HK1114121A - Cleaner burning diesel fuel - Google Patents

Description

Purifier fired diesel fuel

Technical Field

The present invention provides improved diesel fuels based on blends of biodiesel and low aromatic content ultra low sulfur diesel fuels (dieselfuel), particularly fuel additives having a concentrate containing a Fuel Borne Catalyst (FBC).

Background

In U.S. patent application No.10/290,798, a low emission diesel fuel is described that includes Jet a and FBC.

In U.S. patent application No.10/357,027, a low emission diesel fuel is described that includes an emulsion of Jet a and FBC.

In U.S. patent application No.10/401,367, a low emission diesel fuel is described, which includes JetA, biodiesel, and FBC.

These fuels are indeed effective, but there is a continuing need for other diesel fuels, thereby providing for the generation of pollutants, particularly NO_xAnd further reduction in particulate emissions.

Disclosure of Invention

It is an object of the present invention to provide an improved diesel fuel to reduce unburned hydrocarbons, carbon monoxide, particulates and NO_xAnd (4) discharging.

It is another object of the present invention to provide a fuel that employs renewable resource materials with desirable hydrogen/carbon balance, which fuel can in this way reduce carbon dioxide emissions, and provide fuel economy due to the emission of harmful pollutants also being controlled.

These and other objects are achieved by the present invention which provides an improved diesel fuel based on a blend of biodiesel and low aromatic content ultra low sulfur diesel fuel, particularly with a fuel additive containing a Fuel Borne Catalyst (FBC) concentrate.

Preferred aspects of the present invention will be described below.

Detailed Description

The present invention provides improved diesel fuels based on blends of biodiesel and low aromatic content ultra low sulfur diesel fuels, particularly with fuel additives containing a concentrate containing Fuel Borne Catalyst (FBC).

As a major component of the fuel blends of the present invention, Low Aromatic (LA) content, Ultra Low Sulfur Diesel (ULSD) fuels are provided. The term low aromatic content as used herein means that this component of the fuel has an aromatic content of less than 10% by volume, and preferably in the range of 1 to 8%, in particular in the range of 2 to 5%. The following table shows the common analytical compositions of No.2 diesel and low aromatic ultra low sulfur diesel LA ULSD, as well as the preferred formulation according to the present invention (LA ULSD with FBC and 20% biodiesel). Equivalents having the same basic function and those varying compositionally up to 50%, preferably less than 20%, for example not more than 10%, may also be employed.

Fuel	Commonly used No.2 diesel oil	Preferred Low Aromatic (LA) ULSD	Common LA ULSD with FBC and 20% biodiesel
				API gravity	36.36	35-40	35-40
Sulfur, wt.%	0.0323	＜0.0015	＜0.0015
				Cetane number	47.7	＞47	＞50
Carbon, wt.%	86.84	＜87	＜85
				Hydrogen, wt.%	13.16	＞13	＞13
Aromatic hydrocarbons, volume%	29.9	＜10	ND
				Olefin, volume%	0.5	ND	ND
Saturated hydrocarbon, volume%	69.6	ND	ND
				Viscosity at 40 deg.C (centigrade)	2.3	< 10, e.g. 2-3	ND
Flash point, F	157.4	＞180	ND

IBP，℉	351.1	420-430	430
				5％，℉	393.3	ND	449
10％，℉	414.0	＞440	459
				20％，℉	439.0	ND	478
30％，℉	459.5	ND	493
				40％，℉	477.9	ND	509
50％，℉	494.6	＞490	526
				60％，℉	511.3	ND	544
70％，℉	529.0	ND	567
				80％，℉	550.4	ND	592
90％，℉	580.3	＞560	618
				95％，℉	606.7	ND	633
EP，℉	641.7	＜640	643

