Compositions And Methods Of Dispergating Paraffins In Sulphur-Low Fuel Oils

Abstract

The present invention relates to a fuel oil having a sulfur content of less than 50 ppm, comprising i. at least one oil-soluble amide-ammonium salt of a polycarboxylic acid with a mono- and/or dialkylamine (A) and ii. 5-100% by weight, based on the amount of amide-ammonium salt (A), of an oil-soluble amine (B), and iii. a lubricity additive (C) selected from fatty acids, fatty acid partial esters of polyols and fatty acid amides of alkanolamides, and wherein the fuel oil consists of fuel oil of mineral origin, synthetic fuel or a mixture thereof.

Claims

1.-25. (canceled)

26. A fuel oil having a sulfur content of less than 50 ppm, comprising i. at least one oil-soluble amide-ammonium salt of a polycarboxylic acid with a mono- and/or dialkylamine (A) and ii. 5-100% by weight, based on the amount of amide-ammonium salt (A), of an oil-soluble amine (B), and iii. a lubricity additive (C) selected from fatty acids, fatty acid partial esters of polyols and fatty acid amides of alkanolamides, and wherein the fuel oil consists of fuel oil of mineral origin, a synthetic fuel obtainable by catalytic hydrodeoxygenation of vegetable oils and fats or of animal fats, or a synthetic fuel produced by means of Fischer-Tropsch synthesis or a mixture thereof.

27. The fuel oil as claimed in claim 26, wherein the polycarboxylic acid is selected from the group consisting of monomeric dicarboxylic acids, monomeric polycarboxylic acids and copolymerized dicarboxylic acids.

28. The fuel oil as claimed in claim 26, wherein the fuel oil contains 1% to 95% by weight of amide-ammonium salt (A).

29. The fuel oil as claimed in claim 26, wherein the oil-soluble amine (B) has the formula (1) ##STR00006## in which R.sup.4 is an alkyl radical having 8 to 22 carbon atoms or a group of the formula (CH.sub.2).sub.n[NR.sup.7(CH.sub.2).sub.n].sub.mNH.sub.2, R.sup.5 is hydrogen, an alkyl radical having 1 to 22 carbon atoms or a group of the formula (CH.sub.2).sub.n[NR.sup.7(CH.sub.2).sub.n].sub.mNH.sub.2, R.sup.6 is hydrogen or an alkyl radical having 1 to 22 carbon atoms, R.sup.7 is hydrogen or an alkyl radical having 1 to 22 carbon atoms, n is 2 or 3 and m is 0 to 10.

30. The fuel oil as claimed in claim 26, wherein the fuel oil contains 15% to 70% by weight of oil-soluble amine (B) based on the amount of amide-ammonium salt (A).

31. The fuel oil as claimed in one or more of claims 1 to 5, wherein the oil-soluble amine (B) is a primary, secondary or tertiary fatty amine.

32. The fuel oil as claimed in claim 29, in which, in formula (1), R.sup.4 is an alkyl radical having 8 to 22 carbon atoms, R.sup.5 is hydrogen or an alkyl radical having 1 to 22 carbon atoms and R.sup.6 is hydrogen or an alkyl radical having 1 to 22 carbon atoms.

33. The fuel oil as claimed in claim 26, wherein the oil-soluble amine (B) has at least one alkyl radical having 10 to 22 carbon atoms.

34. The fuel oil as claimed in claim 26, wherein the oil-soluble amine (B) is a polyamine.

35. The fuel oil as claimed in claim 26, wherein the fuel oil additionally comprises an alkylphenol resin and/or hydroxybenzoate resin (D).

