Fuel Additive and Fuel Composition

Abstract

A fuel additive for a hydrocarbon based fuel that has one or more of the following Components: Component A; a non-ionic surfactant 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 of 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.

Description

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Application No. 61/526,966 filed on Aug. 24, 2011, the disclosure of which is incorporated herein by reference for all purposes.

BACKGROUND OF THE INVENTION

1. 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.

2. 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-à-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 Ia, IIa, and IIIb 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. Pat. Nos. 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. Pat. No. 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 non-crystalline 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 non-aqueous, 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-à-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
	TEST ID
	1	2	3
	GA-7126 Base	GA-7126-F1	GA-7126-F2
Date	Dec. 13, 2009	Nov. 15, 2009	Apr. 27, 2010
Engine Stand	28	28	28
Stand Run Number	178	177	187
ADDITIVE DATA
Polymer PPM	0	15	25
Polymer Type	0	C10	C10
Coating Agent	0	8	8
(MP22)1 ppm
Mill Screen	0	0.093″	0.093″
NFC2 ppm	0	2	2
H1003 ppm	0	0	0
X-354 ppm	0	2	2
Biocide5 ppm	0	0.25	0.25
WG6 ppm	0	0.065	0.065
AVERAGE
WEIGHTS
Average IVD wt, mg	313.1	265.2	11.3
Piston Top avg wt, mg	731.8	744	629.8
CC average wt, mg	769.7	824.2	654.6
AVERAGE
MERIT RATINGS
Valve Tulips	7.63	8.60	9.78
Intake Port	5.07	5.19	8.30
Runner Entrance	5.82	5.88	9.33
CC rating	6.90	6.86	6.85
Piston Top Rating	7.68	7.21	7.27
1Micronized synthetic wax marketed by Micro Powders, Inc.
2Lomar D, sulfonated naphthalene formaldehyde condensate marketed by Geo Specialty Chemicals
3Hydropalat-100, polymeric dispersing agent marketed by Cognis GmbH
4Nonyl phenol 5 mole ethoxylate marketed by Harcros
5Chemicide 6, marketed by Diversity Technologies Corp.
6Welan 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
	Cylinder Number
	1	2	3	4
Intake Valve Weights
Report (IVD)
Gross Weight (g)	104.3255	102.4564	102.6419	102.3597
Tared Weight	103.9781	102.1842	102.3213	102.0474
Deposit Weights (mg)	1	2	3	4
IVD Weight	347.4	272.2	320.6	312.3
Average IVD Weight	313.1
Piston Top Deposit
(PTD) Weights
Gross Weight (g)	23.1176	23.1192	23.1720	23.0894
Tared Weight	22.3908	22.4367	22.4700	22.2737
Deposit Weights (mg)	1	2	3	4
PTD Weights	726.8	682.5	702.0	815.7
Average PTD Weight	731.8
Combustion Chamber
Deposit (CCD) Weights
Gross Weight (g)	23.1627	23.2124	22.9661	23.1840
Tared Weight	22.4483	22.4528	22.1989	22.3464
Deposit Weights (mg)	1	2	3	4
CCD Weights	714.4	759.6	767.2	837.6
Average CCD Weight	769.7

TABLE 3
Induction System Ratings
Test ID GA-7126
	Valve	Intake	Runner	Combustion	Piston
Cylinder	Tulip	Port	Entrance	Chamber	Top
Number	(merits)	(merits)	(merits)	(merits)	(merits)
1	8.90	5.00	5.88	6.98	7.70
2	7.30	5.10	5.75	6.92	8.00
3	7.10	5.00	5.88	6.80	7.90
4	7.20	5.12	5.75	6.90	7.10
Average	7.63	5.06	5.82	6.90	7.68

