DESC:FIELD
The present disclosure relates to a lubricity additive and a process for its preparation.
DEFINITION
As used in the present disclosure, the following terms are generally intended to have the meaning as set forth below, except to the extent that the context in which they are used indicates otherwise.
Lubricity: The term “lubricity” is often defined as the ability of a lubricant (in this case diesel fuel) to minimize friction and damage to the surfaces in a relative motion under load.
Wear Scar Diameter (WSD): The term “WSD” is the average of the major and minor axis of the wear scar. The WSD value is generally correlated to the lubricity of the fuel as smaller the scar, less wear has occurred which in turn refers to the better lubricity.
BACKGROUND
The background information herein below relates to the present disclosure but is not necessarily prior art.
Conventional processes for the manufacturing Ultra Low Sulphur Diesel (ULSD) have several concerns, out of which the loss of lubricity in the resulting product is the major one. The poor lubricity of ULSD mandates the use of additives or blending with another fuel of sufficient lubricity, to restore the property of lubricity. The engine and fuel systems rely heavily on the lubricity of the fuel for a smooth operation.
Conventionally, a neutral (ester type) lubricity additive and a mono-acid lubricity additive are used. However, these lubricity additives result in insufficient lubricity leading to premature failure of the components in the fuel system.
Therefore, there is felt a need to provide a lubricity additive and a process for its preparation that mitigates the drawbacks mentioned herein above or at least provides a useful alternative.
OBJECTS
Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows.
An object of the present disclosure is to ameliorate one or more problems of the background or to at least provide a useful alternative.
Another object of the present disclosure is to provide a lubricity additive.
Yet another object of the present disclosure is to provide a process for the preparation of a lubricity additive.
Still another object of the present disclosure is to provide a lubricity additive that has improved lubricity and is cost-effective.
Another object of the present disclosure is to provide a lubricity additive for improving the lubricity of Ultra Low Sulphur Diesel (ULSD).
Yet another object of the present disclosure is to provide a simple process for the preparation of a lubricity additive by using easily available raw materials.
Another object of the present disclosure is to provide a commercially scalable process for the preparation of a lubricity additive.
Other objects and advantages of the present disclosure will be more apparent from the following description, which is not intended to limit the scope of the present disclosure.
SUMMARY
The present disclosure relates to a lubricity additive, being a reaction product of at least one organic acid in an amount in the range of 20 mass% to 40 mass%, at least one anhydride in an amount in the range of 10 mass% to 30 mass%, at least one alcohol in an amount in the range of 10 mass% to 20 mass%, a catalyst in an amount in the range of 0.05 mass% to 0.15 mass%, at least one fluid medium in an amount in the range of 10 mass% to 20 mass% and at least one amine in an amount in the range of 15 mass% to 35 mass%, wherein the mass% of each component is with respect to the total mass of the additive.
The present disclosure further relates to a process for the preparation of a lubricity additive. The process comprises mixing predetermined amounts of at least one anhydride and a catalyst in a predetermined amount of at least one first fluid medium under stirring at a speed in the range of 300 rpm to 400 rpm to obtain a first mixture followed by adding a predetermined amount of at least one alcohol to obtain a second mixture. The so obtained second mixture is refluxed at a first predetermined temperature for a first predetermined time period to obtain a homogeneous slurry. A predetermined amount of at least one amine is added followed by addition of a predetermined amount of at least one organic acid to the homogeneous slurry while refluxing and continuing the refluxing for a second predetermined time period to obtain a product mixture. The product mixture is cooled at a second predetermined temperature for a third predetermined time period to obtain a cooled product mixture. The cooled product mixture is purified to obtain the lubricity additive.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWING
The present disclosure will now be described with the help of the accompanying drawing, in which:
Figure 1 (A-F) illustrates high frequency reciprocating rig (HFRR) scar images of
(A) neat ultra low sulfur diesel (ULSD) having ware scar diameter (WSD) of 526 µm;
(B) ULSD with 150 ppm dosage concentration of the lubricity additive of Example: LI 11 having WSD of 435 µm;
(C) ULSD with 150 ppm dosage concentration of the lubricity additive of Example: LI 16 having WSD of 397 µm;
(D) ULSD with 150 ppm dosage concentration of the lubricity additive of Example: LI 18 having WSD of 406 µm;
(E) ULSD with 150 ppm dosage concentration of the lubricity additive of Example: LI 20 having WSD of 376 µm; and
(F) ULSD with 150 ppm dosage concentration of the lubricity additive of Example: LI 23 having WSD of 424 µm, in accordance with an embodiment of the present disclosure.
DETAILED DESCRIPTION
The present disclosure relates to a lubricity additive and a process for its preparation.
Embodiments, of the present disclosure, will now be described with reference to the accompanying drawing.
Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.
The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms "a,” "an," and "the" may be intended to include the plural forms as well, unless the context clearly suggests otherwise. The terms "comprises," "comprising," “including,” and “having,” are open-ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, modules, units and/or components, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the method and process of the present disclosure is not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed elements.
The terms first, second, third, etc., should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.
Conventional processes for manufacturing Ultra low Sulphur Diesel (ULSD) have several concerns, out of which the loss of lubricity in the resulting product is the major one. The poor lubricity of ULSD mandates the use of additives or blending with another fuel of sufficient lubricity, to restore the property of lubricity. The engine and fuel systems rely heavily on the lubricity of the fuel for a smooth operation. Conventionally, a neutral (ester type) lubricity additive and a mono-acid lubricity additive are used. However, these lubricity additives result in insufficient lubricity leading to the premature failure of the components in the fuel system.
The present disclosure provides a lubricity additive and a process for its preparation.
In one aspect, the present disclosure provides the lubricity additive. The lubricity additive is a reaction product of at least one organic acid in an amount in the range of 20 mass% to 40 mass%, at least one anhydride in an amount in the range of 10 mass% to 30 mass%, at least one alcohol in an amount in the range of 10 mass% to 20 mass%, a catalyst in an amount in the range of 0.05 mass% to 0.15 mass%, at least one fluid medium in an amount in the range of 10 mass% to 20 mass% and at least one amine in an amount in the range of 15 mass% to 35 mass%, wherein the mass% of each component is with respect to the total mass of the additive.
In accordance with an embodiment of the present disclosure, the organic acid can be at least one selected from the group consisting of octanoic acid, 2-ethylhexanoic acid, myristic acid, lauric acid, oleic acid and stearic acid. In an exemplary embodiment of the present disclosure, the organic acid is oleic acid and the amount of the organic acid is 28.92 mass% with respect to the total mass of the additive. In another exemplary embodiment of the present disclosure, the organic acid is 2-Ethyl hexanoic acid.
In accordance with an embodiment of the present disclosure, the anhydride can be at least one selected from the group consisting of furan-2,5-dione and succinic anhydride. In an exemplary embodiment of the present disclosure, the anhydride is furan-2,5-dione and the amount of the anhydride is 19.65 mass% with respect to the total mass of the additive.
In accordance with an embodiment of the present disclosure, the alcohol can be at least one selected from the group consisting of ethylene glycol, glycerol, trimethylolpropane, 1,3-propanediol and 1,4-butanediol. In an exemplary embodiment of the present disclosure, the alcohol is ethylene glycol. In another exemplary embodiment of the present disclosure, the alcohol is glycerol and the amount of the alcohol is 12.43 mass% with respect to the total mass of the additive.
In accordance with an embodiment of the present disclosure, the catalyst can be selected from the group consisting of p-toluene sulfonic acid (PTSA), sulfuric acid and phosphoric acid. In an exemplary embodiment of the present disclosure, the catalyst is p-toluene sulfonic acid and the amount of the catalyst is 0.09 mass% with respect to the total mass of the additive.
In accordance with an embodiment of the present disclosure, the fluid medium can be at least one selected from the group consisting of tetrahydrofuran (THF), cyclopentyl methyl ether (CPME) and 1,4-dioxne. In an exemplary embodiment of the present disclosure, the fluid medium is tetrahydrofuran and the amount of the fluid medium is 13.04 mass% with respect to the total mass of the additive.
In accordance with an embodiment of the present disclosure, the amine can be at least one selected from the group consisting of 2-ethyl hexylamine, diethanolamine, diethyl amine, ethanolamine, octylamine and hexylamine. In an exemplary embodiment of the present disclosure, the amine is 2-ethyl hexylamine and the amount of the amine is 25.87 mass% with respect to the total mass of the additive.
The lubricity additive of the present disclosure is used as ULSD lubricity improver. The lubricity additive of the present disclosure is cheaper as compared to the commercial lubricity additives.
In another aspect, the present disclosure relates to a process for the preparation of a lubricity additive.
The process for the preparation of the lubricity additive is described herein below.
Step (i): Predetermined amounts of at least one anhydride and a catalyst are mixed in a predetermined amount of at least one first fluid medium under stirring at a speed in the range of 300 rpm to 400 rpm to obtain a first mixture followed by adding a predetermined amount of at least one alcohol to obtain a second mixture.
In accordance with an embodiment of the present disclosure, the anhydride can be at least one selected from the group consisting of furan-2,5-dione, and succinic anhydride. In an exemplary embodiment of the present disclosure, the anhydride is furan-2,5-dione.
