Fuels

Abstract

An additive composition for a diesel fuel, the additive composition comprising: (i) a first additive comprising one or more of: (a) the reaction product of a polycarboxylic acid having at least one tertiary amino group and a primary or secondary amine; (b) the reaction product of an ?, ? dicarboxylic acid or a derivative thereof and a primary amine; and (c) the reaction product of a polyamine and a fatty acid; and (ii) a second additive 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.

Claims

1. A diesel fuel composition comprising a major proportion of a diesel fuel and: from 50 to 5000 ppm of a first additive (i) comprising one or more of: (a) the reaction product of a carboxylic acid selected from nitrilotriacetic acid, ethylenediamine tetraacetic acid and propylene-1,2-diamine tetraacetic acid and an amine selected from dioleylamine, dipalmitamine, dicoconut fatty amine, distearylamine, dibehenyl amine, ditallow fatty amine and hydrogenated ditallow fatty amine; (b) the reaction product of maleic anhydride and an amine selected from coconut amine, tallow fatty amine, oleyl amine, arachidyl amine, tridecyl amine and behenyl amine; and (c) the reaction product of polyethylene polyamines having 2 to 6 nitrogen atoms and fatty acids having 16 to 20 carbon atoms; and from 50 to 5000 ppm of a second additive (ii) which is a terpolymer obtained by reacting monomers of: (x) ethylene; (y) vinyl or propenyl esters of C1 to C20 carboxylic acids; and (z) a third monomer different to (x) and (y) comprising an alkene functional group selected from: an ?-olefin; an ?,? unsaturated carboxylic acid or an ester thereof; and an ester of an unsaturated alcohol, wherein the diesel fuel comprises mineral diesel and at least 5 vol % of a renewable diesel fuel obtained by the hydrodeoxygenation of fats and oils; and 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).

2. A method of improving the lower temperature flow properties of a diesel fuel composition, the method comprising admixing into the composition: from 50 to 5000 ppm of a first additive (i) comprising one or more of: (a) the reaction product of a carboxylic acid selected from nitrilotriacetic acid, ethylenediamine tetraacetic acid and propylene-1,2-diamine tetraacetic acid and an amine selected from dioleylamine, dipalmitamine, dicoconut fatty amine, distearylamine, dibehenyl amine, ditallow fatty amine and hydrogenated ditallow fatty amine; (b) the reaction product of maleic anhydride and an amine selected from coconut amine, tallow fatty amine, oleyl amine, arachidyl amine, tridecyl amine and behenyl amine; and (c) the reaction product of polyethylene polyamines having 2 to 6 nitrogen atoms and fatty acids having 16 to 20 carbon atoms; and from 50 to 5000 ppm of a second additive (ii) which is a terpolymer obtained by reacting monomers of: (x) ethylene; (y) vinyl or propenyl esters of C1 to C20 carboxylic acids; and (z) a third monomer different to (x) and (y) comprising an alkene functional group selected from: an ?-olefin; an ?,? unsaturated carboxylic acid or an ester thereof; and an ester of an unsaturated alcohol, wherein the diesel fuel comprises mineral diesel and at least 5 vol % of a renewable diesel fuel obtained by the hydrodeoxygenation of fats and oils; and wherein the method provides an improved performance in a low temperature flow test (as defined in ASTM D4539 or CAN CGSB-3.0, no. 140.1-2017).

3. The diesel fuel composition of claim 1 wherein the first additive (i) comprises (a), (b) and (c).

4. The diesel fuel composition of claim 1 wherein monomer (y) is vinyl acetate.

5. The diesel fuel composition of claim 1 wherein monomer (z) is selected from propene, vinyl neononanoate, vinyl 2-ethylhexanoate and 2-ethylhexylacrylate.

6. The method of claim 2 which provides an LTFT depression of at least 2? C.

Description

EXAMPLE 1

(1) An additive composition was prepared comprising the following components:

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

(3) Additive A is a terpolymer comprising 85 mol % ethylene, 10 mol % vinyl acetate and 5 mol % 2-ethylhexylacrylate.

(4) The molecular weight analysis of additive A is as follows:

(5) 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
Additive B comprises 72 wt % of an amide of EDTA and a Cm to Cm dialkyl amine; maleic acid tridecyl amide; and the reaction product of diethylene triamine and oleic acid.

EXAMPLE 2

(6) Mineral diesel fuels were sourced having the following characteristics:

(7) 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)

(8) 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

(9) 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.

(10) The biodiesel was compliant with ASTM D6751 and CAN CGSB-3.524

(11) The renewable diesel contained 12.15% n-paraffins and had a density of 0.78 gcm.sup.?3.

(12) These fuels were then tested according to the LTFT test method set out below, and the results are in table 1.

LTFT Test Method

(13) 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.

(14) 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

(15) An additive composition was prepared comprising the following components:

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

(17) 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

(18) An additive composition was prepared comprising the following components:

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

(20) 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

(21) An additive composition was prepared comprising the following components:

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

(23) 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

(24) An additive composition was prepared comprising the following components:

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

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

EXAMPLE 8 (COMPARATIVE)

(27) An additive composition was prepared comprising the following components:

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

EXAMPLE 9

(29) Further additised fuel compositions were tested according to the method of example 3. The results are shown in table 2.

(30) 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