US20060130394A1

US20060130394A1 - Performance diesel fuels and additives

Info

Publication number: US20060130394A1
Application number: US11/020,655
Authority: US
Inventors: Charles Selvidge; Ken Copeland
Original assignee: Flint Hills Resources LP
Current assignee: Flint Hills Resources LP
Priority date: 2004-12-22
Filing date: 2004-12-22
Publication date: 2006-06-22

Abstract

Diesel fuels with additives to increase cetane number include chemistries to increase surface absorption and improve lubricity in high cetane number fuels. Fuels and additives also contain thermal stability improvers.

Description

BACKGROUND OF THE INVENTION

As the fuel and auto industries operate under continuing pressure for higher efficiency and lower emission fuels, the requirement for better ignition efficiency of diesel fuels has increased. The cetane number of a fuel is an indication of the ignition efficiency of the fuel as defined below.
Cetane improvers are known in the art and have been used for many years to improve the ignition quality of fuels. Cetane improvers include alkyl nitrates such as amyl nitrate, hexyl nitrate and mixed octyl nitrates. A commonly used cetane improver is ethyl hexyl nitrate. It is further known that ethyl hexyl nitrate has a destabilizing effect on diesel fuels and the use of a thermal stabilizer with a cetane improver is described in U.S. Pat. No. 6,676,715. The prior art however, does not address the effect on lubricity of fuels containing cetane improvers, and particularly low sulfur and ultra low sulfur fuels in which lubricity is compromised.

SUMMARY

The present disclosure addresses certain deficiencies in the prior art by providing diesel fuels containing cetane improvers sufficient to improve the ignition quality of the fuel by at least 2 cetane numbers, and further addresses the lack of lubricity of such fuels. The disclosed fuels also contain surface absorption compounds to provide diesel fuels with high cetane number and improved lubricity.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.
FIG. 1 is a graphical presentation of data indicating the effect on lubricity of a cetane improver.
FIG. 2 is a chart of data showing effects of additive compositions.