36. The fuel oil as claimed in claim 26, wherein the fuel oil additionally comprises a polyoxyalkylene compound (E).

37. The fuel oil as claimed in claim 26, wherein the fuel oil additionally comprises a comb polymer (F).

38. The fuel oil as claimed in claim 26, wherein the fuel oil additionally comprises an ethylene copolymer (G).

39. The fuel oil as claimed in claim 26, in which the sulfur content of the fuel is less than 20 ppm.

40. The fuel oil as claimed in claim 26, wherein the fuel oil is a middle distillate.

41. The fuel oil as claimed in claim 26, wherein the fuel oil is diesel oil or heating oil.

42. The fuel oil as claimed in claim 26, wherein the fuel oil is or comprises a synthetic fuel.

43. A method of improving the low-temperature properties of a fuel oil having a sulfur content of less than 50 ppm, comprising a lubricity additive (C) selected from fatty acids, fatty acid partial esters of polyols and fatty acid amides of alkanolamides, by adding to the fuel oil a low-temperature additive comprising i. at least one oil-soluble amide-ammonium salt of a polycarboxylic acid with a mono- and/or dialkylamine (A) and ii. 5-100% by weight, based on the amount of amide-ammonium salt (A), of an oil-soluble amine (B), and wherein the fuel oil consists of a fuel of mineral origin, or a synthetic fuel obtainable by catalytic hydrodeoxygenation of vegetable oils and fats or of animal fats, or a synthetic fuel produced by means of Fischer-Tropsch synthesis or a mixture thereof.

44. The method as claimed in claim 43, wherein the fuel oil contains between 50 and 1000 ppm of a lubricity additive (C).

45. The method as claimed in claim 43, in which the lubricity additive (C) is a fatty acid.

46. A method of improving the response characteristics of a fuel oil comprising a lubricity additive (C) and having a sulfur content of less than 50 ppm on the addition of an amide-ammonium salt (A), characterized in that 5% to 100% by weight of an oil-soluble amine (B) is added to the fuel oil, based on the amide-ammonium salt (A), where the lubricity additive (C) is selected from the group consisting of fatty acids, fatty acid partial esters of polyols and fatty acid amide of alkanolamides, and where the fuel oil consists of a fuel of mineral origin, or a synthetic fuel obtainable by catalytic hydrodeoxygenation of vegetable oils and fats or of animal fats, or a synthetic fuel produced by means of Fischer-Tropsch synthesis or a mixture thereof.

Description

EXAMPLES

[0167] For assessment of the improvement in the low-temperature properties of fuel oils by the additives of the invention, the fuel oils characterized in table 1 were used. Measurements of the cloud point were made according to ISO 3015, and those of the CFPP value (cold filter plugging test) according to EN 116. Molecular weights were determined by means of gel permeation chromatography (GPC) in THF against poly(styrene) standards. The amounts of oil-soluble amine B (ppm) used in the experiments in tables 3 to 8 are additionally displayed as % by weight based on the amount (active ingredient content) of amide-ammonium salt (A) added to the fuel oil.

[0168] Paraffin dispersancy was determined in sedimentation tests that were conducted as follows:

[0169] 350 ml of the fuel oil was heated to 60? C. in a graduated measuring cylinder, and the amounts of the additives characterized in tables 2A to 2D that are specified in tables 4, 7 and 8 were added. The dosage rates specified in the tables indicate the masses of active ingredients added in each case, based on the amount of the fuel oil (ppm by mass).

[0170] The fuel oil thus treated was cooled down to room temperature. 50 ml of the sample was taken for determination of CFPP and cloud point (before). The remaining 300 ml in the graduated measuring cylinder was cooled down to the respective storage temperature at a cooling rate of ?1.5? C./minute in a refrigerator. After the storage time specified in tables 4 and 7, the sample was assessed visually. This involved determining and assessing the volume of the sedimented paraffin phase and the appearance of the fuel oil phase above it. Quantification was effected in percent by volume of sediment. A small amount of sediment and a fuel oil phase having maximum homogeneity of cloudiness show good paraffin dispersancy.

[0171] In addition, directly after the cold storage, the upper and lower 20% by volume of the sample were isolated, and cloud point and CFPP of the two phases were determined.

[0172] The sedimentation test was considered to have been passed if the following five criteria were satisfied: [0173] Criterion 1: The visual assessment of dispersion (vis) must have uniform cloudiness of the sample or a sediment volume of <1% (d). In the case of presence of a greater amount of sediment (s), the test is considered to have been failed. [0174] Criterion 2: The CP of the lower phase may be not more than 2 K above the CP of the oil before the storage (?CP.sub.u). [0175] Criterion 3: The CP of the upper phase may be not more than 2 K below the CP of the oil before the storage (?CP.sub.o). [0176] Criterion 4: The CFPP of the lower phase may be not more than 2 K above the CFPP of the oil before the storage (?CFPP.sub.u). [0177] Criterion 5: The CFPP of the upper phase may be not more than 2 K below the CFPP of the oil before the storage (?CFPP.sub.u).

