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

Abstract

The present invention relates to a low-temperature additive for fuel oils 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) 0.1 to 10 parts by weight, based on the amount of amide-ammonium salt (A), of a resin formed from at least one aromatic compound bearing an alkyl radical and an aldehyde and/or ketone (D).

Claims

1.-4. (canceled)

5. 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) and a resin formed from at least one aromatic compounds bearing an alkyl radical and an aldehyde and/or ketone (D), wherein the method comprises the step of adding a low-temperature additive to the fuel oil, and in which the low-temperature additive comprises 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) 0.1 to 10 parts by weight, based on the amount of amide-ammonium salt (A), of a resin formed from at least one aromatic compound bearing an alkyl radical and an aldehyde and/or ketone (D) wherein the fuel oil contains between 50 and 1000 ppm of a lubricity additive (C) which is selected from the group consisting of fatty acids, oligomers of unsaturated fatty acids, alk(en)ylsuccinic acids, partial esters of polyols with fatty acids, oligomers of unsaturated fatty acids, alk(en)ylsuccinic acids, fatty acid amides of alkanolamines and mixtures thereof.

6. The method as claimed in claim 5, in which the lubricity additive (C) is a fatty acid.

7. A fuel oil having a sulfur content of less than 50 ppm, comprising a lubricity additive (C) and a low-temperature additive, in which the low-temperature additive comprises 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) 0.1 to 10 parts by weight, based on the amount of amide-5 ammonium salt (A), of a resin formed from at least one aromatic compound bearing an alkyl radical and an aldehyde and/or ketone (D), and in which the lubricity additive (C) is selected from the group consisting of fatty acids, oligomers of unsaturated fatty acids, alk(en)ylsuccinic acids, partial esters of polyols with fatty acids, oligomers of unsaturated fatty acids and/or alk(en)ylsuccinic acids, fatty acid amides of alkanolamines, and mixtures thereof.

8. The method as claimed in claim 5, wherein the polycarboxylic acid is selected from the group consisting of monomeric dicarboxylic acids, monomeric polycarboxylic acids and copolymerized dicarboxylic acids.

9. The method as claimed in claim 5, wherein the low-temperature additive contains 1% to 95% by weight of amide-ammonium salt (A).

10. The method as claimed in claim 5, in which 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.m—NH.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.m—NH.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.

11. The method as claimed in claim 5, wherein the low-temperature additive contains 15% to 70% by weight of oil-soluble amine (B) based on the amount of amide-5 ammonium salt (A).

12. The method as claimed in claim 5, wherein the oil-soluble amine (B) is a primary, secondary or tertiary fatty amine.

13. The method as claimed in claim 10, 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.

14. The method as claimed in claim 5, wherein the oil-soluble amine (B) has at least one alkyl radical having 10 to 22 carbon atoms.

15. The method as claimed in claim 5, wherein the oil-soluble amine (B) is a polyamine.

16. The method as claimed in claim 5, wherein constituent iii) is an alkylphenol resin or a hydroxybenzoate resin.

17. The method as claimed in claim 5, wherein the low-temperature additive additionally comprises a polyoxyalkylene compound (E).

18. The method as claimed in claim 5, wherein the low-temperature additive additionally comprises a comb polymer (F).

19. The method as claimed in claim 5, wherein the low-temperature additive additionally comprises an ethylene copolymer (G).

20. The fuel oil as claimed in claim 7, in which the sulfur content of the fuel is less than 20 ppm.

21. The fuel oil as claimed in claim 7, wherein the fuel oil contains 50 to 1500 ppm (m/m), of the low-temperature additive (A).

22. The fuel oil as claimed in claim 7, wherein the fuel oil is of mineral origin.

23. The fuel oil as claimed in claim 7, wherein the fuel oil comprises synthetic fuel.

24. The fuel oil as claimed in claim 7, wherein the fuel oil is a middle distillate.

25. The fuel oil as claimed in claim 7, wherein the fuel oil is diesel oil or heating oil.

26. The fuel oil as claimed in claim 7, wherein the polycarboxylic acid is selected from the group consisting of monomeric dicarboxylic acids, monomeric polycarboxylic acids and copolymerized dicarboxylic acids.

27. The fuel oil as claimed in claim 7, wherein the low temperature additive contains 1% to 95% by weight of amide-ammonium salt (A).

