FUELS

Abstract

An additive composition for a diesel fuel, the additive composition comprising: a first additive comprising one or more of: the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine; the reaction product of an ?, ? dicarboxylic acid or a derivative thereof and a primary amine; and the reaction product of a polyamine and a fatty acid; and a second additive which is a terpolymer obtained by reacting monomers of: an ?-olefin; an ester of an unsaturated alcohol; and a third monomer different to (x) and (y) comprising an alkene functional group.

Claims

1. A diesel fuel composition comprising a major proportion of a diesel fuel comprising mineral diesel and from 1 to 30 wt % of a fuel selected from biodiesel, renewable diesel and mixtures thereof, and: a first additive (i) comprising: (a) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine; a second additive (ii) which is a terpolymer obtained by reacting monomers of: (x) an ?-olefin; (y) an ester of an unsaturated alcohol; and (z) a third monomer different to (x) and (y) comprising an alkene functional group.

2. A method of improving the lower temperature flow properties of a diesel fuel composition comprising mineral diesel and from 1 to 30 wt % of a fuel selected from biodiesel, renewable diesel and mixtures thereof, the method comprising admixing into the composition: a first additive (i) comprising: (a) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine; and a second additive (ii) which is a terpolymer obtained by reacting monomers of: (x) an ?-olefin; (y) an ester of an unsaturated alcohol; and (z) a third monomer different to (x) and (y) comprising an alkene functional group.

3. A composition according to claim 1 wherein component (a) comprises the reaction product of a polycarboxylic acid selected from nitrilotriacetic acid, ethylenediamine tetraacetic acid and propylene-1,2-diamine tetraacetic acid and a secondary amine of formula HNR.sub.2 in which each R is independently a straight chain or branched C.sub.10 to C.sub.30 alkyl or alkenyl group, preferably a C.sub.14 to C.sub.24 alkyl or alkenyl group.

4. A composition according to claim 1 wherein component (a) comprises the reaction product of 1 mole of ethylenediamine tetraacetic acid and 4 moles of hydrogenated tallow fatty amine.

5. A composition according to claim 1 wherein additive (i) further comprises (b) the reaction product of an ?, ? dicarboxylic acid or a derivative thereof and a primary amine.

6. A composition according to claim 1 wherein additive (i) further comprises (c) the reaction product of a polyamine and a fatty acid.

7. A composition according to claim 1 wherein additive (i) further comprises (a) the reaction product of an ?, ? dicarboxylic acid or a derivative thereof and a primary amine; and (b) the reaction product of a polyamine and a fatty acid.

8. A composition according to claim 1 wherein the diesel fuel composition has an improved performance in a low temperature flow test (as defined in ASTM D4539 or CAN CGSB-3.0, no. 140.1-2017) as compared to the same fuel without the first additive (i) and the second additive (ii).

9. A composition according to claim 1 wherein monomer (x) is ethylene.

10. A composition according to claim 1 wherein monomer (y) is vinyl acetate.

11. A composition according to claim 2 wherein monomer (z) is selected from propene, vinyl neononanoate, vinyl 2-ethylhexanoate and 2-ethylhexylacrylate, preferably wherein (z) is 2-ethylhexylacrylate.

12. A method according to claim 2 wherein component (a) comprises the reaction product of a polycarboxylic acid selected from nitrilotriacetic acid, ethylenediamine tetraacetic acid and propylene-1,2-diamine tetraacetic acid and a secondary amine of formula HNR.sub.2 in which each R is independently a straight chain or branched C.sub.10 to C.sub.30 alkyl or alkenyl group, preferably a C.sub.14 to C.sub.24 alkyl or alkenyl group.

13. A method according to claim 2 wherein component (a) comprises the reaction product of 1 mole of ethylenediamine tetraacetic acid and 4 moles of hydrogenated tallow fatty amine.

14. A method according to claim 2 wherein additive (i) further comprises (b) the reaction product of an ?, ? dicarboxylic acid or a derivative thereof and a primary amine.

15. A method according to claim 2 wherein additive (i) further comprises (c) the reaction product of a polyamine and a fatty acid.

16. A method according to claim 2 wherein additive (i) further comprises (a) the reaction product of an ?, ? dicarboxylic acid or a derivative thereof and a primary amine; and (b) the reaction product of a polyamine and a fatty acid.

17. A method according to claim 2 which provides an improved performance in a low temperature flow test (as defined in ASTM D4539 or CAN CGSB-3.0, no. 140.1-2017) as compared to the same fuel without the first additive (i) and the second additive (ii).