[0178] Only a small variance in the cloud point and in the cold filter plugging point of the lower phase and of the upper phase from the blank value of the oil shows good paraffin dispersancy.

TABLE-US-00001 TABLE 1 Characterization of the test oils used: Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Test oil 6 Distillation IBP [? C.] 196.7 176.8 176.2 187.3 201.4 173.2 20% [? C.] 240.8 219.6 223.1 246.7 249.7 223.2 90% [? C.] 327.2 318.9 331.0 332.8 333.8 332.9 (90 ? 20)% [? C.] 86.4 99.3 107.9 86.1 84.1 109.7 FBP [? C.] 355.1 340.1 358.1 360.6 354.9 357.4 Cloud point [? C.] ?11.2 ?16.0 ?7.1 ?7.1 ?8 ?7.8 CFPP [? C.] ?11 ?18 ?10 ?8 ?8 ?8 Pour point [? C.] ?21 ?24 ?15 ?15 ?12 ?18 Density @15? C. [g/cm.sup.3] 0.8398 0.8412 0.8304 0838 0.8563 0.8328 Sulfur content [ppm] 9 7 9 8 7 9 Aromatic content [% by wt.] 32.75 29.9 24.7 28.67 23.94 19.09 of which mono [% by wt.] 26.4 24.3 22.5 23.8 20.76 17.89 di [% by wt.] 5.87 4.32 2.0 4.53 3.01 1.2 poly [% by wt.] 0.48 0.38 0.2 0.34 0.17 0 n-Paraffin content [% by wt.] 23.2 24.3 26.5 23.7 26.3 22.5

TABLE-US-00002 TABLE 2A Characterization of the amide-ammonium salts (A) used A1 Reaction product of a copolymer of C.sub.14/C.sub.16-?-olefin and maleic anhydride with 2 equivalents of hydrogenated ditallowamine A2 Reaction product of ethylenediaminetetraacetic acid with 4 equivalents of ditallowamine to give the amide-ammonium salt A3 Reaction product of phthalic anhydride and 2 equivalents of di(hydrogenated tallow)amine

TABLE-US-00003 TABLE 2B Characterization of the oil-soluble amines (B) used B1 Di(tallowamine) B6 Tallowpropylenediamine B2 Di(stearylamine) B7 Dimethylhexadecylamine B3 Tallowamine B8 Dimethylcocoamine I4 Dimethyllaurylamine B9 Triethylenetetramine B5 Dimethyltetradecylamine

TABLE-US-00004 TABLE 2C Characterization of the lubricity additives (C) used C1 Tall oil fatty acid C2 C.sub.18-Alkenylsuccinic acid bis(ethylene glycol ester) C3 Oleic acid diethanolamide C4 Oleic acid

TABLE-US-00005 TABLE 2D Characterization of the further cold flow improvers used (D)-(G) D1 Nonylphenol-formaldehyde resin, M.sub.w = 4500 g/mol, 60% in higher-boiling aromatic solvent D2 Dodecyl benzoate-formaldehyde resin, M.sub.w = 2100 g/mol, 50% in higher-boiling aromatic solvent E1 Behenic ester of alkoxylated glycerol, M.sub.p = 3100 g/mol; 50% in higher-boiling aromatic solvent E2 PEG 400-dibehenate, 50% in higher-boiling aromatic solvent F1 Copolymer of ditetradecyl fumarate, 50% in higher-boiling aromatic solvent F2 Poly(C12/14-alkyl acrylate), M.sub.w = 85 000 g/mol, 50% in higher-boiling aromatic solvent G1 Copolymer of ethylene and 13.5 mol % of vinyl acetate having a melt viscosity V.sub.140 measured at 140? C. of 125 mPas, 65% in kerosene. Density (40? C.) = 0.85 g/cm.sup.3 G2 Terpolymer of ethylene, 13 mol % of vinyl acetate and 2 mol % of vinyl neodecanoate having a melt viscosity V.sub.140 measured at 140? C. of 95 mPas, 65% in kerosene. Density (40? C.) = 0.86 g/cm.sup.3 G3 Mixture of equal parts G1 and G2 G4 Terpolymer of ethylene, 13 mol % of vinyl acetate and 5 mol % of propylene having a melt viscosity V.sub.140 measured at 140? C. of 110 mPas, 65% in kerosene. Density (40? C.) = 0.87 g/cm.sup.3

[0179] Both the amide-ammonium salts (A) and the oil-soluble amines (B) were used in the form of 60% concentrates in a high-boiling aromatic solvent mixture for the purpose of easier handling. Lubricity additives (C) were used without prior dilution. The dosage rates specified in tables 3-8 are based on the amount of active ingredient added in each case.

