EP86308059A patent/EP0220892A3/de not_active Withdrawn
  • 1986-10-20 DK DK500886A patent/DK500886A/da not_active Application Discontinuation
  • 1986-10-20 FI FI864242A patent/FI864242L/fi not_active IP Right Cessation
  • 1986-10-20 NO NO864181A patent/NO864181L/no unknown

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