18. A method according to claim 2 wherein monomer (x) is ethylene.

19. A method according to claim 2 wherein monomer (y) is vinyl acetate.

20. A composition according to claim 2 wherein monomer (z) is selected from propene, vinyl neononanoate, vinyl 2-ethylhexanoate and 2-ethylhexylacrylate, preferably wherein (z) is 2-ethylhexylacrylate.

21. A method of improving the performance in an LTFT test of a diesel fuel composition comprising mineral diesel and from 1 to 30 wt % of a fuel selected from biodiesel, renewable diesel and mixtures thereof, the method comprising: dosing into the diesel fuel composition: a first additive (i) comprising: (a) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine; a second additive (ii) which is a terpolymer obtained by reacting monomers of: (x) an ?-olefin; (y) an ester of an unsaturated alcohol; and (z) a third monomer different to (x) and (y) comprising an alkene functional group; and measuring the degree to which the LTFT is depressed compared with an otherwise identical fuel except for the presence of additive (i) and additive (ii).

22. A method according to claim 21 which provides an LTFT depression of at least 2? C.

Description

EXAMPLE 1

[0249] An additive composition was prepared comprising the following components:

TABLE-US-00001 Composition 1 wt % Additive A 38.2 Additive B 6.2 Aromatic solvents 6.2 including naphthalene Xylene 49.4

[0250] Additive A is a terpolymer comprising 85 mol % ethylene, 10 mol % vinyl acetate and 5 mol % 2-ethythexylacrylate.

[0251] The molecular weight analysis of additive A is as follows:

TABLE-US-00002 M.sub.n M.sub.w M.sub.p M.sub.z M.sub.z+1 PD 4,006 8,368 8,055 15,343 23,586 2.06

[0252] Additive B comprises 72 wt % of an amide of EDTA and a C.sub.16 to C.sub.18 dialkyl amine; maleic acid tridecyl amide; and the reaction product of diethylene triamine and oleic acid.

EXAMPLE 2

[0253] Mineral diesel fuels were sourced having the following characteristics:

TABLE-US-00003 Fuel A Fuel B Fuel C Fuel D Fuel E Fuel F IBP 118.6 93.6 97.5 120.7 117.6 96.8 T90 343.3 351.6 331.1 328.7 354.6 319.5 T95 357.9 370.8 350.6 347.8 372.3 352.6 FBP 400.6 412.0 399.3 381.9 418.6 376.2 n-paraffin 6.093 7.779 9.279 6.970 7.858 12.267 content (wt %) Density at 0.847 0.850 0.845 0.844 0.855 0.838 15? C. (gcm.sup.?3) Fuel G Fuel H Fuel I Fuel J Fuel K Fuel L IBP 102.5 100.8 106.9 126.6 125.4 105.5 T90 337.8 331.3 322.4 344.6 330.6 327.9 T95 354.7 353.8 339.5 361.6 350.8 345.3 FBP 390.1 382.3 363.4 406.9 407.5 395.6 n-paraffin 8.918 10.616 5.631 5.910 5.899 7.703 content (wt %) Density at 0.859 0.849 0.854 0.855 0.850 0.848 15? C. (gcm.sup.?3)

[0254] All of these mineral diesel fuels had a sulfur content of less than 50 ppm by weight and complied with ASTM D975 or CAN CGSB 5.517.

EXAMPLE 3

[0255] The additive of example 1 was dosed into various fuels including those listed in example 2, and blends thereof with biodiesel and/or renewable diesel.

[0256] The biodiesel was compliant with ASTM D6751 and CAN CGSB-3.524

[0257] The renewable diesel contained 12.15% n-paraffins and had a density of 0.78 gcm.sup.?3.

[0258] These fuels were then tested according to the LTFT test method set out below, and the results are in table 1.

LTFT Test Method

[0259] 200 mL of fuel was cooled at a rate of 1? C./hour, beginning at least 10? C. above the measured cloud point of the fuel. At 1? C. intervals, measured from a reference sample in the same cooling medium/chamber, the sample of fuel was filtered at 20 kPa across a 17 ?m stainless steel twill Dutch weave filter into a receiving beaker. If 180 mL (or more) of fuel is filtered within 60 seconds this is noted as a Pass. If 60 seconds elapse and 180 mL of fuel (90% of the total volume) has not passed to the receiving beaker, this is noted as a Fail. The LTFT temperature is the last temperature at which a Pass is followed on the subsequent 1? C. test temperature by a Fail.