28. The fuel oil as claimed in claim 7, in which the oil-soluble amine (B) has the formula (1) ##STR00007## 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.m—NH.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.m—NH.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.

29. The fuel oil as claimed in claim 7, wherein the low-temperature additive contains 15% to 70% by weight of oil-soluble amine (B) based on the amount of amide-5 ammonium salt (A).

30. The fuel oil as claimed in claim 7, wherein the oil-soluble amine (B) is a primary, secondary or tertiary fatty amine.

31. The fuel oil as claimed in claim 28, 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.

32. The fuel oil as claimed in claim 7, wherein the oil-soluble amine (B) has at least one alkyl radical having 10 to 22 carbon atoms.

33. The fuel oil as claimed in claim 7, wherein the oil-soluble amine (B) is a polyamine.

34. The fuel oil as claimed in claim 7, wherein constituent iii) is an alkylphenol resin or a hydroxybenzoate resin.

35. The fuel oil as claimed in claim 7, wherein the low-temperature additive additionally comprises a polyoxyalkylene compound (E).

36. The fuel oil as claimed in claim 7, wherein the low-temperature additive additionally comprises a comb polymer (F).

37. The fuel oil as claimed in claim 7, wherein the low-temperature additive additionally comprises an ethylene copolymer (G).

Description

EXAMPLES

[0151] All figures in percent and also in ppm are based on parts by weight, unless indicated otherwise.

[0152] 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.

[0153] 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.

[0154] Paraffin dispersancy was determined in sedimentation tests that were conducted as follows:

[0155] 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).

[0156] 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.

[0157] 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.

[0158] The sedimentation test was considered to have been passed if the following five criteria were satisfied: [0159] 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. [0160] Criterion 2: The CP of the lower phase may be not more than 2 K above the CP of the oil before the storage (ΔCP.sub.u). [0161] Criterion 3: The CP of the upper phase may be not more than 2 K below the CP of the oil before the storage (ΔCP.sub.o). [0162] Criterion 4: The CFPP of the lower phase may be not more than 2 K above the CFPP of the oil before the storage (ΔCFPP.sub.u). [0163] Criterion 5: The CFPP of the upper phase may be not more than 2 K below the CFPP of the oil before the storage (ΔCFPP.sub.u).

[0164] 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 Test Test Test Test Test Test oil 1 oil 2 oil 3 oil 4 oil 5 oil 6 oil 7 Distillation IBP [° C.] 196.7 176.8 176.2 187.3 201.4 173.2 183.4 20% [° C.] 240.8 219.6 223.1 246.7 249.7 223.2 239.2 90% [° C.] 327.2 318.9 331.0 332.8 333.8 332.9 328.1 (90-20) % [° C.] 86.4 99.3 107.9 86.1 84.1 109.7 88.9 FBP [° C.] 355.1 340.1 358.1 360.6 354.9 357.4 358.7 Cloud point [° C.] −11.2 −16.0 −7.1 −7.1 −8 −7.8 −7.0 CFPP [° C.] −11 −18 −10 −8 −8 −8 −8 Pour point [° C.] −21 −24 −15 −15 −12 −18 −15 Density @15° C. [g/cm.sup.3] 0.8398 0.8412 0.8304 0838 0.8563 0.8328 0837 Sulfur content [ppm] 9 7 9 8 7 9 9 Aromatic content [% by wt.] 32.75 29.9 24.7 28.67 23.94 19.09 29.5 of which mono [% by wt.] 26.4 24.3 22.5 23.8 20.76 17.89 22.9 di [% by wt.] 5.87 4.32 2.0 4.53 3.01 1.2 6.4 poly [% by wt.] 0.48 0.38 0.2 0.34 0.17 0 0.2 n-Paraffin content [% by wt.] 23.2 24.3 26.5 23.7 26.3 22.5 23.5

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-α-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) B2 Di(stearylamine) B3 Tallowamine B4 Dimethyllaurylamine B5 Dimethyltetradecylamine B6 Tallowpropylenediamine B7 Dimethylhexadecylamine B8 Dimethylcocoamine B9 Triethylenetetramine

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

[0165] 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 3-9 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 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

[0166] 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 (CFI 1; density@40° C.=0.91 g/cm.sup.3).

