Composition of fuel oils

Abstract

The present invention relates to a fuel oil additive comprising A) a copolymer of ethylene and from 13 to 17 mol % of at least one acrylic ester or vinyl ester having a C1-C18-alkyl radical and a melt viscosity V140 of not more than 80 mPas, andB) a comb polymer comprising structural units formed fromB1) at least one olefin as monomer 1, which bears at least one C8-C18-alkyl radical on the olefinic double bond, andB2) at least one ethylenically unsaturated dicarboxylic acid as monomer 2, which bears at least one C8-C16-alkyl radical bonded via an ester group,in which the parameter Q

Description

EXAMPLES

TABLE 1
Characterization of the ethylene copolymers used
			CH3/100	Content of
Example	Comonomer(s)	V140	CH2	vinyl ester
A1 (C)	Ethylene/	110 mPas	4.2	13.3 mol %
	VAC/
	vinyl
	neodecanoate
A2	Ethylene/	35 mPas	3.9	16.6 mol %
	VAC
A3 (C)	Ethylene/	154 mPas	3.0	16.7 mol %
	VAC
A4 (C)	Ethylene/	125 mPas	3.0	13.8 mol %
	VAC
VAC = vinyl acetate

The vinyl ester content was measured by means of pyrolysis and subsequent titration.

The viscosity (V₁₄₀) was measured with a Haake Reostress 600 viscometer.

The degree of branching (CH₃/100CH₂) was measured on a ¹H NMR unit at 400 MHz in CDCl₃, and calculated by means of integration of the individual signals.

TABLE 2
Characterization of the comb polymers used
				Acid
				number
				[mg
Example	Comonomers	Alcohol	Q	KOH/g]
B1	MSA-co-C14/16-α-	C12/C16	25.6	49.9
	olefin (1:0.5:0.5)	alcohol
		(85%:15%)
B2	MSA-co-C14/16-α-	C12 alcohol	25.0	48.2
	olefin (1:0.5:0.5)
B3	MSA-co-C14/16-α-	C12 alcohol	23.0	51.1
	olefin (1:05:05)

TABLE 3
Acrylates
C1 Poly(octadecyl acrylate), K value 32
C2 Poly(behenyl acrylate), K value 18

TABLE 4
Characterization of the test oils
	Oil No.:	CFPP [° C.]	Composition
	E1	−8	Soya Me/RME 30:70
	E2	−7	RME/PME 85:15
	E3	−11	RME/AME 60:40
	E4	−10	RME/AME 50:50
	E5	−8	RME/AME 40:60
	E6	−8	RME/AME 45:55
	SoyaME = soya methyl ester
	RME = rapeseed oil methyl ester
	PME = palm oil methyl ester
	AME = used oil methyl ester

TABLE 5
Methyl ester distribution of the test oils
	E1	E2	E3	E4	E5	E6
C16:0	6.53	6.21	6.74	7.33	8.13	7.76
C18:0	1.19	2.36	2.71	2.97	3.32	3.16
C18:1	45.19	48.73	52.53	50.84	45.36	46.77
C18:2	36.33	28.77	26.45	28.17	32.27	31.00
C18:3	8.37	9.18	6.36	5.49	5.45	5.89
C20:1/2/3	0.79	1.25	1.14	1.04	0.97	1.03
C20:0	0.39	0.57	0.58	0.56	0.53	0.57
C22:0	0.15	0.39	0.48	0.51	0.50	0.49

In the tables which follow, the mixing ratio according to weight of the additives A, B and C is A:B=4:1, or, when C is present in the mixtures, A:B:C=4:1:0.2. The total amount of additive is evident from the top row of the table.

TABLE 6
CFPP testing in test oil E1
	Comb	Ethylene		2000	3000
Ex.	polymer	copolymer	Polyacrylate	ppm	ppm	4000 ppm
1 (C)	B2	A4	—	−12	−13	−12
2 (C)	B2	A3	—	−16	−18	−10
3	B2	A2	—	−17	−18	−18
4	B1	A2	—	−14	−15	−17
5 (C)	B1	A1	—	−13	−13	−11
6 (C)	B2	A1	—	−11	−17	−11
7	B2	A2	C1	−18	−20	−20
8	B3	A2	—	−18	−20	−20

