WO2013028453A1

WO2013028453A1 - Fuel additive and fuel composition

Info

Publication number: WO2013028453A1
Application number: PCT/US2012/051107
Authority: WO
Inventors: Brad A. Bucher; Tom M. Weatherford
Original assignee: Flowchem, Ltd.
Priority date: 2011-08-24
Filing date: 2012-08-16
Publication date: 2013-02-28
Also published as: US20140318003A1

Abstract

A fuel additive for a hydrocarbon based fuel that has one or more of the following components: Component A; a non-ionic surfactant Component B; a compound selected from the group consisting of partially sulfonated naphthalene formaldehyde condensates, polymer condensates of linear alkyl benzene sulfonic acids, and naphthalene sulfonic acids with formaldehyde and mixtures thereof; Component C; a polycarboxylate-type material comprising at least one of a ammonium polyacrylate, a polyacrylate derivative, a hydrophobic copolymer, or a hydrophobically modified acrylic polymer having a pH of from about 6.0 to about 7.0; Component D; a finely divided polyalpha olefin; or Component E; any combination of A, B, C, or D.

Description

FUEL ADDITIVE AND FUEL COMPOSITION

Cross Reference To Related Application

This application claims priority to U.S. Application No. 61 /526,966 filed on August 24, 201 1 , the disclosure of which is incorporated herein by reference for all purposes. Background of the Invention

Field of the Invention

The present invention relates to fuel additives and more particularly, to fuel additives exhibiting excellent detergency in the intake systems and combustion chambers of gasoline engines and in nozzles of diesel engines. The invention also relates to fuel compositions containing such additives.

Description of the Prior Art

Sludge and/or other objectionable deposits formed in internal combustion engine fuel systems and combustion chambers of automobiles are responsible for engine trouble, of abnormal rise in carbon monoxide and unburned hydrocarbon concentrations in the exhaust gases. It has thus far been proposed to use certain fuel additives, typically gasoline detergents for removing or otherwise preventing deposits in carburetors, electronic fuel injectors, intake valves, combustion chambers and other operative parts of automobiles.

Intensive research efforts have been made in the automobile industry to eliminate or alleviate the adverse effect of exhaust gases from the human body and the environment, together with efforts for fuel consumption reduction. Accordingly, there has been a growing demand for effective and advantageous fuel additives, which are more effective and advantageous vis-a-vis preventing the buildup of sludge or other such deposits in the injector, intake system and combustion chamber of a gasoline engine.

Such additives are also useful in preventing the buildup of engine deposits formed in the injection nozzles of diesel engines caused by changes and delays in fuel flow rate which results in deteriorating running performance and more harmful exhaust gases.

Brief Summary of the Invention

In one aspect, the present invention is directed to a fuel additive which can dramatically reduce the buildup of deposits in an internal combustion engine, particularly in the intake system and combustion chamber thereof.

In another aspect, the present invention involves a composition comprising an internal combustion fuel; e.g., gasoline, and an additive to reduce buildup of sludge and other unwanted deposits in the combustion chamber of the engine.

In yet another aspect, the present invention involves an additive for use in diesel fuel to reduce diesel engine deposits in injection nozzles of diesel engines.

Description of Preferred Embodiments

The fuel additive of the present invention comprises a compound which can be:

Component A a non-ionic surfactant having hydrophobic-hydrophilic constituents in the molecule and having the formula:

wherein R is an alkyl radical having from 4 to 20 carbon atoms, preferably 6 to

10 carbon atoms, and n is an integer of from 2 to 8;

Component B a compound selected from the group consisting of partially sulfonated naphthalene formaldehyde condensates, polymer condensates of linear alkyl benzene sulfonic acids, and naphthalene sulfonic acids with formaldehyde and mixtures thereof;

Component C a polycarboxylate-type material comprising at least one of a ammonium polyacrylate, a polyacrylate derivative, a hydrophobic copolymer, or a hydrophobically modified acrylic polymer having a pH from about 6.0 to about

7.0;

Component D a finely divided poly alpha olefin; or

Component E any combination of A, B, C, or D. Polymers D which are used to prepare the finely divided polymer particles used in the compositions of the present invention are obtained by polymerizing or copolymerizing mono-olefins containing from about 2 to about 30 carbon atoms. More usually, the mono-olefins, which are preferably alpha olefins, contain from about 4 to about 20 carbon atoms, most preferably from about 6 to about 14 carbon atoms.

