JP2005029796A - Distillate fuel composition for improved combustion and engine cleanliness - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide distillate fuels for improved combustion and engine scavenging. <P>SOLUTION: The fuel composition comprises a distillate fuel additive composition, a distillate fuel, an overbased calcium sulfonate scavenger, a succinimide dispersant and an organomanganese compound. Also provided is a method for improving the cleanliness of diesel fuel intake systems by burning, in the systems, the distillate fuel containing the fuel additive composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a synergistic interaction between a highly basic calcium sulfonate detergent and an ashless succinimide dispersant that allows for the formulation of an improved distillate fuel additive package. In addition to the metal detergent and the ashless dispersant, the additive composition contains an organometallic complex of manganese. The distillate fuel treated with the additive composition exhibits improved fuel system cleanliness due to improved combustion by the detergent and the organometallic manganese compound and detergent / dispersant interaction.

  A great deal of prior art has been directed to formulating distillate fuel additive compositions that provide environmental benefits when fuel is burned. Such benefits include, for example, reduced emissions of harmful pollutants such as nitrogen oxides and particulates, reduced acidity of emitted particles, and improved fuel economy (resulting in emissions of carbon dioxide per amount of fuel burned). Resulting in a decrease in quantity). The effects of these fuels on fuel system cleanliness, such as carbon and lacquer deposition on fuel injectors found in diesel engines, have not been well studied.

  There is a need for a distillate fuel additive composition that simultaneously achieves combustion, improved fuel and combustion system cleanliness, improved fuel economy, and reduced pollutant generation.

  The embodiments presented herein provide a fuel additive composition comprising an organometallic manganese compound, an alkyl-substituted succinimide ashless dispersant, and a TBN of about 200 or more highly basic calcium sulfonate detergents. In another embodiment, the highly basic calcium sulfonate has a TBN of about 300.

  Another embodiment is a minor fuel additive composition comprising a major amount of middle distillate fuel and an organometallic manganese compound, an alkyl-substituted succinimide ashless dispersant, and a TBN of about 200 or more highly basic calcium sulfonate detergents. Providing fuel containing goods.

  Thus, in one example herein, a fuel comprising a fuel additive composition comprising an organometallic manganese compound, an alkyl-substituted succinimide ashless dispersant, and a TBN about 300 highly basic calcium sulfonate detergent. By using in a fuel intake system, a method is provided for improving the cleanliness of the fuel intake system.

  It is understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the claimed invention. Should.

  In one aspect, provided herein is a distillate fuel additive composition for use in distillate fuel that provides enhanced fuel combustion and at the same time superior cleanliness of the fuel intake system. . Distillate fuel is defined herein as a petroleum-based hydrocarbon fuel having a boiling point in the range of about 140-360 ° C. [284-680 ° F.] and diesel and biodiesel fuel, jet fuel, marine fuel And household heating oil. Distillate fuels containing the additive composition of the present invention exhibit enhanced combustion characteristics.

  If certain components of the additive package described herein are present in a specific ratio, the fuel containing the additive package has excellent fuel injector cleanliness as measured by the Cummins L10 diesel detergency test. Also shown. Injector cleanliness is shown as an injector rating of at most 10.0 in the Cummins L10 diesel washability test.

  Other aspects herein include cleaning the fuel intake system by using an additive composition, a distillate fuel containing the additive composition, and a fuel containing the additive composition. Provide a way to improve sex.

In some embodiments, the additive composition includes at least an organometallic complex of manganese, a highly basic calcium sulfonate detergent and an ashless succinimide dispersant, and the additive composition is dissolved in a distillate fuel. The case is such that the following relationship is satisfied. :
−0.159x + 0.243y−0.0143xy ≦ −8.4
Where x = succinimide concentration (pounds per thousand barrels),
y = high basic calcium sulfonate concentration (in PTB),
x = 20-35, preferably 25-30, and y = 10-120, preferably 30-50
It is limited to.

  This organometallic manganese compound does not affect injector cleanliness. In some embodiments, the organometallic manganese compound may be present in the fuel at a concentration up to about 20 PTB.

  It has been found that a known combustion improving conventional additive package does not necessarily pass the Cummins L10 diesel cleanability test (where pass is defined as an average injector rating of 10.0 or less). .

  An experimental design was performed to identify the components in the additive composition that affect the injector rating. A synergistic effect (ie, non-linear interaction) was observed between the highly basic calcium sulfonate detergent and the succinimide dispersant. This was a surprising result not expected by any prior art.