TABLE 7
CFPP testing in test oil E2
	Comb	Ethylene	Poly-	2000	3000
Ex.	polymer	copolymer	acrylate	ppm	ppm	4000 ppm
9	B1	A2	—	−7	−7	−11
10 (C)	B2	A3	—	−7	−10	−10
11	B1	A2	—	−7	−9	−12
12	B1	A2	C2	−9	−10	−12
13	B3	A2	—	−9	−9	−12

TABLE 8
CFPP testing in test oil E3
	Comb	Ethylene	Poly-	2000
Ex.	polymer	copolymer	acrylate	ppm	3000 ppm
14 (C)	B1	A1	—	−18	−11
15	B1	A2	—	−19	−20
16	B3	A2	—	−18	−20

TABLE 9
CFPP testing in test oil E4
	Comb	Ethylene
Ex.	polymer	copolymer	Polyacrylate	2000 ppm	3000 ppm
17 (C)	B1	A1	—	−17	−10
18	B1	A2	—	−18	−20
19 (C)	B1	A4	—	−17	−10

TABLE 10
CFPP testing in test oil E5
	Comb	Ethylene
Ex.	polymer	copolymer	Polyacrylate	2000 ppm	3000 ppm
20 (C)	B2	A1	—	−12	−9
21 (C)	B1	A1	—	−10	−9
22	B1	A2	—	−12	−19
23	B1	A2	C2	−13	−19
24 (C)	B1	A3	—	−10	−9

TABLE 11
CFPP testing in test oil E6
		Comb	Ethylene
	Ex.	polymer	copolymer	Polyacrylate	4000 ppm
	25 (C)	B2	A1	—	−8
	26 (C)	B1	A1	—	−9
	27	B2	A2	—	−19
	28 (C)	B1	A4	—	−8

Claims

1. A fuel oil additive comprising A) a copolymer of ethylene and from 13 to 17 mol % of at least one acrylic ester or vinyl ester having a C1-C18-alkyl radical and a melt viscosity V140 of not more than 80 mPas, andB) a comb polymer comprising structural units formed fromB1) at least one olefin as monomer 1, which bears at least one C8-C18-alkyl radical on the olefinic double bond, andB2) at least one ethylenically unsaturated dicarboxylic acid as monomer 2, which bears at least one C8-C16-alkyl radical bonded via an ester group, in which the parameter Q

2. The fuel oil additive as claimed in claim 1, wherein Q assumes values of from 24 to 26.

3. The fuel oil additive as claimed in claim 1, wherein constituent A) comprises from 15 to 17 mol % of at least one vinyl ester.

4. The fuel oil additive of claim 1, wherein constituent A) comprises from 0.5 to 10 mol % of olefins having from 3 to 10 carbon atoms.

5. The fuel oil additive of claim 1, wherein component A) has a degree of branching of less than 6 CH3/100 CH2 groups, determined by means of 1H NMR spectroscopy.

6. The fuel oil additive of claim 1, wherein the constituent B1) is an α-olefin.

7. The fuel oil additive of claim 1, wherein the monomer B1) and the comonomer B2) are present in copolymer B) in a molar ratio of between 1.5:1 and 1:1.5.

8. The fuel oil additive of claim 1, wherein copolymer B, as well as comonomers B1) and B2), also comprises up to 20 mol % of a further comonomer other than B1) and B2), selected from the group consisting of an olefin having less than 10 and more than 20 carbon atoms, an allyl polyglycol ether, a C1-C30-alkyl(meth)acrylate, a vinylaromatic ether, a C1-C20-alkyl vinyl ether, and a polyisobutene having a molecular weight of up to 5000 g/mol.

9. The fuel oil additive of claim 1, wherein constituent A) has a melt viscosity V140 of from 5 to 80 mPas.

10. The fuel oil additive of claim 1, wherein constituent A) has a molecular weight Mw of from 1000 to 10 000 g/mol.

11. The fuel oil additive of claim 1, in which constituent B) has a molecular weight of from 1200 to 200 000 g/mol.

12. A fuel oil composition comprising a fuel oil of vegetable or animal origin or a mixture thereof and a fuel oil additive as claimed in claim 1.

13. The fuel oil composition as claimed in claim 12, wherein the fuel oil comprises a mixture of fatty acid esters of C1- to C4-alcohols.

14. The fuel oil composition as claimed in claim 13, wherein the fatty acid esters include stearic acid methyl ester and palmitic acid methyl ester in a proportion of at least 7% by weight.

15. A method for improving the cold behavior of a fuel oil of vegetable or animal origin or a mixture thereof, said method comprising adding the fuel oil additive of claim 1 to the fuel oil.