The other major component of the low emission diesel fuel of the present invention is what is known in the art as "biodiesel". The proportion of biodiesel in the diesel blend is small, typically about 1 to 35%, for example, about 15 to 25%. Blending ofTypically, the biomass contains about 20% biodiesel, wherein such biologically derived fuel components include "mono-alkyl ester-based oxygenated fuels," i.e., fatty acid esters, preferably fatty acids derived from triglycerides, such as soybean oil, canola oil, and/or tallow. The term "fatty acid ester" as used herein is intended to include any compound in which the alcohol moiety is readily removed, including polyols and substituted alcohols and the like, but is preferably a volatile alcohol, such as C₁-C₄Esters (preferably methyl esters) of alcohols, 2-methoxyethyl and benzyl esters of fatty acids containing about 8 or more (e.g., 8 to 22) carbon atoms, and mixtures of such esters. Volatile alcohols are highly desirable. Methyl esters are the most preferred ester reactants. Suitable ester reactants may be prepared by the reaction of diazoalkanes and fatty acids, or from the alcoholysis of naturally occurring fatty acids in fats and oils.

Suitable fatty acid esters may be derived from synthetic or natural, saturated or unsaturated fatty acids and include positional and geometric isomers. Suitable preferred saturated fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, isomyristic acid, isotelic acid, myristic acid, caprylic acid, and anteisoarachidic acid (anteisoarachidic acid). Suitable preferred unsaturated fatty acids include myristoleic acid, palmitoleic acid, ricinoleic acid, linoleic acid, oleic acid, elaidic acid, linolenic acid, eleasteric acid, arachidonic acid, erucic acid, and erythrogenic acid. Fatty acid mixtures from soybean oil, palm oil, safflower oil, rapeseed oil, canola oil (low erucic acid), and corn oil are particularly preferred for use in the present invention. The fatty acids can be used directly, and/or after hydrogenation, and/or after isomerization, and/or after purification. For example, rapeseed is C₂₂Fatty acids provide a good raw material; c₁₆-C₁₈The fatty acid may be provided by tallow, soybean oil, or cottonseed oil; and shorter chain fatty acids may be provided by coconut, palm kernel, or babassu oil. Lard, olive oil, peanut oil, sesame oil, and sunflower oil are other natural sources of fatty acids.

Preferred esters for inclusion in biodiesel are lower alkyl esters, for example, the methyl, ethyl, propyl and butyl esters, especially the methyl ester, of soy and/or tallow fatty acids. The following is a specification for Biodiesel (B100) set by the National Biodiesel commission (National Biodiesel Board) in month 12 of 2001, which was also adopted to clarify and define the present invention. Thus, biodiesel is defined as a mono-alkyl ester of a long chain fatty acid derived from vegetable oils or animal fats, for use in compression-ignition (diesel) engines. This specification applies to pure (100%) biodiesel prior to use or blending with diesel fuel. There is a great deal of experience in the united states for a 20% blend of biodiesel with 80% diesel fuel (B20). While biodiesel (B100) can be used, blends with greater than 20% biodiesel of diesel fuel should be individually evaluated until further experience is available. Equivalents having the same basic function and those varying compositionally by up to 25%, preferably less than 10%, may also be employed. In some cases, as low as 2% biodiesel can be used with a blend of 98% diesel fuel of distillate origin (distillate origin).

Performance of	ASTM method	Limiting	Unit of
				Flash point	D93	Lowest 130	Degree centigrade
Water and sediment	D2709	Max 0.050	Volume%
				Kinematic viscosity, 40 deg.C	D445	1.9-6.0	Millimeter2Second/second
Sulphated ash	D874	Maximum 0.020	Mass%
				Sulfur	D5453	Maximum 15	ppm
Level S15		Maximum 500
				S500 level
Corrosion of copper strip	D130	Maximum number 3
				Cetane number	D613	Minimum 47
Cloud point	D2500	Preferably-2 ℃ or reported value (report)	Degree centigrade

Carbon residue	D45301	Max 0.050	Mass%
				100% of the sample
Acid value	D664	Maximum 0.80	mg KOH/gm
				Free glycerin	D6584	Maximum 0.020	Mass%
Total glycerin	D6584	Maximum 0.240	Mass%
				Phosphorus content	D4951	Maximum 0.001	Mass%
Distillation temperature, atmospheric equivalent temperature, 90% recovery	D1160	Maximum 360	Degree centigrade

¹Adjustment of individual constraints to meet specific operating conditions may be achieved between the buyer, seller and manufacturer.