Using the results of this experimental design, a model for the average injector score was created as follows.
Score = −0.159x + 0.243y−0.0143xy + 18.4 (1)
Where x = succinimide concentration (1000 pounds per barrel, or PTB),
y = concentration of highly basic calcium sulfonate (in PTB).
Since this average injector score must be 10.0 or less to pass the Cummins L10 test, this equation is 10.0 ≧ −0.159x + 0.243y−0.0143xy + 18.4 (2)
Or -0.159x + 0.243y-0.0143xy <=-8.4 (3)
It becomes.
This detergent / dispersant synergy is represented by this xy term.
This model was confirmed by testing three new formulations that satisfied the above equation.
1. x = 28PTB, y = 32PTB
2. x = 26 PTB, y = 40 PTB
3. x = 25 PTB, y = 48 PTB
According to this model, all three formulations gave an average injector rating of 10.0 or less. Of course, in Equation 3, there are an infinite number of solutions for x and y. Examples of current practical solutions are in the following ranges.
x = 20-35, preferably 25-30,
y = 10-120, preferably 30-50.

The amount of organometallic manganese compound has been shown not to have a significant adverse effect on the injector score and is therefore not constrained by the model represented by Equation 3. As merely an economic matter, the amount of manganese compound is limited to 20 PTB or less in some embodiments. Benefits derived from the inclusion of manganese compounds include, but are not directly related to the injector ratings, reduction of particle emissions, reduction of the NO _x and SO _X reduction of hydrocarbons, improved fuel economy, and the combustion improvement It is much more effective in the area.

  Succinimide produced from methylcyclopentadienyl manganese tricarbonyl (MMT (registered trademark)) as an organometallic manganese compound, 850 to 2100 MW PIBSA as an ashless dispersant, and a polyalkylene polyamine close to tetraethylenepentamine in composition. , And highly basic calcium sulfonates up to about 300 TBN as detergents are particularly useful herein. MMT® is available from Ethyl Corporation (Richmond, VA). Although the diesel fuel used in the Cummins L10 test was a high sulfur (0.4 wt% sulfur) fuel, any diesel fuel (including low and ultra low sulfur fuels) may be used. Another L10 experiment showed that the addition of 2-ethylhexyl cetane nitrate improver to fuels containing the additive of the present invention did not degrade the performance of this detergent.

  The following examples further illustrate aspects of the invention but do not limit the invention.

  Since the Cummins L10 test was designed to evaluate additives and fuels for on-road use in North America, HiTEC® 4080 fuel additive was used in this example. This additive is a Greenburn® road diesel fuel additive package without an antifoam agent from Ethyl Corporation and is used at a recommended treat rate of 500 ppm (w / w). This formulation is shown in Table 1.

  For the purposes of this example, the European component D-5021 (demulsifier) and HiTEC® 536 (corrosion inhibitor) were replaced on a weight basis by the North American component Tolad 9310 and 50% dodecenyl succinic acid, respectively. . In all tests, these components were held constant at the above concentrations. Ingredients expected to have a significant impact on the Cummins L10 score are HiTEC® 9645 (succinimide-based dispersant), HiTEC® 611 (highly basic calcium sulfonate) and HiTEC® 3062. (62% MMT in aromatic solvent).

The resulting 2-level-3 factor (2 ³ ) design is shown in FIG. 1; the number along the axis indicates the concentration in PTB.

  All tests were conducted with the same Cummins L10 engine and the same batch of high sulfur Cat1K fuel. The test order was randomized. The results are shown in Table 2.

Analysis of variance (ANOVA) for the data in Table 2 showed that the average flow reduction was independent of all three factors. ANOVA for the CRC score is shown below.

  HiTEC® 3062 and the higher order terms AC, BC and ABC are significant at a confidence level of less than 85% and therefore exclude them. The model coefficients are as follows:

This regression coefficient expects HiTEC® 611 to increase this score, while HiTEC® 9645 anticipates a CRC response (a beneficial effect because a low CRC score indicates less injector buildup). On the other hand, it shows a decrease There is a significant negative interaction between HiTEC® 9645 and HiTEC® 611, which is a deleterious effect of HiTEC® 611 on CRC scores at low concentrations of dispersant. Is more than offset at high dispersant concentrations. In other words, HiTEC® 611 improves the CRC score in the presence of high amounts of HiTEC® 9645. This effect is illustrated by the interaction diagram of FIG. Typically, a p value of 0.13 results in HiTEC® 611 alone being excluded from this model: this value indicates that this coefficient differs from zero only at the 87% confidence level. However, if this model includes an interaction between HiTEC® 9645 and HiTEC® 611, the HiTEC® 611 term is also used to maintain the model hierarchy. Must be included.
Formulation of Modified Dispersant Package to Pass Cummins L10 Test Therefore, for example, the components of HiTEC (R) 4080 are adjusted to achieve the desired CRC goal from the model developed above Is possible. As stated above, the highest CRC score for a Cummins L10 pass is 10.0. The constant response curve for CRC as a function of HiTEC® 9645 and HiTEC® 611 concentrations (in PTB) is shown in FIG. Based on the above model for CRC, any combination of HiTEC® 9645 and HiTEC 611 to the right of the 10.0 isoline (dotted line) in FIG. 3 must give a passing Cummins L10 rating. Three points were selected on the 9.0 isoline (solid line) in the L10 test. The combinations of additives corresponding to these points are as follows.
1.28 PTBHiTEC (registered trademark) 9645 + 32 PTBHiTEC (registered trademark) 611
2.26 PTBHiTEC (registered trademark) 9645 + 40 PTBHiTEC (registered trademark) 611
3.25 PTBHiTEC (registered trademark) 9645 + 48 PTBHiTEC (registered trademark) 611
All three packages contained 6.6 PTB Ethyl MMT® as HiTEC® 3062, plus solvent, demulsifier and corrosion inhibitor as described above. The resulting Cummins L10 data is shown in Table 3.