TABLE-US-00004 TABLE 1 Treat rate additive Mineral % vol % vol % vol ppm by LTFT fuel mineral biodiesel renewable volume (? C.) A 95 5 0 0 ?24 A 95 5 0 250 ?26 A 95 5 0 500 ?29 B 95 5 0 0 ?20 B 95 5 0 500 ?24 B 95 5 0 1000 ?28 C 95 5 0 0 ?24 C 95 5 0 500 ?32 D 98 2 0 0 ?41 D 98 2 0 1250 ?48 D 95 5 0 0 ?40 D 95 5 0 750 ?45 E 98 2 0 0 ?23 E 98 2 0 1000 ?33 E 95 5 0 0 ?25 E 95 5 0 1000 ?34 F 100 0 0 0 ?34 F 100 0 0 1500 ?48 G 100 0 0 0 ?25 G 100 0 0 750 ?35 H 100 0 0 0 ?28 H 100 0 0 1000 ?41 I 98 2 0 0 ?37 I 98 2 0 500 ?43 J 70 0 30 0 ?25 J 70 0 30 2000 ?30 K 90 10 0 0 ?37 K 90 10 0 1500 ?43 K 85.5 4.5 10 0 ?34 K 85.5 4.5 10 900 ?39 K 85.5 4.5 10 1900 ?42 L 90 10 0 0 ?28 L 90 10 0 1000 ?41

EXAMPLE 4

[0260] An additive composition was prepared comprising the following components:

TABLE-US-00005 Composition 2 wt % Additive A 38.2 Additive D 6.2 Aromatic solvents 2.5 including naphthalene Xylene 53.1

[0261] Additive D comprises 71 wt % of the reaction product of ethylenediamine tetra(acetic acid) (EDTA) and 4 eq of di(hydrogenated tallow)amine.

EXAMPLE 5

[0262] An additive composition was prepared comprising the following components:

TABLE-US-00006 Composition 3 wt % Additive E 38.2 Additive B 6.2 Aromatic solvents 6.2 including naphthalene Xylene 49.4

[0263] Additive E is a terpolymer prepared from ethylene (?86 mol %), vinyl acetate (?12 mol %) and vinyl 2-ethylhexanoate (?2 mol %) and having a number average molecular weight (Mn) ?3,200.

EXAMPLE 6

[0264] An additive composition was prepared comprising the following components:

TABLE-US-00007 Composition 4 wt % Additive F 38.2 Additive B 6.2 Aromatic solvents 6.2 including naphthalene Xylene 49.4

[0265] Additive F is a terpolymer prepared from ethylene (?85 mol %), vinyl acetate (?14 mol %) and vinyl neodecanoate (?1 mol %) and having a number average molecular weight (Mn) ?4,200.

EXAMPLE 7

[0266] An additive composition was prepared comprising the following components:

TABLE-US-00008 Composition 5 wt % Additive A 38.2 Additive G 6.2 Aromatic solvents 18.9 including naphthalene Xylene 36.7

[0267] Additive G comprises 25 wt % of the reaction product of phthalic anhydride and 2 eq of di(hydrogenated tallow)amine.

EXAMPLE 8 (COMPARATIVE)

[0268] An additive composition was prepared comprising the following components:

TABLE-US-00009 Composition 6 wt % Additive B 6.2 Aromatic solvents 44.4 including naphthalene Xylene 49.4

EXAMPLE 9

[0269] Further additised fuel compositions were tested according to the method of example 3. The results are shown in table 2.

TABLE-US-00010 TABLE 2 Treat rate % vol % vol additive Mineral % vol bio- renew- Additive ppm by LTFT fuel mineral diesel able composition volume (? C.) D 95 5 0 No additive 0 ?40 D 95 5 0 Example 1 750 ?45 D 95 5 0 Example 8 1000 ?38 (comparative) D 95 5 0 Example 4 1000 ?45 D 95 5 0 Example 5 1000 ?45 D 95 5 0 Example 6 1000 ?44 D 95 5 0 Example 7 1000 ?45 L 90 10 0 No additive 0 ?28 L 90 10 0 Example 1 1000 ?41 L 90 10 0 Example 8 1000 ?28 (comparative) L 90 10 0 Example 4 1000 ?38 L 90 10 0 Example 5 1000 ?39 L 90 10 0 Example 6 1000 ?44 L 90 10 0 Example 7 1000 ?44