One such product is available under the trademark BioDiesel from members of the national BioDiesel Committee and is identified as "methyl soyate, methyl rapeseed oil fatty acid (RME), methyl bovine fatty acid. The fuel is also referred to by the manufacturer as a "mono-alkyl ester based oxygenated fuel, a fuel derived from vegetable oils or animal fats". It is said to contain 11% by weight of oxygen. They described the product as a methyl ester from a lipid source, CAS number 67784-80-9.

The Fuel Borne Catalyst (FBC) comprises fuel soluble platinum and/or cerium and/or iron. The cerium and/or iron are typically used at a concentration of 2 to 25ppm, with the platinum being 0.05 to 2ppm, the preferred level of cerium or iron being 2 to 10ppm, such as 3 to 8ppm, and the platinum being used at a level of 0.1 to 0.5ppm, such as 0.15 ppm. The preferable ratio of cerium and/or iron to platinum is 75: 1-10: 1. The LA ULSD component is typically used in a volume ratio to the fatty acid ester of from about 2: 1 to about 5: 1, for example about 4: 1. The entire range of blends, extending from 50: 1 to 1: 50, has several benefits. The LAULSD fuel component of the blend preferably contains 50 to 1500ppm detergent, up to about 500ppm lubricity additive and 0.1 to 1ppm platinum COD and 5 to 20ppm cerium oleate or octanoate. An advantage of the present invention is that the fatty acid ester is LA ULSD which increases lubricity and reduces the need for a separate lubricity additive.

The catalyzed blends of the present invention are effective in reducing regulated emissions pollutants, which are NO_xParticulate, hydrocarbon and carbon monoxide. Preferably, the fuel simultaneously reduces NO_xAnd microparticles, which is an unusual combination. Preferred blends are effective to achieve at least 4% or greater NO as compared to the baseline for No.2 diesel fuel_xReduction and at least 25% reduction in particulates. More preferably 5-25% NO_xThe reduction and the reduction of particles of 20 to 60 percent. By using the fuel in engines equipped with diesel particulate filters or diesel oxidation catalysts, higher particulate reductions can be achieved. These reductions are preferably with or without an increase in NO₂The discharge is obtained simultaneously.

Preferred detergents that may be used include polyolefinic amide hydrocarbylene amines (about 65-80%), with the remainder being petroleum distillates. Equivalents which have the same basic function may also be employed. One preferred form is TFA-4690-C, available from Texaco, at a concentration of about 50 to 300ppm, more narrowly 75 to 150ppm, e.g., about 100ppm, which provides the following analysis:

performance of	Method of producing a composite material	Normal value
			Density nitrogen content at 15 ℃, wt% flash point, DEG C, minimum TBN, mgKOH/g kinematic viscosity, cSt at 40 ℃	D4052D5291D93D2896D445	0.91-0.942.3-2.46250-60600-850

Preferred lubricity additives that may be employed include tall oil fatty acids, which are commercially available as mixtures of fatty acids including oleic acid, linoleic acid, and the like. Equivalents which have the same basic function may also be employed. One preferred form is TFA-4769, available from Texaco, at a concentration of about 25 to 500ppm, such as about 150 to 250ppm, which is provided with the following analysis:

performance of	Method	Common value
			Specific gravity, 60/60F lbs/gallon, 60F flash point, F, minimum kinematic viscosity, cSt at 40 ℃	D1298 calculation D93D445	0.917.5414217.85

Specific cerium compounds are: cerium III acetylacetonate, cerium III naphthenate, as well as cerium octoate, cerium oleate and other soaps such as stearates, neodecanoates, and octanoates (2-ethylhexanoates). Many of the cerium compounds satisfy the formula: ce (OOCR)₃Wherein R ═ hydrocarbon, preferably C₂～C₂₂And include aliphatic, cycloaliphatic, aryl, and alkaryl groups. The preferred concentration of cerium is 2-15 ppm cerium w/v of the fuel. Preferably, the cerium is provided as a cerium hydroxy oleate propionate complex (40% by weight cerium). Preferred levels are toward the lower end of the range.

Specific iron compounds are: ferrocene, iron-and ferrous acetyl acetonates, iron soaps such as octanoates and stearates (generally commercially available as Fe (III) compounds), iron pentacarbonyl Fe (CO)₅Iron naphthenate (iron naphthenate), and iron fatty acid in tall oil.