Any of several well known methods for polymerizing the mono-olefins may be employed to produce the polymeric/co-polymeric agents used in the compositions of the present invention. A particularly suitable method is the Ziegler-Natte process which employs a catalyst system comprising the combination of a compound of a metal of Groups IVb, Vb, VIb, or VIII of the Periodic Chart of Elements, with an organo metal compound of a rare earth metal or a metal from Groups la, lla, and 1Mb of the Periodic Chart of the Elements. Particularly suitable catalyst systems are those comprising titanium halides and organo aluminum compounds. A typical polymerization procedure is to contact the monomeric mixture with a catalyst in a suitable inert hydrocarbon solvent for the monomers and the catalyst in a closed reaction vessel at reduced temperatures autogenous pressure and in a nitrogen or inert atmosphere. Methods and catalysts used in the preparation of suitable polyolefin polymers useful in the present invention are disclosed in the following U.S. patents: 4,289,679; 4,358,572; 4,415,704; 4,433,123; 4,493,903; and 4,493,904, all of which are incorporated herein by reference for all purposes. Polyalphaolefins used in the compositions of the present invention can be produced by a so- called solution polymerization technique, or by bulk polymerization methods as described, for example, in U.S. Patent 5,539,044, the disclosure of which is incorporated herein by reference for all purposes.

The polymers which are used in preparing the compositions of the present invention are generally those of relatively high molecular weight. In general, the effectiveness of the polymers in the fuel composition increases as the molecular weight increases beyond a certain point therein. The average molecular weight of the polymers is usually over 100,000 and is generally in the range of from about 300,000 to about 2 million. The average molecular weight of the polymers used in the processes and compositions of the present invention is preferably in the range of about 500,000 to about 1 .5 million. In general, useful polyolefins in the present invention can be characterized as high molecular weight noncrystalline polymers.

The polyolefin of the present invention can comprise a coating or partitioning agent, e.g., a wax. The term "wax" includes any low melting, e.g., <500 °C, organic mixture or compound of high molecular weight which is solid at ambient temperature. The waxes contemplated by the present invention can be natural, i.e., derived from animal, vegetable or mineral sources, e.g., fatty acid waxes, or synthetic as, for example, ethylenic polymers, waxes obtained from the Fischer-Tropsch synthesis, etc. Non-limiting examples of suitable waxes include paraffin, micro-crystalline wax, slack or scale wax, polymethylene wax, polyethylene wax, fatty acid wax, etc. Typically, the waxes used in the compositions of the present invention are hydrocarbon in nature and are powders or particulates at room temperature. In addition to waxes, non-limiting examples of other suitable coating agents include talc, alumina, metal salts of a fatty acid, e.g, metal stearates, silica gel, polyanhydride polymers, etc. It will be understood that the term "coating agent" is intended to and does include components which while not actually coating the polymeric material, interact with the polymeric material in such a way, be it chemical or physical, which prevents the polyolefin, when ground to a desired particle size, from agglomerating to the extent that the agglomerated material constitutes a solid or substantially solid non-dispersable mass.

Generally speaking and when used, the coating or partitioning agent will be present in the compositions of the present invention in an amount of from about 1 to about 25 ppm, preferably from about 5 to about 10 ppm.