TABLE-US-00006 TABLE 3 Suppression of the antagonism caused by lubricity additives in respect of the CFPP value by amines in test oil 1 As a further flow improver, the test oil contained 260 ppm by volume of a mixture of 1 part by weight of D1 and 6 parts by weight of G4 (CFI1; density@40? C. = 0.91 g/cm.sup.3). A1 B1 C1 CFPP Ex. [ppm] [ppm] [% by wt.] [ppm] [? C.] 1 24 ?29 (comp.) 2 24 4 17 ?29 (comp.) 3 24 10 42 ?29 (comp.) 4 24 20 83 ?29 (comp.) 5 24 200 ?24 (comp.) 6 24 4 17 200 ?26 7 24 10 42 200 ?28 8 24 20 83 200 ?29 9 24 350 ?22 (comp.) 10 24 4 17 350 ?24 11 24 10 42 350 ?26 12 24 20 83 350 ?29

TABLE-US-00007 TABLE 4 Suppression of the antagonism caused by lubricity additives in respect of paraffin dispersancy by amines in test oil 2 As a further flow improver, the test oil contained 210 ppm by volume of a mixture of 3.5 parts by weight of D1, 1 part by weight of E2 and 17 parts by weight of G3 (CFI2; density@40? C. = 0.90 g/cm.sup.3). The storage temperature was ?22? C. and the storage time 16 h. B Sediment A [% by C1 % by Cloud point [? C.] ?CP.sub.o ?CP.sub.u CFPP [? C.] ?CFPP.sub.o ?CFPP.sub.u Ex. [ppm] wt.; ppm] [ppm] vis vol. before top bottom [? C.] [? C.] before top bottom [? C.] [? C.] PASS 0(C) A1 [54] d 0 ?16.7 ?16.9 ?16.4 0.2 0.3 ?38 ?37 ?37 1.0 1.0 + 1(C) A1 [54] 350 s 8 ?16.5 ?18.5 12.5 2.0 4.0 ?33 ?34 ?25 1.0 8.0 ? 2 A1 [54] B1 [31; 17] 350 d 0 ?16.7 ?16.4 ?16.7 0.3 0.0 ?37 ?35 ?35 2.0 2.0 + 3 A1 [54] B2 [31; 17] 350 d <1 ?16.4 ?17.0 ?15.3 0.6 1.1 ?36 ?38 ?37 2.0 1.0 + 4 A1 [54] B4 [31; 17] 350 d 0 ?16.3 ?16.8 ?15.6 0.5 0.7 ?35 ?35 ?34 0.0 1.0 + 5 A1 [54] B9 [31; 17] 350 d 2 ?16.2 ?17.7 ?14.5 1.5 1.7 ?33 ?35 ?31 2.0 2.0 + 6 A1 [72] d 0 ?16.7 ?16.9 ?16.4 0.2 0.3 ?36 ?36 ?35 0.0 1.0 ? 7 A1 [72] 350 d 0 ?16.5 ?18.9 ?14.1 2.4 2.1 ?34 ?34 ?21 0.0 13.0 ? 8 A2 [72] 350 d 0 ?16.6 ?18.6 ?15.3 2.0 1.3 ?34 ?36 ?28 2.0 6.0 ? 9 A3 [72] 350 d 2 ?16.2 ?16.4 ?14.1 0.2 2.1 ?33 ?33 ?28 0.0 5.0 ? 10 A2 [72] B1 [21; 15] 350 d 0 ?16.5 ?16.6 ?16.3 0.1 0.3 ?35 ?35 ?34 0.0 1.0 + 11 A3 [72] B1 [21; 15] 350 d <1 ?16.3 ?16.4 15.6 0.1 0.7 ?35 ?34 ?33 1.0 2.0 +