TABLE-US-00007 TABLE 4 Suppression of the antagonism caused by lubricity additives in respect of paraffin dispersancy by amines in test oil 2 B Sediment A [% by wt.; C1 % by Cloud point [° C.] ΔCP.sub.o ΔCP.sub.u CFPP [° C.] ΔCFPP.sub.o ΔCFPP.sub.u Ex. [ppm] 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 +

[0167] 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 (CFI 1; density@40° C.=0.90 g/cm.sup.3). The storage temperature was −22° C. and the storage time 16 h.

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 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

[0168] 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 E1and 15 parts by weight of G2 (CFI 3; density@40° C.=0.91 g/cm.sup.3).

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 CFI 4 A B C [ppm by CFPP Ex. [ppm] [ppm] [% by wt.] [ppm] vol.] [° C.] 1 A1 [30] — — — 250 −27 (comp.) 2 A1 [36] — — — 300 −27 (comp.) 3 A1 [30] B2 [9] B2 [31] — 250 −27 (comp.) 4 A1 [30] B8 [9] B8 [31] — 250 −27 (comp.) 5 A1 [30] — — C1 [200] 250 −23 (comp.) 6 A1 [36] — — C1 [200] 300 −23 (comp.)  7 A1 [30] B2 [9] B2 [31] C1 [200] 250 −27  8 A1 [30] B8 [9] B8 [31] C1 [200] 250 −26 9 A1 [30] C1 [350] 250 −22 (comp.) 10 A1 [36] C1 [350] 300 −22 (comp.) 11 A1 [30] B2 [9] B2 [31] C1 [350] 250 −27 12 A1 [30] B8 [9] B8 [31] C1 [350] 250 −28

[0169] As a further flow improver, a mixture of 3.5 parts by weight of D1, 1 part by weight of E1and 17 parts by weight of G4 (CFI 4; density@40° C.=0.91 g/cm.sup.3) was added to the test oil.

TABLE-US-00010 TABLE 7 Suppression of the antagonism caused by lubricity additives in respect of paraffin dispersancy by amines in test oil 5 B Sediment A [% by wt.; C % by Cloud point [° C.] ΔCP.sub.o ΔCP.sub.u CFPP [° C.] ΔCFPP.sub.o ΔCFPP.sub.u Ex. [ppm] 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 +

[0170] 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(CFI 5; density@40° C.=0.90 g/cm.sup.3). The storage temperature was −18° C., the storage time 24 h.

TABLE-US-00011 TABLE 8 Suppression of the antagonism caused by lubricity additives in respect of paraffin dispersancy by amines in test oil 6 B Sediment A [% by wt ; C % by Cloud point [° C.] ΔCP.sub.o ΔCP.sub.u CFPP [° C.] ΔCFPP.sub.o ΔCFPP.sub.u Ex. [ppm] 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 −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 +

[0171] 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(CFI 6; density@40° C.=0.90 g/cm.sup.3). The storage temperature was −18° C. and the storage time 24 h.

TABLE-US-00012 TABLE 9 Suppression of the antagonism caused by lubricity additives in respect of the CFPP value by amines and resins in test oil 7 B CFI 7 A [% by wt.; C D [ppm by CFPP [ppm] ppm] [ppm] [ppm] vol.] [° C.]  1 (C) A1 [48] — — — 230 −20  2 (C) A1 [48] — — D1 [50] 230 −23  3 (C) A1 [48] — C1 [300] — 230 −15  4 A1 [48] — C1 [300] D1 [50] 230 −18  5 A1 [48] B1 [50; 24] C1 [300] — 230 −19  6 A1 [48] B1 [50; 24] C1 [300] D1 [50] 230 −24  7(C) A2 [48] — — — 230 −19  8(C) A2 [48] — — D2 [50] 230 −22  9 (C) A2 [48] — C2 [300] — 230 −15 10 A2 [48] — C2 [300] D2 [50] 230 −17 11 A2 [48] B1 [50; 24] C2 [300] — 230 −19 12 A2 [48] B1 [50; 24] C2 [300] D2 [50] 230 −22

[0172] As a further flow improver, the test oil contained a mixture of 1.5 parts by weight of E1 and 17 parts by weight of G4 (CFI 7; density@40° C.=0.90 g/cm.sup.3).

[0173] The experiments in table 9 show that the antagonistic effect caused by the lubricity additive (C) on the improvement in low-temperature properties achieved by the amide-ammonium salt (A) in combination with the further flow improvers can be counteracted both by addition of an amine (A) and by addition of a resin (D). Only by addition of amine (A) and resin (D) can the antagonistic effect be overcome.