DETAILED DESCRIPTION

The present disclosure is directed to diesel fuel compositions containing chemical additives that give the fuel a better ignition performance to meet the demands of more efficient and/or higher performance diesel engines and that provide the proper chemistry to increase the lubricity and thermal stability of the diesel fuel. It is a surprising discovery of the present inventors that treating diesel fuel to improve ignition performance results in a significant detriment to the fuel's lubricity and thermal stability properties. The additives disclosed herein address these unexpected problems by providing chemistries to overcome the detrimental effects of cetane improvers in diesel fuels.
As is well known in the art, cetane number is a measure of fuel ignition quality, or an indication of the time delay from ignition to combustion for a particular diesel fuel. The rating compares the diesel fuel's performance in a standard engine with that of a mixture of cetane and alpha-methyl-naphthalene. The cetane number is the percentage by volume of cetane in the mixture that has the same performance as the fuel being tested. As diesel fuels become more refined and thus contain less sulfur, and as diesel engines evolve, there are requirements for fuels with higher cetane numbers. It is known in the industry that the cetane number of a fuel can be increased by additives such as 2-ethyl hexyl nitrate, tertiary butyl peroxide, diethylene glycol methyl ether, cyclohexanol, or mixtures thereof, for example. As disclosed herein, however, the use of cetane improvers has detrimental effects on other qualities of the fuel, such as the lubricity and thermal stability, for example. It is an aspect of the present disclosure that fuels with improved cetane number must also incorporate additional chemistries to compensate for these effects.
The present disclosure may be described in certain embodiments, therefore, as including a diesel fuel additive composition that includes a base oil, a cetane improver such as those listed above, effective to increase the cetane number of the diesel fuel by at least 2 cetane numbers, and an amount of a surface absorption compound effective to improve the lubricity of a diesel fuel containing the additive to less than 520 microns, to less than 460 microns, or even to less than 400 microns in an HFRR wear test. An HFRR wear test is a measure of a fuel's lubricity using a High Frequency Reciprocating Rig. The HFRR test results in a measure in microns of the wear scar size developed on a steel ball vibrating on a flat plate, lubricated with the test fuel. The preferred ASTM test method for lubricity by the HFRR method is ASTM D 6079.
In certain embodiments, the surface absorption compound may include one or more of alkyl esters, fatty acids, mono acids or alkyl esters of fatty acids, functionalized synthetic polymers or combinations thereof. The surface absorption compounds may be synthetic, petroleum based, or they may be plant based alkyl esters of fatty acids, such as methyl esters or ethyl esters of fatty acids, for example.
The fuel additives disclosed herein may also contain thermal stabilizers, detergents or deposit control chemistries, microbicides, dispersants, de-icers, and marker chemicals. Such diesel additives are known in the art and are included in the disclosed additives in various combinations and proportions dependent on the particular base oils for which the additive is designed. Examples of such ingredients include fuel detergent and dispersants such as Lubrizol® 9531A, Lubrizol® 9570, and low temperature flow improvers such as Lubrizol® 8052J. Preferred thermal stabilizers include organic amines, and organic amines in kerosene solvents. Broad spectrum microbicides suitable for refined oils such as those containing methylene bis(thiocyanate) or 2-(thiocyanomethylthio)benzothiazole may be added for control of microorganisms in the fuel. For cold weather applications a de-icer such as ethylene glycol monobutyl ether may be added and chemical markers may also be added for product identification. Suitable markers include Mortrace® SB marketed by Rohm Haas.
The present disclosure may also be described in certain preferred embodiments as a diesel fuel to which a cetane improver has been added to improve the ignition quality of the fuel by at least 2 cetane numbers and which includes surface absorption compounds to achieve a lubricity of less than 500 microns, or less than 460 microns, or even less than 400 microns in an HFRR wear test.
The disclosed fuels may also contain various additives as needed, which have been added sequentially, or in a single additive composition. Such additives to the fuel may include from about 100 to about 6000 ppm cetane improver, in which the cetane improver is 2-ethyl hexyl nitrate, tertiary butyl peroxide, diethylene glycol methyl ether, cyclohexanol, or combinations thereof.
The fuels may additionally include from about 100 to about 6000 ppm 2-ethyl hexyl nitrate, tertiary butyl peroxide, diethylene glycol methyl ether, cyclohexanol, or combinations thereof, and optionally from about 10 to about 500 ppm alkyl esters, mono acids of fatty acids, alkyl esters of fatty acids, functionalized synthetic polymers or combinations thereof, including synthetic alkyl esters, or plant derived alkyl ester. The fuels of the present disclosure may further include from about 10 to about 200 ppm thermal stabilizer, from about 50 to about 500 ppm of a detergent, from about 2 to about 15 ppm microbicide, a chemical marker substance, or a dispersant in any combination.
Certain preferred embodiments of the present disclosure can thus be described as a diesel fuel that includes a base oil and an additive comprising a cetane improver and a surface absorption compound and in which the ignition quality is improved by at least 2 cetane numbers and in which the lubricity is below 500 microns.
Any of the various base oils or diesel fuels may be used as the base oil in the disclosed compositions. For example, the base oil may be a #2 diesel product, a #1 diesel product, or a low sulfur diesel product, a low temperature diesel product, or a diesel product with less than 15 ppm sulfur.
The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.

EXAMPLE 1

The present example demonstrates additives altering the chemistry of a diesel fuel that contains cetane improvers such that the fuels have very high lubricity in spite of the detrimental effects of added cetane improvers, and especially in fuels in which the ignition qualities of the fuel have increased by at least 2 cetane numbers.
As shown in Table 1, when a multi-component additive is added to a diesel fuel base oil A, the lubricity is compromised. The numbers in Table 1 are the wear scar in microns resulting from an HFRR test as described above. Additive A is a performance enhancing additive for diesel fuels that increases fuel economy and power when added to #2 diesel, and includes a thermal stabilizer, a cetane improver and other ingredients. The #2 diesel base oil A used in the studies of the present example is a specially formulated diesel fuel that combines an exclusive refining process and additives that provide improved cold weather performance and engine efficiency. As additional cetane improver is added to the fuel, the lubricity decreases significantly (increasing wear scar to 629 microns). These data represent an unexpected side effect that is detrimental to the quality of the fuel when attempts are made to improve the cetane number.