Although the fuel additive compound(s) can be added per se to the fuel, e.g., gasoline, as it is being formulated at the refinery, in many cases it is more advantageous to add the compositions in conjunction with a carrier, which can be aqueous or non-aqueous. The use of a carrier is especially desirable if it is desired to market the fuel additive compositions of the present invention for addition by the vehicle owner as for example when filling up at a service station or the like. For example, if it is desired to market the fuel additive composition in a pre-packaged form for use by the end user, the carrier can be aqueous or nonaqueous, or can be a mixture of aqueous and non-aqueous carriers or suspending mediums. Thus for example a hydrocarbon such as gasoline could be used as a carrier to form a "syrup" for use in pre-packaged form for end users.

Whether coated or uncoated, the polyolefin powders or particulates of the present invention may have an average particle size of from about 25 microns to about 100 microns.

Compounds of type B are generically naphthalene-formaldehyde condensates such water-sulfonated naphthalene-formaldehyde condensate marketed under the name LomarD by Geo Specialty Chemicals. Other B type compounds include sulfonated or partially sulfonated naphthalene formaldehyde condensates, polymeric condensates of linear alkyl benzene sulfonic acids and naphthalene sulfonic acids with formaldehyde and mixtures thereof.

C type compounds include poly carboxylate-type materials such as polyacrylates and polyacrylate derivatives. Such polymeric molecules comprises repeating units of a carbon-based backbone, some or all of the repeating units having a carboxylic acid group. The carboxylic acid groups can be neutralized to form the salts or neutralized with other bases to form other salts, e.g.., sodium salts, ammonium salts, etc. The acid groups can also be reacted with other materials, e.g., alcohols, anhydrides, etc. to form esters, etc. In addition, various co-monomers can be employed to alter the character and composition of the resulting polymer. Nonlimiting examples of C type compounds are marketed under the name Hydropalat® by Cognis Deutchland GmbH. In particular it has been found that Hydropalat® 100 and Hydropalat® 34 are particularly useful. The latter are described as hydrophobic ammonium copolymers or hydrophobically modified acrylic acid polymers having a pH of from about 6.0 to about 7.0.

While not wanting to be bound by any theory, it is believed that of the components A, B, C, D listed above, one of the more useful compositions is Component D, i.e., the polyalphaolefin, in combination with B, or C or both.

In the discussion which follows and in respect of the right amount of components A, B, C, or D employed, all amounts are given in terms of a weight/weight basis based on the weight of fuel. In general, the following ranges for the various components has been found to be effective.

A from 0 - 3 ppm

B from 0.1 - 8 ppm

C from 0.01 - 5 ppm

D from 2 - 80 ppm

From the above it can be seen that, relative to one another, when the fuel additive comprises components B and D, Component B will be present in an amount of from about 4 wt% to about 10 wt% and Component D will be present in an amount of from about 90 wt% to about 99 wt%. When the fuel additive comprises components C and D, Component C will be present in an amount of from about 0.2 wt% to about 1 wt% and Component D will be present in an amount of from about 92 wt% to about 99 wt%. When the fuel additive comprises components B, C and D, Component B will be present in an amount from about 4.5 wt% to about 9 wt%, Component C will be present in an amount from about 0.2 wt% to 1 wt%, and Component D will be present in an amount from about 85 wt% to about 99 wt%.

It will be appreciated that the particular type and amount of components, e.g., A, B, C, D, or E, used will depend upon the fuel type, e.g., gasoline, diesel, etc. Furthermore, the amounts can be easily tailored by those of skill in the art so that for a given gasoline formulation, optimum results are obtained vis-a-vis preventing fouling and deposition.

The compositions of the present invention can include, with advantage, particularly in the case of diesel fuels, a biocide in an amount of from about 0.05 to about 0.3 ppm. Nonlimiting examples of typical biocides include glutaraldehyde, and glutaraldehyde / quarternary ammonium compound blend, isothiazolin, tetrahydromethyl phosphonium sulfate (THPS), 2,2-dibromo-3- nitrilopropionamide, bronopol and mixtures thereof.

Additionally, although not necessary the compositions can contain thickening agents such as welan gum. When present, the thickening agent will generally be present in an amount of 0.01 - 1 ppm.

