阅读说明：本技术 银腐蚀抑制剂组合物和使用方法 (Silver corrosion inhibitor compositions and methods of use ) 是由 R·古铁雷斯 H·G·巴加里亚 M·阿德沃尔 R·格罗普 于 2018-08-09 设计创作，主要内容包括：本发明涉及一种增效性燃料添加剂组合物,所述组合物具有硫添加剂和不含硫的添加剂,其中所述硫添加剂与所述无硫添加剂的比率为约1:1至约1:100。一种使燃料组合物中的硫含量降低的方法,所述方法规定将燃料添加剂加入燃料组合物,所述燃料组合物具有银腐蚀抑制剂,所述燃料添加剂具有：硫添加剂和不含硫的添加剂,其中所述硫添加剂与所述不含硫的添加剂的比率为约1:1至约1:100；其中所述燃料添加剂向所述燃料组合物提供低于5 ppm的硫添加,并且其中所述燃料组合物不造成银腐蚀。(The present invention relates to a synergistic fuel additive composition having a sulfur additive and a sulfur-free additive, wherein the ratio of the sulfur additive to the sulfur-free additive is from about 1:1 to about 1: 100. A method of reducing the sulfur content of a fuel composition, the method providing for the addition of a fuel additive to a fuel composition, the fuel composition having a silver corrosion inhibitor, the fuel additive having: a sulfur additive and a non-sulfur containing additive, wherein the ratio of the sulfur additive to the non-sulfur containing additive is from about 1:1 to about 1: 100; wherein the fuel additive provides less than 5 ppm sulfur addition to the fuel composition, and wherein the fuel composition does not cause silver corrosion.)

1. A synergistic fuel additive composition comprising:

a sulfur additive; and

an additive which does not contain sulfur, wherein the additive contains sulfur,

wherein the ratio of the sulfur additive to the sulfur-free additive is from about 1:1 to about 1: 100.

2. A fuel additive composition as in claim 1 wherein the sulfur additive comprises the formula:

，

wherein R1 and R2 are independently selected from the group consisting of a disulfide bond forming 4-20 carbon alkylmercapto group, hydrogen, and a 4-20 carbon hydrocarbyl group.

3. A fuel additive composition as in claim 1 wherein the sulfur-free additive comprises a plurality of fatty acids from C8 to C22 monocarboxylic acids and/or C8 to C22 dicarboxylic acids or anhydrides.

4. A fuel additive composition as in claim 1, wherein the composition does not cause silver corrosion.

5. A fuel additive composition as in claim 1, wherein the fuel additive composition reduces the sulfur content of the fuel composition by at least 50%.

6. A method of reducing the sulfur content of a fuel composition, the method comprising:

adding a fuel additive to a fuel composition, the fuel composition requiring a silver corrosion inhibitor,

wherein the fuel additive provides a sulfur addition of less than 5 ppm.

7. The method as recited in claim 6, wherein the fuel additive comprises a sulfur additive and a non-sulfur containing additive.

8. The method as set forth in claim 7 wherein the ratio of the sulfur additive to the sulfur-free additive is from about 1:1 to about 1: 100.

9. The method as set forth in claim 7 wherein the sulfur additive comprises the formula:

wherein R1 and R2 are independently selected from the group consisting of a disulfide bond forming 4-20 carbon alkylmercapto group, hydrogen, and a 4-20 carbon hydrocarbyl group.

10. A method as set forth in claim 7 wherein the sulfur-free additive comprises a plurality of fatty acids from a C8 to C22 monocarboxylic acid.

11. The method as claimed in claim 7, wherein the sulfur-free additive comprises a plurality of fatty acids from C8 to C22 dicarboxylic acids or anhydrides.

12. The method as recited in claim 6, wherein the fuel additive provides a sulfur addition of less than 2 ppm.

13. The method as recited in claim 6, wherein the fuel additive provides a sulfur addition of less than 0.50 ppm.

14. A method of reducing the sulfur content of a fuel composition, the method comprising:

adding a fuel additive to a fuel composition, the fuel composition requiring a silver corrosion inhibitor, the fuel additive comprising:

a sulfur additive and a non-sulfur containing additive, wherein the ratio of the sulfur additive to the non-sulfur containing additive is from about 1:1 to about 1: 100;

wherein the fuel additive provides less than 5 ppm sulfur addition to the fuel composition; and is

Wherein the fuel composition does not cause silver corrosion.

15. The method as set forth in claim 14 wherein the sulfur additive comprises the formula:

，

wherein R1 and R2 are independently selected from the group consisting of C4 to C20 carbon alkyl mercapto, hydrogen and C4 to C20 carbon hydrocarbyl forming a disulfide bond.