Any platinum group metal composition, for example, 1, 5-cyclooctadieneplatinum biphenyl (platinum COD), described in U.S. patent No. US4,891,050 to Bowers et al, U.S. patent No. US5,034,020 to Epperly et al, and US5,266,093 to Peter-Hoblyn et al, may be used as the platinum source. Other suitable platinum group metal catalyst compositions include commercially available or readily synthesized acetylacetonates of platinum group metals, dibenzylidene acetonates of platinum group metals, and fatty acid soaps of tetramine platinum metal complexes, such as tetramine platinum oleate. The preferred concentration of platinum is 0.1 to 2.0ppm platinum w/v (mg/l) of the fuel, for example, up to about 1.0 ppm. Preferred levels are toward the lower end of this range, e.g., 0.15 to 0.5 ppm. Platinum COD is the preferred form of platinum added to the fuel. Cerium or iron is typically used at metal concentrations providing 2 to 25ppm, while platinum is 0.05 to 2ppm, with preferred levels of cerium or iron being 5 to 10ppm, such as 7.5ppm, and platinum being used at levels of 0.1 to 0.5ppm, such as 0.15 ppm. The preferable ratio of cerium and/or iron to platinum is 75: 1-10: 1.

In addition to utilizing low emission fuels in accordance with the present invention, delaying engine timing (engine timing), for example, by 2-6 °, can further reduce NO_xAnd the use of a diesel particulate filter and/or a diesel oxidation catalyst may provide further reductions in carbon monoxide, unburned hydrocarbons, and particulates.

The low emission fuel according to the present invention may be used as an emulsion with water, wherein the oil phase is emulsified with water, the water comprising 1-30% water based on the weight of the aviation kerosene. In a preferred form, the emulsion is predominantly water-in-oil and preferably contains, in addition to the other components described above, surfactants, lubricity additives and/or corrosion inhibitors. Suitable emulsion forms and additives are discussed in US5,743,922. Water-in-oil emulsions typically provide about 1% NO per 1% added water_xAnd decreases. The combination of technologies will provide greater emissions reduction than either alone. The platinum/cerium fuel borne catalyst or other catalyst is preferred but optional. If desired, a combination of a blend of fatty acid esters and jet fuel can be employed to achieve good results without the need for a catalyst carried by the fuel. The fuel thus formed in any of the above embodiments may be used with timing change, EGR, oxidation catalysts or particulate filters to enhance emission control.

The term "diesel particulate filter" is meant to refer to those devices known in the art for use as exhaust filters that reduce particulate emissions by trapping a portion of the particulates within a complex internal structure. Since deposits can accumulate, they must be regenerated or replaced. The use of the above fuel borne catalyst in combination with the base fuel, also described-forming the fuel of the invention-enables a significant reduction in emissions in the case of enhanced filter operation.

The term "diesel oxidation catalyst" is meant to refer to those devices known in the art for use as gas treatment catalysts that reduce the emissions of particulates, hydrocarbons, and carbon monoxide by replacing the trapping of particulates in a diesel particulate filter with contact with a catalyzed surface. The use of the above-mentioned fuel borne catalyst in combination with the base fuel, also described-forming the fuel of the invention-enables a significant reduction in emissions in the case of enhanced operation of the oxidation catalyst.

Retarding engine timing, e.g. about 2 to about 6, is for NO reduction_xUnfortunately, it itself leads to the generation of pollutants due to poor combustion. This trade-off plagues the art as control of emissions becomes important. It is an advantage of the present invention that reduced NO can be achieved by using the fuel of the present invention in combination with one or more of the above techniques and/or exhaust gas recirculation where a portion of the exhaust gas is intermixed with combustion gases_xAnd other contaminants.

In carrying out the present invention in a preferred form, FBCs are provided as described in U.S. Pat. No. 6,003,303 and the references cited therein.

The invention has particular use in the operation of a ship transport vehicle which is brought to a central location for periodic, e.g. daily, refuelling.

In this exemplary arrangement, the concentration of FBC catalyst metal in the fuel is desirably maintained at 4-10 ppm.