TABLE-US-00008 TABLE 5 Suppression of the antagonism caused by lubricity additives in respect of the CFPP value by amines in test oil 3 As a flow improver, the test oil contained 260 ppm by volume of a mixture of 3.5 parts by weight of D1, 1 part by weight of E1 and 15 parts by weight of G2 (CFI3; density@40? C. = 0.91 g/cm.sup.3). A B C CFPP Ex. [ppm] [ppm] % by wt. [ppm] [? C.] 1 A1 [24] ?27 (comp.) 2 A1 [24] B2 [7.5] B2 [31] ?27 (comp.) 3 A1 [24] B4 [7.5] B4 [31] ?26 (comp.) 4 A1 [24] B5 [7.5] B5 [31] ?27 (comp.) 5 A1 [24] B6 [7.5] B6 [31] ?28 (comp.) 6 A1 [24] B7 [7.5] B7 [31] ?27 (comp.) 7 A1 [24] B8 [7.5] B8 [31] ?27 (comp.) 8 A1 [24] C1 [200] ?13 (comp.) 9 A1 [24] B2 [7.5] B2 [31] C1 [200] ?27 10 A1 [24] B4 [7.5] B4 [31] C1 [200] ?26 11 A1 [24] B5 [7.5] B5 [31] C1 [200] ?27 12 A1 [24] B6 [7.5] B6 [31] C1 [200] ?27 13 A1 [24] B7 [7.5] B7 [31] C1 [200] ?26 14 A1 [24] B8 [7.5] B8 [31] C1 [200] ?26 15 A1 [24] C1 [350] ?15 (comp.) 16 A1 [24] B1 [7.5] B1 [31] C1 [350] ?27 17 A1 [24] B5 [7.5] B4 [31] C1 [350] ?27 18 A1 [24] B6 [7.5] B5 [31] C1 [350] ?27 19 A1 [24] B4 [7.5] B6 [31] C1 [350] ?26 20 A1 [24] B7 [7.5] B7 [31] C1 [350] ?27 21 A1 [24] B8 [7.5] B8 [31] C1 [350] ?26

TABLE-US-00009 TABLE 6 Suppression of the antagonism caused by lubricity additives in respect of the CFPP value by amines in test oil 4 As a further flow improver, a mixture of 3.5 parts by weight of D1, 1 part by weight of E1 and 17 parts by weight of G4 (CFI4; density@40? C. = 0.91 g/cm.sup.3) was added to the test oil. CFI 4 A B C [ppm CFPP Ex. [ppm] [ppm] [% by wt.] [ppm] by vol.] [? C.] 1 (comp.) A1 [30] 250 ?27 2 (comp.) A1 [36] 300 ?27 3 (comp.) A1 [30] B2 [9] B2 [31] 250 ?27 4 (comp.) A1 [30] B8 [9] B8 [31] 250 ?27 5 (comp.) A1 [30] C1 [200] 250 ?23 6 (comp.) A1 [36] C1 [200] 300 ?23 7 A1 [30] B2 [9] B2 [31] C1 [200] 250 ?27 8 A1 [30] B8 [9] B8 [31] C1 [200] 250 ?26 9 (comp.) A1 [30] C1 [350] 250 ?22 10 (comp.) A1 [36] C1 [350] 300 ?22 11 A1 [30] B2 [9] B2 [31] C1 [350] 250 ?27 12 A1 [30] B8 [9] B8 [31] C1 [350] 250 ?28