To illustrate the present invention, the following nonlimiting examples are presented: In examples 1 and 2, the testing was conducting according to ASTM D6201 -04 "Standard Test Method for Dynamometer Evaluation of Unleaded- Existing Engine Fuel for Intake Valve Deposit Formation" using a four cylinder Ford 2.3 L engine.

EXAMPLE 1 In this example, the fuel tested was Shell V Power having an anti-fouling package and formulated in 2009-2010 and purchased at a Shell refining outlet. This Shell V Power is designated herein as Shell V Power-1 . Table 1 summarizes the results of testing conducting using the Shell V Power-1 (Test ID GA-7126), Shell V Power-1 plus fuel additive Formulation 1 (Test ID GA-7126- F1 ) Shell V Power plus additive Formulation 2 (Test ID GA-7126-F2).

Table 1

¹ Micronized synthetic wax marketed by Micro Powders, Inc.

² Lomar D, sulfonated naphthalene formaldehyde condensate marketed by Geo Specialty Chemicals

³ Hydropalat-100, polymeric dispersing agent marketed by Cognis GmbH

⁴ Nonyl phenol 5 mole ethoxylate marketed by Harcros

⁵ Chemicide 6, marketed by Diversity Technologies Corp.

⁶ Welan gum Testing results based on the formulations shown in Table 1 are set forth in Tables 2-7.

TABLE 2

Deposit Weight Summary

Test ID GA-7126

TABLE 3

Induction System Ratings Test ID GA-7126

TABLE 4

Deposit Weight Summary Test ID GA-7126-F1

TABLE 5

Induction System Ratings Test ID GA-7126-F1

TABLE 6

Deposit Weight Summary Test ID GA-7126-F2

TABLE 7

Induction System Ratings

Test ID GA-7126-F2

EXAMPLE 2 This example shows another comparison using Shell V Power gasoline

(Shell V Power-2) purchased at a Shell refinery outlet but having a reformulated anti-fouling package which differs from the package contained in the Shell V Power-2 used in Example 1 . The results of the various tests are shown in Table 8. In Table 8, results are shown for the base gasoline Shell V Power-2 (Test ID GA-7624 Base), Shell V Power-2 with additive Formulation 3 (Test ID GA-7624- F3), Shell V Power-2 plus additive Formulation 4 (Test ID GA-7624-F4) and Shell V Power-2 plus additive Formulation 5 (Test GA-7624-F5).

Table 8

GA-7624 Base GA-7622 (35N) GA-7642(100N) GA-7624+(100)

TEST ID

Date 2/27/201 1 3/14/2011 3/22/2011 4/5/2011

Engine Stand 31 31 31 31

Stand Run Number 160 161 162 163

ADDITIVE DATA

Polymer PPM Load In Fuel 0 25 25 25

Polymer Type 0 C10 C10 C10

Coating Agent⁷ (ppm) 0 8 8 8

Mill Screen 0 0.093" 0.093" 0.093"

NFC (ppm) 0 2 2 0

H100 (ppm) 0 0 0.5 0.5

X-35 (ppm) 0 2 0 0

Biocide (ppm) 0 0.25 0.25 0.25

WG (ppm) 0 0.065 0.065 0.065

AVERAGE WEIGHTS

Average IVD wt, mg 131 .7 112.4 78.6 106.8

Piston Top avg wt, mg 910.4 769.6 575.4 652.8

CC average wt, mg 965 814.6 609.1 673.3

AVERAGE MERIT RATINGS

Valve Tulips 8.83 7.78 8.88 7.93

Intake Port 6.55 5.97 7.84 7.90

Runner Entrance 8.39 6.60 9.67 9.53

CC rating 6.68 6.49 6.60 6.21

Piston Top Rating 7.07 6.98 7.08 7.04

EXAMPLE 3

In this example, testing was conducted pursuant to European standards procedure CEC F-05-93 for testing inlet valve cleanliness using an MB 102 E engine. The gasoline employed was Unleaded Regular MG 91 to which contains 300 ppm of an anti-fouling additive, Keropur® marketed by BASF to form a base gasoline. The base gasoline was then mixed with various other components of

⁷ Calcium Stearate the present invention in various amounts and tested for intake valve deposits (IVD). The results are shown in Table 9, below.