TABLE 4
Deposit Weight Summary
Test ID GA-7126-F1
	Cylinder Number
	1	2	3	4
Intake Valve Deposit
(IVD) Weights
Gross Weight	102.4331	102.1305	102.5896	102.5416
Tared Weight	102.1774	101.8909	102.3217	102.2438
Deposit Weights (mg)	1	2	3	4
IVD Weight	255.7	239.6	267.9	297.8
Average IVD Weight	265.2
Piston Top Deposit
(PTD) Weights
Gross Weight (g)	22.8888	23.0568	22.9392	23.0545
Tared Weight	22.2029	22.3510	22.2262	22.1832
Deposit Weights (mg)	1	2	3	4
PTD Weights	685.9	705.8	713.0	871.3
Average PTD Weight	744.0
Combustion Chamber
Deposit (CCD) Weights
Gross Weight (g)	23.2042	23.1393	23.2850	23.2757
Tared Weight	22.4616	22.4067	22.5165	22.2224
Deposit Weights (mg)	1	2	3	4
CCD Weights	742.6	732.6	768.5	1053.3
Average CCD Weight	824.2

TABLE 5
Induction System Ratings
Test ID GA-7126-F1
	Valve	Intake	Runner	Combustion	Piston
Cylinder	Tulip	Port	Entrance	Chamber	Top
Number	(merits)	(merits)	(merits)	(merits)	(merits)
1	8.60	5.40	5.75	6.88	7.50
2	8.70	5.15	5.75	6.88	7.28
3	8.60	5.05	6.12	6.88	7.15
4	8.50	5.15	5.90	6.80	6.90
Average	8.60	5.19	5.88	6.86	7.21

TABLE 6
Deposit Weight Summary
Test ID GA-7126-F2
	Cylinder Number
	1	2	3	4
Intake Valve Deposit
(IVD) Weights
Gross Weight	102.5241	102.3995	104.4911	102.1830
Tared Weight	102.5119	102.3876	104.4807	102.1723
Deposit Weights (mg)	1	2	3	4
IVD Weight	12.2	11.9	10.4	10.7
Average IVD Weight	11.3
Piston Top Deposit
(PTD) Weights
Gross Weight (g)	23.1069	22.9331	23.0252	23.2095
Tared Weight	22.5250	22.4231	22.4120	22.3953
Deposit Weights (mg)	1	2	3	4
PTD Weights	581.9	510.0	613.2	814.2
Average PTD Weight	629.8
Combustion Chamber
Deposit (CCD) Weights
Gross Weight (g)	22.9981	22.9638	23.2264	22.9785
Tared Weight	22.4709	22.3584	22.5138	22.2053
Deposit Weights (mg)	1	2	3	4
CCD Weights	527.2	605.4	712.6	773.2
Average CCD Weight	654.6

TABLE 7
Induction System Ratings
Test ID GA-7126-F2
	Valve	Intake	Runner	Combustion	Piston
Cylinder	Tulip	Port	Entrance	Chamber	Top
Number	(merits)	(merits)	(merits)	(merits)	(merits)
1	9.80	8.18	9.01	6.80	7.10
2	9.70	8.18	9.48	6.99	7.40
3	9.80	8.18	9.68	6.85	7.38
4	9.80	8.34	9.15	6.75	7.18
Average	9.78	8.30	9.33	6.85	7.27

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
TEST ID	GA-7624 Base	GA-7622 (35N)	GA-7642 (100N)	GA-7624 + (100)
Date	Feb. 27, 2011	Mar. 14, 2011	Mar. 22, 2011	Apr. 5, 2011
Engine Stand	31	31	31	31
Stand Run Number	160	161	162	163
ADDITIVE DATA
Polymer PPM	0	25	25	25
Load In Fuel
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
7Calcium Stearate

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 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,	NFC,	PAO,	Average IVD
	ppm	ppm	ppm	wt in mg
	Base	0	0	0	245
	Formula 1	1.66	0.33	5	116
	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	113
	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

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;

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

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.

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.

11. 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.