In accordance with an embodiment of the present disclosure, the predetermined amount of the anhydride is in the range of 10 mass% to 30 mass% with respect to the total mass of the additive. In an exemplary embodiment of the present disclosure, the predetermined amount of the anhydride is 19.65 mass%.
In accordance with an embodiment of the present disclosure, the catalyst is acid catalyst, wherein the acid catalyst can be selected from the group consisting of p-toluene sulfonic acid (PTSA), sulfuric acid and phosphoric acid. In an exemplary embodiment of the present disclosure, the catalyst is p-toluene sulfonic acid.
In accordance with an embodiment of the present disclosure, the predetermined amount of the catalyst is in the range of 0.05 mass% to 0.15 mass% with respect to the total mass of the additive. In an exemplary embodiment of the present disclosure, the predetermined amount of the catalyst is 0.09 mass%.
In accordance with an embodiment of the present disclosure, the first fluid medium can be at least one selected from the group consisting of tetrahydrofuran (THF), cyclopentyl methyl ether (CPME) and 1,4-dioxne. In an exemplary embodiment of the present disclosure, the fluid medium is tetrahydrofuran.
In accordance with an embodiment of the present disclosure, the predetermined amount of the first fluid medium is in the range of 10 mass% to 20 mass% with respect to the total mass of the additive. In an exemplary embodiment of the present disclosure, the predetermined amount of the first fluid medium is 13.04 mass%.
In accordance with an embodiment of the present disclosure, the alcohol can be at least one selected from the group consisting of ethylene glycol, glycerol, trimethylolpropane, 1,3-propanediol and 1,4-butanediol. In an exemplary embodiment of the present disclosure, the alcohol is ethylene glycol. In another exemplary embodiment of the present disclosure, the alcohol is glycerol.
In accordance with an embodiment of the present disclosure, the predetermined amount of the alcohol is in the range of 10 mass% to 20 mass% with respect to the total mass of the additive. In an exemplary embodiment of the present disclosure, the predetermined amount of the alcohol is 12.43 mass%.
Step (ii): The second mixture is refluxed at a first predetermined temperature for a first predetermined time period to obtain a homogeneous slurry.
In accordance with an embodiment of the present disclosure, the first predetermined temperature is in the range of 50 ºC to 80 ºC. In an exemplary embodiment of the present disclosure, the first predetermined temperature is 65 ºC.
In accordance with an embodiment of the present disclosure, the first predetermined time period is in the range of 30 minutes to 90 minutes. In an exemplary embodiment of the present disclosure, the first predetermined temperature is 60 minutes.
Step (iii): A predetermined amount of at least one amine is added followed by addition of a predetermined amount of at least one organic acid to the homogeneous slurry while refluxing and continued the refluxing for a second predetermined time period to obtain a product mixture.
In accordance with an embodiment of the present disclosure, the amine can be at least one selected from the group consisting of 2-ethyl hexylamine, diethanolamine, diethyl amine, ethanolamine, octylamine and hexylamine. In an exemplary embodiment of the present disclosure, the amine is 2-ethyl hexylamine.
In accordance with an embodiment of the present disclosure, the predetermined amount of the amine is in the range of 15 mass% to 35 mass% with respect to the total mass of the additive. In an exemplary embodiment of the present disclosure, the predetermined amount of the amine is 25.87 mass%.
In accordance with an embodiment of the present disclosure, the organic acid can be at least one selected from the group consisting of octanoic acid, 2-ethylhexanoic acid, myristic acid, lauric acid, oleic acid and stearic acid. In an exemplary embodiment of the present disclosure, the organic acid is oleic acid. In another exemplary embodiment of the present disclosure, the organic acid is 2-Ethyl hexanoic acid.
In accordance with an embodiment of the present disclosure, the predetermined amount of the organic acid is in the range of 20 mass% to 40 mass% with respect to the total mass of the additive. In an exemplary embodiment of the present disclosure, the predetermined amount of the organic acid is 28.92 mass%.
In accordance with an embodiment of the present disclosure, the second predetermined time period is in the range of 24 hours to 48 hours. In an exemplary embodiment of the present disclosure, the second predetermined temperature is 32 hours.
Step (iv): The product mixture is cooled at a second predetermined temperature for a third predetermined time period to obtain a cooled product mixture.
In accordance with an embodiment of the present disclosure, the second predetermined temperature is in the range of 20 ºC to 50 ºC. In an exemplary embodiment of the present disclosure, the second predetermined temperature is 30 ºC.
In accordance with an embodiment of the present disclosure, the third predetermined time period is in the range of 30 minutes to 60 minutes. In an exemplary embodiment of the present disclosure, the third predetermined temperature is 40 minutes.
Step (v): The cooled product mixture is purified to obtain the lubricity additive.
In accordance with an embodiment of the present disclosure, the purification of the cooled product mixture is described herein below.