The following examples are provided to further illustrate and explain the present invention and are not to be construed in any way as limiting the invention. All parts and percentages are by weight unless otherwise indicated.

Example 1

Purifier fired biodiesel fuel blends using Platinum Plus ® Fuel Borne Catalyst (FBC) (0.15 ppm Pt added as Pt COD) and lightly catalyzed (3-5 grams Pt) Diesel Oxidation Catalyst (DOC) produced 51% Particulate (PM) reduction and 9% NO reduction relative to baseline emissions of standard No.2D fuel_xIs reduced. This combination has a reduction in the exposure to regulated pollutants of over 100 pounds per year in a conventional school bus and over 200 pounds per year in a local delivery vehicle. The NO can be increased by 2-4% by using conventional biodiesel_x。

Three federal test cycles were performed on a 1995 Navistar DT-466 engine commonly used in school buses, drinks and local service ships. The fuels used are listed in the table below.

Fuel	No.2	LA ULSD	LA ULSD	LA ULSD with FBC and 20% biodiesel
					API gravity	36.36	37.84	39.30	36.0
Sulfur, wt.%	0.0323	0.0001	0.00001	0.00034
					Cetane number	47.7	ND	ND	55.2
Carbon, wt.%	86.84	86.02	86.0	83.7
					Hydrogen, wt.%	13.16	13.98	14.0	13.6
Aromatic hydrocarbons, volume%	29.9	3.26	5.20	ND
					Olefin, volume%	0.5	ND	ND	ND
Saturated hydrocarbon, volume%	69.6	ND	ND	ND
					Viscosity at 40 degrees Celsius	2.3	2.94	3.00	ND
Flash point, F	157.4	198	188	ND
					IBP，℉	351.1	423	424	430
5％，℉	393.3	ND	ND	449
					10％，℉	414.0	455	456	459
20％，℉	439.0	ND	ND	478
					30％，℉	459.5	ND	ND	493
40％，℉	477.9	ND	ND	509
					50％，℉	494.6	500	512	526
60％，℉	511.3	ND	ND	544
					70％，℉	529.0	ND	ND	567
80％，℉	550.4	ND	ND	592
					90％，℉	580.3	563	586	618
95％，℉	606.7	ND	ND	633
					EP，℉	641.7	601	624	643

In the first two test sequences, a blend of 20% biodiesel was combined with low aromatic ultra low sulfur diesel (LA ULSD) and Platinum Plus ® FBC (0.15% ppm Pt as Pt COD) and the engine was equipped with mild catalysis (3-5 g/ft)³) And (7) a DOC. At this time, the overall emissions were reduced to 66% HC, 63% CO, 9% NO_x51% PM and 95% SO_x. NO in exhaust gas₂A reduction of over 60% was also found in the composition,NO₂are strong lung irritants and can be increased with conventional heavily catalyzed aftertreatment devices. The test procedure used a lightly catalyzed DOC which reduced the cost and made NO₂The formation of (a) is minimized.

These tests demonstrated earlier experimental work on engines from Cummins and Detroit Diesel, which showed that cleaner-burning biodiesel blends made with Platinum Plus ® FBC and No.1D or ULSD consistently reduced NO_xAnd the ability to emit PM.

The above description is intended to teach those of ordinary skill in the art to practice the invention and does not intend to detail all of the obvious modifications and variations that will become apparent to those of ordinary skill in the art upon reading this specification. It is intended, however, that all such obvious modifications and variations be included within the scope of the present invention which is defined by the following claims. The claims cover the indicated components and steps in any arrangement and combination that is effective to meet the objectives intended for the invention, unless the context specifically indicates the contrary.

Claims (4)

1. An improved diesel fuel blend comprising biodiesel and low aromatic content ultra-low sulfur diesel fuel, particularly with a fuel additive containing a concentrate containing Fuel Borne Catalyst (FBC).

2. A diesel fuel blend according to claim 1, wherein the FBC comprises platinum and/or iron, and/or cerium.

3. A diesel fuel blend according to claim 1 comprising 15 to 20% biodiesel.

4. A diesel fuel blend according to claim 1 wherein the low aromatics ultra low sulfur diesel component comprises less than 10 vol% aromatics.