16. The method as claimed in claim 14, wherein the sulfur-free additive comprises a plurality of fatty acids from C8 to C22 monocarboxylic acids and/or C8 to C22 dicarboxylic acids or anhydrides.

17. The method as claimed in claim 16, wherein the fatty acid comprises alkenyl or alkyl succinic acid.

18. A method as claimed in claim 17, wherein said alkenyl or alkyl succinic acid comprises dodecenyl succinic acid or dodecyl succinic acid.

19. A method as set forth in claim 16 wherein the fatty acid comprises an alkenyl or alkyl succinic anhydride.

20. A method as set forth in claim 19 wherein the alkenyl or alkyl succinic anhydride comprises dodecenyl succinic anhydride or dodecyl succinic anhydride.

21. A method as set forth in claim 16 wherein the fatty acid comprises a monocarboxylic acid.

22. A method as set forth in claim 21 wherein the monocarboxylic acid comprises oleic acid, linoleic acid, or linolenic acid.

23. The method as set forth in claim 14 wherein the fuel additive provides a sulfur addition of less than 2 ppm.

24. The method as set forth in claim 14 wherein the fuel additive provides a sulfur addition of less than 0.50 ppm.

25. The method as set forth in claim 14 wherein the fuel additive provides a sulfur addition of less than 0.1 ppm.

Technical Field

The disclosed technology, generally described below, provides synergistic fuel additive compositions, and more specifically, synergistic fuel additive compositions and methods of reducing sulfur content, wherein the fuel additive reduces the sulfur content while still meeting silver corrosion specifications.

Background

In general, spark ignition fuels, often referred to as gasoline, have silver corrosion and sulfur specifications that refiners and importers must meet before introducing gasoline into commerce. In some cases, refinery processing units are unable to remove trace contaminants, which renders gasoline unable to meet silver corrosion specifications, such as those contained in the standard specifications for ASTM D4814 automotive spark ignition engine fuels.

In many of these cases, refiners and gasoline importers are turning to the use of corrosion inhibitor additives to help meet specifications. The commercially predominant silver corrosion inhibitor alkyldithiothiadiazoles contain sulfur and typically introduce several ppm of sulfur into the treated gasoline. The treated gasoline thus meets corrosion specifications, but may not meet sulfur regulations, such as those found in the Tier 3 gasoline sulfur regulations of the U.S. EPA. Non-compliance with sulfur regulations may result in high fines in the form of sulfur credits being purchased from other refiners and/or importers, where such sulfur credit purchases may cost millions of dollars.

Disclosure of Invention

The disclosed technology, generally described below, provides synergistic fuel additive compositions and methods for reducing the sulfur content in fuel compositions, wherein the fuel additive reduces the sulfur content while still meeting silver corrosion specifications.

In one aspect of the disclosed technology, a synergistic fuel additive composition is provided. A synergistic fuel additive composition comprising a sulfur additive and a non-sulfur containing additive, wherein the ratio of sulfur additive to non-sulfur additive is from about 1:1 to about 1: 100.

In some embodiments, the sulfur additive comprises the formula:

，

wherein R1 and R2 are independently selected from the group consisting of a disulfide bond forming 4-20 carbon alkylmercapto group, hydrogen, and a 4-20 carbon hydrocarbyl group.

In some embodiments, the sulfur-free additive comprises a plurality of fatty acids from C8 to C22 monocarboxylic acids and/or C8 to C22 dicarboxylic acids or anhydrides. In some embodiments, the composition does not cause silver corrosion. In some embodiments, the fuel additive composition reduces the sulfur content in the fuel composition by at least 50%.

In another aspect of the disclosed technology, a method of reducing the sulfur content of a fuel composition is provided. The method includes adding a fuel additive to a fuel composition, the fuel composition requiring a silver corrosion inhibitor, wherein the fuel additive provides less than 5 ppm sulfur addition.

In some embodiments, the fuel additive comprises a sulfur additive and a sulfur-free additive. In some embodiments, the ratio of sulfur additive to sulfur-free additive is from about 1:1 to about 1: 100.

In some embodiments, the sulfur additive comprises the formula:

wherein R1 and R2 are independently selected from the group consisting of a disulfide bond forming 4-20 carbon alkylmercapto group, hydrogen, and a 4-20 carbon hydrocarbyl group.

In some embodiments, the sulfur-free additive comprises a plurality of fatty acids from C8 to C22 monocarboxylic acids. In some embodiments, the sulfur-free additive comprises a plurality of fatty acids from C8 to C22 dicarboxylic acids or anhydrides. In some embodiments, the fuel additive provides less than 2 ppm sulfur addition. In some embodiments, the fuel additive provides a sulfur addition of less than 0.50 ppm.