TABLE 1

#2 Diesel Base Oil

#2 Diesel Base Oil #2 Diesel Base Oil A + Cetane

A A + Additive A Improver

515

529 603

539

613

555

534 629
There is, in fact a direct relationship between the amount of cetane improver added to diesel fuel A and the loss of lubricity as shown in Table 2. These data also appear in a graphical representation in FIG. 1.

TABLE 2

Cetane Improver (ppm) Lubricity (microns)

0 526

270 581

540 599

1185 637

1557 629

The data in Table 3 demonstrate the ability to counteract the detrimental effects of cetane improvers by altering the surface absorption chemistry of the diesel fuels containing cetane improvers. In Table 3, H4103 is a cetane improver. The mono-acid chemistry improves surface absorption, and includes mono-acids of fatty acids, such as found in the commercial product, LZ539S.

	TABLE 3


	Additive

							2400
							ppm
		2400				2393	Additive
		ppm				ppm	A + 147
		Addi-	540	1185	1557	Addi-	ppm
Trial		tive	ppm	ppm	ppm	tive	mono-
No.	None	A	H4103	H4103	H4103	A	acids

1	515
2	529	603
3		539
4		613
5		555
6	534				629
7			599	637
8						545	370
9						608	353
Avg	526	577.5	599	637	629	576.5	361.5

The data in Table 4 indicate an even greater lubricity effect at a lower concentration of additive when using functionalized polymeric surface absorption chemistry such as that found in the commercial product, Octel 9070.

	TABLE 4


	Additive

				2400	2400
		2400		ppm	ppm	1400 ppm
		ppm	2400 ppm	Addi-	Addi-	cetane
		Additive	Additive	tive	tive	improver +
		A +	A + 100	A + 50	A + 100	310 ppm
		50 ppm	ppm	ppm	ppm	9531A + 100
Trial		mono-	mono-	Octel	Octel	ppm mono-
No	None	acids	acids	9070	9070	acids

1	520		364
2	504
3					316	333
4			350		321	393
5		423		376
Avg	512	423	357	376	319	363

EXAMPLE 2

Cetane improvers also affect the thermal stability of a diesel fuel. An aspect of the disclosure is a fuel or fuel additive containing a cetane improver and a surface absorption compound and that also contains a compound to increase thermal stability. In the present example, an organic amine compound was added to the fuel. As shown in the data in FIG. 2, addition of this compound in combination with the surface absorption compounds described in Example 1 produced a synergistic effect on the lubricity.
All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the methods described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

Claims

1. A diesel fuel additive composition comprising:

a base oil;

cetane improver effective to increase cetane number of a diesel fuel by at least 2 cetane numbers; and

an amount of a surface absorption compound effective to improve the lubricity of a diesel fuel containing the additive to less than 520 microns in an HFRR wear test.

2. The additive of claim 1, wherein the surface absorption compound is effective to improve the lubricity of a diesel fuel containing the additive to less than 460 microns in an HFRR wear test.

3. The additive of claim 1, wherein the surface absorption compound is effective to improve the lubricity of a diesel fuel containing the additive to less than 400 microns in an HFRR wear test.

4. The additive of claim 1, wherein the cetane improver is 2-ethyl hexyl nitrate, tertiary butyl peroxide, diethylene glycol methyl ether, cyclohexanol, or combinations thereof.

5. The additive of claim 1, wherein the surface absorption compound comprises alkyl esters, mono acids of fatty acids, alkyl esters of fatty acids, or combinations thereof.