TABLE-US-00010 TABLE 7 Suppression of the antagonism caused by lubricity additives in respect of paraffin dispersancy by amines in test oil 5 As a further flow improver, the test oil contained 280 ppm by volume of a mixture of 4.0 parts by weight of G1, 1 part by weight of D1, 0.5 parts by weight of F1 and 1 part by weight of E1 (CFI5; density@40? C. = 0.90 g/cm.sup.3). The storage temperature was ?18? C., the storage time 24 h. B Sediment A [% by C % by Cloud point [? C.] ?CP.sub.o ?CP.sub.u CFPP [? C.] ?CFPP.sub.o ?CFPP.sub.u Ex. [ppm] wt.; ppm] [ppm] vis vol. before top bottom [? C.] [? C.] before top bottom [? C.] [? C.] PASS 0(C) A1 [36] d 0 ?7.9 ?8.1 ?7.6 0.2 0.3 ?25 ?26 ?25 1.0 0.0 + 1(C) A1 [36] C1 [350] s 4 ?7.7 9.3 ?5.5 1.6 2.2 ?22 ?22 ?18 0.0 4.0 ? 2(C) A1 [36] C2 [350] s 9 ?7.9 ?9.5 ?5.3 1.6 2.6 ?23 ?22 ?18 1.0 5.0 ? 3(C) A1 [36] C3 [350] s 7 ?7.8 ?9.6 ?5.5 1.8 2.3 ?22 ?21 ?18 1.0 4.0 ? 4 A1 [36] B1 [31; 9] C1 [350] d 0 ?7.9 ?7.9 ?7.6 0.0 0.3 ?26 ?25 ?25 1.0 1.0 + 5 A1 [36] B1 [31; 9] C2 [350] d >1 ?7.8 ?7.9 ?7.5 0.1 0.3 ?25 ?25 ?24 0.0 1.0 + 6 A1 [36] B1 [31; 9] C3 [350] d 0 ?7.7 ?7.9 ?7.6 0.2 0.1 ?25 ?26 ?24 1.0 1.0 + 7 A2 [36] B8 [31; 9] C1 [350] d <1 ?7.8 ?8.1 ?7.5 0.3 0.3 ?26 ?25 ?25 1.0 1.0 + 8 A2 [36] B8 [31; 9] C2 [350] d 0 ?7.7 ?8.2 ?7.3 0.5 0.4 ?25 ?26 24 1.0 1.0 + 9 A2 [36] B8 [31; 9] C3 [350] d 2 ?7.8 ?8.2 ?7.5 0.4 0.3 ?26 ?24 ?24 2.0 2.0 +

TABLE-US-00011 TABLE 8 Suppression of the antagonism caused by lubricity additives in respect of paraffin dispersancy by amines in test oil 6 As a further flow improver, the test oil contained 320 ppm of a mixture of 3.5 parts by weight of G3, 1 part by weight of D2, 1 part by weight of F2 and 1 part by weight of E1 (CFI6; density@40? C. = 0.90 g/cm.sup.3). The storage temperature was ?18? C. and the storage time 24 h. B Sediment A [% by C % by Cloud point [? C.] ?CPo ?CP.sub.u CFPP [? C.] ?CFPP.sub.o ?CFPP.sub.u Ex. [ppm] wt.; ppm] [ppm] vis. vol. before top bottom [? C.] [? C.] before top bottom [? C.] [? C.] PASS 0(C) A1 [48] d 0 ?8.0 ?7.6 ?8.2 0.4 0.2 ?25 ?26 ?25 1 0 + 1(C) A1 [48] C1 [300] s 8 ?7.7 ?5.1 ?5.3 2.6 2.4 ?21 ?23 ?18 4 3 ? 2(C) A1 [48] C2 [300] s 9 ?7.6 ?5.2 ?3.5 2.4 4.1 ?20 ?22 ?17 2 3 ? 3(C) A1 [48] C3 [300] s 7 ?7.5 ?4.4 1.8 3.1 5.8 ?22 ?18 ?16 4 6 ? 4(C) A1 [48] C4 [300] s 10 ?7.9 ?5.2 ?4.8 2.7 3.1 ?23 ?20 ?21 3 1 ? 5 A1 [48] B1 [50; 24] C1 [300] d 0 ?7.9 ?8.0 ?7.9 0.1 0.0 ?25 ?24 ?26 1 1 + 6 A1 [48] B1 [50; 24] C2 [300] d >1 ?8.0 ?8.3 ?7.4 0.7 0.6 ?26 ?26 ?25 0 1 + 7 A1 [48] B1 [50; 24] C3 [300] d 0 ?7.8 ?8.1 ?8.0 0.3 0.2 ?27 ?26 ?27 1 0 + 8 A1 [48] B1 [50; 24] C4 [300] d 1 ?7.9 ?8.1 ?7.5 0.2 0.4 ?26 ?25 ?26 1 0 + 9 A1 [48] B3 [50; 24] C4 [300] d 1 ?8.0 ?8.5 ?7.3 0.5 0.7 ?25 ?25 ?24 0 1 +