In yet another aspect of the present technology, a method of reducing the sulfur content of a fuel composition is provided. The method includes adding a fuel additive to a fuel composition, the fuel composition requiring a silver corrosion inhibitor; the fuel additive comprises a sulfur additive and a non-sulfur containing additive, wherein the ratio of the sulfur additive to the non-sulfur containing additive is from about 1:1 to about 1: 100; wherein the fuel additive provides less than 5 ppm sulfur addition to the fuel composition, and wherein the fuel composition does not cause silver corrosion.

In some embodiments, the sulfur additive comprises the formula:

，

wherein R1 and R2 are independently selected from the group consisting of C4 to C20 carbon alkyl mercapto, hydrogen and C4 to C20 carbon hydrocarbyl forming a disulfide bond.

In some embodiments, the sulfur-free additive comprises a plurality of fatty acids from C8 to C22 monocarboxylic acids and/or C8 to C22 dicarboxylic acids or anhydrides. In some embodiments, the fatty acid comprises an alkenyl or alkyl succinic acid. In some embodiments, the alkenyl or alkyl succinic acid comprises dodecenyl succinic acid or dodecyl succinic acid.

In some embodiments, the fatty acid comprises an alkenyl or alkyl succinic anhydride. In some embodiments, the alkenyl or alkyl succinic anhydride comprises dodecenyl succinic anhydride or dodecyl succinic anhydride. In some embodiments, the fatty acid comprises a monocarboxylic acid. In some embodiments, the monocarboxylic acid comprises oleic acid, linoleic acid, or linolenic acid.

In some embodiments, the fuel additive provides less than 2 ppm sulfur addition. In some embodiments, the fuel additive provides a sulfur addition of less than 0.50 ppm. In some embodiments, the fuel additive provides a sulfur addition of less than 0.1 ppm.

Brief Description of Drawings

These and other features and advantages of the disclosed technology are now more particularly described in the embodiments that will now be described, by way of example, with reference to the accompanying schematic drawings in which:

fig. 1 is a table providing results of illustrative embodiments of the disclosed technology.

Detailed description of illustrative embodiments

The disclosed technology, generally described below, provides a fuel additive composition. The fuel additive composition provides a synergistic effect that reduces the amount of sulfur added to the fuel composition, but still meets the silver corrosion specification requirements required by the U.S. EPA and potentially other regulatory entities. By using the fuel additive composition of the present invention, the amount of sulfur addition is significantly reduced while still exhibiting improved performance according to ASTM D7671 and/or ASTM D7667 test methods.

The synergistic fuel additive composition comprises a sulfur additive and a sulfur-free additive. In some embodiments, the ratio of sulfur additive to sulfur-free additive is from about 1:1 to about 1: 100.

In some embodiments, the sulfur additive comprises the following formula (I):

，

wherein R1 and R2 are independently selected from the group consisting of a disulfide bond forming 4-20 carbon alkylmercapto group, hydrogen, and a 4-20 carbon hydrocarbyl group.

In some embodiments, the sulfur-free additive comprises a plurality of fatty acids from C8 to C22 monocarboxylic acids and/or C8 to C22 dicarboxylic acids or anhydrides. In some embodiments, the sulfur-free additive comprises a plurality of fatty acids or anhydrides having between C8 and C22 with one or two carboxylic acid groups, and in other embodiments, succinic acid or anhydride having between C8 and C18.

In some embodiments, the plurality of fatty acids comprises alkenyl or alkyl succinic acids or anhydrides, such as, but not limited to, dodecenyl succinic acid or anhydride (DDSA), dodecyl succinic acid or anhydride, hexadecenyl succinic acid or anhydride, hexadecyl succinic acid or anhydride. In other embodiments, the plurality of fatty acids comprise monocarboxylic acids such as, but not limited to, oleic acid, linoleic acid, and/or linolenic acid.

In some embodiments, the sulfur-free additive is dodecenyl succinic acid or anhydride (DDSA) or Tall Oil Fatty Acid (TOFA). In some embodiments, the sulfur-free additive comprises a plurality of fatty acids having between C8 and C22 with one or two carboxylic acid groups. In some embodiments, the synergistic fuel additive composition comprises an alkyldithiothiadiazole and dodecenylsuccinic acid (DDSA) or TOFA.

The synergistic fuel additive compositions of the disclosed technology do not cause silver corrosion. In some embodiments, the synergistic fuel additive composition reduces the sulfur content in the fuel composition by at least 50%, and in other embodiments, by at least 80%.