6. The additive of claim 1, wherein the absorption compound comprises a monoacid of a fatty acid.

7. The additive of claim 1, wherein the absorption compound comprises an alkyl ester of a fatty acid.

8. The additive of claim 7, wherein the alkyl ester is a methyl ester or an ethyl ester.

9. The additive of claim 7, wherein the alkyl ester is synthetic.

10. The additive of claim 7, wherein the alkyl ester is plant derived.

11. The additive of claim 1, further comprising a thermal stabilizer.

12. The additive of claim 11, wherein the thermal stabilizer comprises organic amines in kerosene solvent.

13. The additive of claim 1, further comprising a detergent or deposit control chemistry.

14. The additive of claim 1, further comprising a microbicide.

15. The additive of claim 1, further comprising a marker substance.

16. The additive of claim 1, further comprising a dispersant.

17. A diesel fuel additive composition comprising:

an amount of a surface absorption compound effective to improve the lubricity of a diesel fuel containing the additive to less than 520 microns in an HFRR wear test;

wherein the additive further comprises one or more of:

a thermal stabilizer;

a detergent;

a microbicide;

a marker substance; and

a dispersant.

18. A diesel fuel comprising:

diesel base oil;

a cetane improver effective to increase cetane number of the diesel fuel by at least 2 cetane numbers; and

wherein the lubricity of the diesel fuel is less than 520 microns in an HFRR wear test.

19. The diesel fuel of claim 18, wherein the fuel has a lubricity of less than 460 microns in an HFRR wear test.

20. The diesel fuel of claim 18, wherein the fuel has a lubricity of less than 400 microns in an HFRR wear test.

21. The diesel fuel of claim 18, comprising from about 100 to about 6000 ppm cetane improver.

22. The diesel fuel of claim 18, wherein the cetane improver is 2-ethyl hexyl nitrate, tertiary butyl peroxide, diethylene glycol methyl ether, cyclohexanol, or combinations thereof.

23. The diesel fuel of claim 18, comprising from about 100 to about 6000 ppm 2-ethyl hexyl nitrate, tertiary butyl peroxide, diethylene glycol methyl ether, cyclohexanol, or combinations thereof.

24. The diesel fuel of claim 18, comprising from about 10 to about 500 ppm alkyl esters, mono acids of fatty acids, alkyl esters of fatty acids, or combinations thereof.

25. The diesel fuel of claim 24 comprising a synthetic alkyl ester.

26. The diesel fuel of claim 24, comprising a plant derived alkyl ester.

27. The diesel fuel of claim 18, comprising from about 10 to about 200 ppm thermal stabilizer.

28. The diesel fuel of claim 27, wherein the stabilizer is organic amines in kerosene solvent.

29. The additive of claim 18, further comprising from about 50 to about 500 ppm of a detergent.

30. The diesel fuel of claim 18, further comprising from about 2 to about 15 ppm microbicide.

31. The diesel fuel of claim 18, further comprising a chemical marker substance.

32. The diesel fuel of claim 18, further comprising a dispersant.

33. The diesel fuel of claim 18, comprising a base oil and an additive comprising a cetane improver and a surface absorption compound.

34. The diesel fuel of claim 18, further comprising a base oil and an additive comprising a cetane improver, a surface absorption compound, a thermal stabilizer, a detergent, a microbicide, a marker substance, and a dispersant.

35. The diesel fuel of claim 18, wherein the base oil is #2 diesel.

36. The diesel fuel of claim 18, wherein the base oil is #1 diesel.

37. The diesel fuel of claim 18, wherein the base oil is a blend of # 2 diesel and light cycle oil.

38. The diesel fuel of claim 18, wherein the base oil incorporates one or more cold flow improvers.

39. The diesel fuel of claim 18, wherein the base oil is a low sulfur diesel.

40. The diesel fuel of claim 18, wherein the base oil sulfur is less than 15 ppm.

41. A process for improving the chemistry of a diesel fuel with enhanced ignition quality, wherein the fuel comprises a diesel base oil and a cetane improver effective to improve the ignition quality by at least 2 cetane numbers, comprising adding from about 10 to about 500 ppm alkyl esters, mono acids of fatty acids, alkyl esters of fatty acids, or combinations thereof, effective to increase the lubricity of the enhanced diesel fuel.

42. The process of claim 41 wherein the lubricity of the diesel fuel is less than 520 microns in an HFRR wear test.

43. The process of claim 41, wherein the fuel has a lubricity of less than 460 microns in an HFRR wear test.

44. The process of claim 41, wherein the fuel has a lubricity of less than 400 microns in an HFRR wear test.