TABLE 9

X-35, Dom NFC, DOm PAO, DOm Averaae IVD wt in ma

Base 0 0 0 245

Formula 1 1 .66 0.33 5 1 16

Formula 2 0.33 1 .66 5 50

Formula 3 0 4 5 90

Formula 4 0 8 5 51

Formula 5 0 24 5 1 13

Formula 6 0 8 10 125

Formula 7 2 2 25 195

As can be seen from the above data, the fuel additive compositions of the present invention show remarkable results in terms of reducing engine deposits in the combustion train of the engine.

As the data shows, various combinations of the various components A, B, C, or D can be employed and, as noted above, can be tailored by those skilled in the art of fuel blending to achieve optimum results. However, in virtually all cases, the results achieved using the compositions of the present invention, regardless of the amount or type of the various components, gives better results in terms of reducing combustion train deposits.

Although specific embodiments of the invention have been described herein in some detail, this has been done solely for the purposes of explaining the various aspects of the invention, and is not intended to limit the scope of the invention as defined in the claims which follow. Those skilled in the art will understand that the embodiment shown and described is exemplary, and various other substitutions, alterations and modifications, including but not limited to those design alternatives specifically discussed herein, may be made in the practice of the invention without departing from its scope.

Claims

WHAT IS CLAIMED IS:

1 . A fuel additive for a hydrocarbon based fuel comprising at least one of:

wherein R is an alkyl radical having from 4 to 20 carbon atoms, preferably 6 to

10 carbon atoms, and n is an integer of from 2 to 8;

7.0;

Component D a finely divided poly alpha olefin; or

Component E any combination of A, B, C, or D.

2. The fuel additive of claim 1 , comprising Component D and at least one of Component B or Component C.

3. The fuel additive of claim 2, comprising Component D and Component B.

4. The fuel additive of claim 2, comprising Component D and Component C.

5. The fuel additive of claim 2, comprising Component D, Component

B and Component C.

6. The fuel additive of claim 1 , wherein said polyalpha olefin is produced from alpha olefins containing between 4 - 20 carbon atoms.

7. The fuel additive of claim 6, wherein said polyalpha olefin contains between 6 -14 carbon atoms.

8. The fuel additive of claim 1 , wherein said polyalpha olefin is produced from alpha olefins having an average of 10 carbon atoms.

9. The fuel additive of claim 6, wherein the molecular weight of the polyalpha olefin is from about 300,000 to about 2,000,000.

10. The fuel additive of claim 6, wherein said polyalpha olefin has a particle size of from 25 microns to 100 microns.

1 1 . The fuel additive of claim 5, wherein Component B is present in an amount of from about 4.5 wt% to about 9.0 wt%, Component C is present in an amount from about 0.2 wt% to about 1 .0 wt%, and Component D is present in an amount from about 85 wt% to about 99 wt%.

12. The fuel additive of claim 3, wherein Component B is present in an amount from about 4.0 wt% to about 10 wt%, and Component D is present in an amount from about 90 wt% to about 99 wt%.

13. The fuel additive of claim 4, wherein Component D is present in an amount from about 92 wt% to about 99 wt% and Component C is present in an amount from about 0.2 wt% to about 1 .0 wt%.

14. The fuel additive composition of claim 1 comprising an adjunct selected from the group consisting of biocides, thickening agents and mixtures thereof.

15. A fuel composition comprising a hydrocarbon containing fuel and a fuel additive according to claim 1 .

16. The fuel composition of claim 15, wherein the hydrocarbon fuel comprises diesel.

17. The fuel composition of claim 15, wherein the hydrocarbon fuel comprises gasoline.