The fuel additive composition of the disclosed technology allows for a synergistic effect of reducing the sulfur content of the fuel composition by at least 80% to yield a pass rate of about 1 (based on ASTM D7667 or ASTM D7671 silver corrosion test methods), while at the same time enabling a reduction in the amount of treating agent. By reducing the amount of treatment, the amount of sulfur provided in the blended gasoline will be reduced.

In some embodiments, the fuel additive composition is added to the fuel composition at a treatment dosage of about 10 ppmv. By reducing the amount of treatment of the fuel additive composition, the refiner will be able to meet the required sulfur specifications without incurring regulatory penalties for exceeding sulfur limits.

In other embodiments, the fuel additive composition is added to the fuel composition at a treat dose of between about 10 and about 80 ppmv. One of ordinary skill will appreciate that other dosages may be required to pass the required corrosion specification.

In some embodiments, the treatment dosage of the fuel additive composition can be reduced by at least 50% upon addition of the fuel.

In yet another embodiment of the disclosed technology, a method of reducing the sulfur content of a fuel composition is provided. The method comprises adding a fuel additive to a fuel composition, the fuel composition comprising a silver corrosion inhibitor, wherein the fuel additive provides less than 5 ppm of sulfur addition. It will be understood by those skilled in the art that "sulfur addition" is defined as a by-product of typical silver corrosion inhibition products that tend to have sulfur species therein. As the dosage of the inhibitor is increased to protect against corrosion, the total amount of sulfur in the fuel increases. As government regulations tighten down, which continually reduce the amount of acceptable sulfur in fuel products, successful fuel additives should provide low sulfur addition.

In other embodiments, the fuel additive provides less than 2 ppm sulfur addition, in other embodiments, less than 1 ppm sulfur addition, in other embodiments, less than 0.50 ppm sulfur addition, and in other embodiments, less than 0.1 ppm sulfur addition.

In some embodiments, the fuel composition comprises gasoline or a gasoline blend as defined by ASTM D4814. In some embodiments, the fuel additive of the present method comprises a sulfur additive and a sulfur-free additive. In some embodiments, as previously described, the sulfur additive comprises the following formula (I):

，

wherein R1 and R2 are independently selected from the group consisting of a disulfide bond forming 4-20 carbon alkylmercapto group, hydrogen, and a 4-20 carbon hydrocarbyl group.

In some embodiments, the sulfur-free additive comprises a plurality of fatty acids having between C8 and C22 with one or two carboxylic acid groups. In some embodiments, the sulfur-free additive comprises a plurality of fatty acids having between C8 and C18 with one or two carboxylic acid groups.

In some embodiments, the fatty acid comprises an alkyl succinic acid or a monocarboxylic acid. In some embodiments, the fatty acid is dodecenyl succinic acid (DDSA) and/or dodecyl succinic acid. In some embodiments, the fatty acid comprises a monocarboxylic acid, such as, but not limited to, oleic acid, linoleic acid, and/or linolenic acid.

In a particular embodiment, a method of reducing the sulfur content of a fuel composition is provided. The method includes adding a fuel additive to a fuel composition, the fuel composition requiring a silver corrosion inhibitor; the fuel additive comprises a sulfur additive and a non-sulfur containing additive, wherein the ratio of the sulfur additive to the non-sulfur containing additive is from about 1:1 to about 1: 100; wherein the fuel additive provides less than 5 ppm sulfur addition to the fuel composition, and wherein the fuel composition does not cause silver corrosion.

Examples

The present invention will be further described in the following examples, which are to be considered illustrative and should not be construed to narrow the scope of the disclosed technology or to limit the scope to any particular embodiment.

FIG. 1 provides a graph of a catalyst containing 10 ppmw H₂Silver flake test results in hydrocarbon of S liquid.

As shown in FIG. 1, the standard industry product alkylthiothiadiazole (run #3) when used alone exhibits an unacceptable silver flake corrosion rating of 2 with 2.50 ppm of sulfur added. In addition, when DDSA was used alone (experiment #2), it still did not provide an acceptable silver flake rating (i.e., it did not provide a silver flake rating of 1) although it did not add any additional sulfur.

However, as shown in the comparative examples (experiments #5-8), the fuel additive compositions of the present technology provide synergistic effects. A synergistic fuel additive comprising a blend of 80% DDSA and 20% alkylthio thiadiazole exhibits a qualified silver flake corrosion rating of 1 while providing an added sulfur content of between 0.50 ppm and 4.0 ppm.

While embodiments of the disclosed technology have been described, it is to be understood that the disclosure is not so limited and modifications may be made without departing from the disclosed technology. The scope of the disclosed technology is defined by the appended claims, and all devices, processes, and methods that come within the meaning of the claims, either literally or by equivalence, are intended to be embraced therein.