  As expected from the model and calculations above, all three packages pass the Cummins L10 test.

Simple 2 ³ experimental design was determined quantitative effects of various components of the additive in the package Greenburn (TM) diesel fuel on Cummins L10 performance. While this highly basic calcium sulfonate detergent (HiTEC® 611) reduces the injector score, this succinimide dispersant (HiTEC® 9645) has a beneficial effect on these scores. It turned out to be affected. In addition, a strong interaction between these two components was observed that reduced the undesirable effects of this detergent. MMT® (as HiTEC® 3062) did not have a significant effect on injector cleanliness. A model derived from this experimental design was used to formulate a modified Greenburn® type package that passed the Cummins L10 test.

Other aspects of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. Unless otherwise stated, all numbers representing amounts of ingredients, properties such as molecular weight, percentages, ratios, reaction conditions, etc. used in the specification and claims are all adjusted by the term “about”. It should be understood that Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations and may vary depending upon the desired properties sought to be obtained by the present invention. At a minimum, and not as an attempt to limit the application of the principle of equality to the claims, each numeric parameter takes into account the significant number of digits shown and the usual rounding method By applying, should be at least interpreted. In spite of the fact that the numerical ranges and parameters indicating the broad scope of the present invention are approximate, the numerical values shown in the specific examples are shown as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
The main features and aspects of the present invention are as follows.
1. A distillate fuel additive composition comprising an organometallic manganese compound, an alkyl-substituted succinimide ashless dispersant, and a highly basic calcium sulfonate detergent.
2. 2. The fuel additive according to 1 above, wherein the organometallic manganese compound comprises methylcyclopentadienyl manganese tricarbonyl.
3. The fuel additive according to 1 above, wherein the succinimide is produced from polyisobutylene succin anhydride and a polyalkylene polyamine.
4). 2. The fuel additive according to 1 above, wherein the succinimide is produced from polyisobutylene succin anhydride and tetraethylenepentamine.
5. The fuel additive according to claim 1, wherein the polyisobutylene of the alkyl-substituted succinimide is produced from polyisobutylene having a molecular weight of about 850 to 2100.
6). The fuel additive according to claim 1, wherein the polyisobutylene of the alkyl-substituted succinimide is produced from a polyisobutylene having a molecular weight of about 850 to 1300.
7. The fuel additive according to claim 1, wherein the polyisobutylene of the alkyl-substituted succinimide is produced from polyisobutylene having a molecular weight of about 950.
8). When the composition contains an organometallic complex of manganese, a highly basic calcium sulfonate detergent, and an ashless alkyl-substituted succinimide dispersant, and the additive composition is dissolved in a distillate fuel, the following relationship: 0.159x + 0.243y−0.0143xy ≦ −8.4
(Where x = succinimide concentration (pounds per thousand barrels))
y = high basic calcium sulfonate concentration (in PTB),
(limited to x = 20-35 and y = 10-120)
The fuel additive according to 1 above, which satisfies the above.
9. The fuel additive of claim 1, wherein the highly basic calcium sulfonate has a TBN of about 200 or more.
10. The fuel additive of claim 1, wherein the highly basic calcium sulfonate has a TBN of about 300.
11. A fuel comprising a major amount of middle distillate fuel and a small amount of fuel additive composition comprising an organometallic manganese compound, an alkyl substituted succinimide ashless dispersant, and a TBN about 300 highly basic calcium sulfonate detergent.
12 Using a fuel containing a distillate fuel additive composition comprising an organometallic manganese compound, an alkyl-substituted succinimide ashless dispersant, and a TBN about 300 highly basic calcium sulfonate detergent in the fuel intake system. To improve the cleanliness of the fuel intake system.

Experimental design for HiTEC® 4080 components Interaction between A: H-9645 and B: H-611 Estimated response surface contours for CRC scores

Claims (3)

  A distillate fuel additive composition comprising an organometallic manganese compound, an alkyl-substituted succinimide ashless dispersant, and a highly basic calcium sulfonate detergent.   The fuel additive according to claim 1, wherein the organometallic manganese compound comprises methylcyclopentadienyl manganese tricarbonyl.   The fuel additive according to claim 1, wherein the highly basic calcium sulfonate has a TBN of about 300.

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