A predetermined amount of a second fluid medium is added to the cooled product mixture followed by adding water to obtain a biphasic mixture comprising an organic layer and an aqueous layer.
In an embodiment of the present disclosure, water is demineralized water.
In accordance with an embodiment of the present disclosure, the second fluid medium can be selected from ethyl acetate, methyl acetate and diethyl ether. In an exemplary embodiment of the present disclosure, the second fluid medium is ethyl acetate.
The organic layer obtained is separated and treated with hydrochloric acid having a concentration in the range of 2% to 10% to obtain a treated organic layer.
In accordance with an embodiment of the present disclosure, the amount of hydrochloric acid is in the range of 15 % (100 ml) to 30 % (300 ml) with respect to the amount of organic layer. In an exemplary embodiment of the present disclosure, the amount of hydrochloric acid is 22.5 % (200 ml) with respect to the amount of organic layer and the concentration of hydrochloric acid is 5%.
Hydrochloric acid is used to remove acid impurities present in the organic layer.
The treated organic layer is washed with a sodium bicarbonate solution having a concentration in the range of 2% to 10% to obtain a washed organic layer.
In accordance with an embodiment of the present disclosure, the sodium bicarbonate solution is present in an amount in the range of 15 % (100 ml) to 30 % (300 ml) with respect to the amount of the treated organic layer. In an exemplary embodiment of the present disclosure, the amount of the sodium bicarbonate solution is 22.5 % (200 ml) with respect to the amount of the treated organic layer and the concentration of the sodium bicarbonate solution is 5%.
Sodium bicarbonate is used to remove the impurities present in the treated organic layer.
The second fluid medium from the washed organic layer is separated to obtain the lubricity additive.
In accordance with an embodiment of the present disclosure, the washed organic layer is filtered through sodium sulphate to remove the moisture, if any.
In accordance with an embodiment of the present disclosure, the second fluid medium present in the washed organic layer is evaporated by using rotary evaporator to yield the lubricity additive.
In an embodiment of the present disclosure, the final form of lubricity additive is a viscous liquid and free from any fluid media.
The purification step is carried out so that the unreacted anhydride, acid and the catalyst should be removed to get the pure form of the additive. These impurities are not soluble in ULSD.
The lubricity additive of the present disclosure is used as ULSD lubricity additive, which is cheaper in comparison with the commercially available lubricity additives.
Conventionally, the lubricity additives are prepared starting from maleic anhydride and oleic acid. Oleic acid is first treated with the maleic anhydride to get alkenyl succinic anhydride. It is the addition reaction of maleic anhydride to double bond of oleic acid. Later anhydride linkage is reacted with either alcohols or amines to yield the final compound. Maleic anhydride is reacted with only unsaturated fatty acids and it does not react with any other saturated organic acids such as 2-ethyl hexanoic acid, octanoic acid, stearic acid and the like.
However, in the process of the present disclosure, firstly maleic anhydride undergoes esterification reaction with diols or triols to get the condensation product as oilgomers. Later, free –OH, acid groups are reacted with acid/amines to get the final product. Thus, the process of preparing the lubricity additive in accordance with the present disclosure is totally different from the conventionally known process.
The process for preparation of the lubricity additive is economical, simple and easily scalable. Further, the raw materials used in the process for the preparation of lubricity additive, are easily available.
The foregoing description of the embodiments has been provided for purposes of illustration and not intended to limit the scope of the present disclosure. Individual components of a particular embodiment are generally not limited to that particular embodiment but are interchangeable. Such variations are not to be regarded as a departure from the present disclosure, and all such modifications are considered to be within the scope of the present disclosure.
The present disclosure is further described in light of the following experiments which are set forth for illustration purpose only and not to be construed for limiting the scope of the disclosure. The following experiments can be scaled up to industrial/commercial scale and the results obtained can be extrapolated to industrial scale.
EXPERIMENTAL DETAILS
Experiment 1: Process for the preparation of the lubricity additive in accordance with the present disclosure
Example 1 (LI 1): Preparation of a lubricity additive
196.5 g of furan-2,5-dione (anhydride), 0.9 g of PTSA (catalyst) were mixed in 147 ml (130.4 g) of THF (first fluid medium) under stirring at 350 rpm to obtain a first mixture followed by adding 124.3 g of ethylene glycol (alcohol) to obtain a second mixture. The so obtained second mixture was refluxed at 65 °C for 60 minutes to obtain a homogeneous slurry.
258.7 g of ethanolamine (amine) was added followed by addition of 289.2 g of 2-ethylhexanoic acid (organic acid) to the homogeneous slurry while refluxing and continued the refluxing for 32 hours to obtain a product mixture. The so obtained product mixture was cooled to room temperature to obtain a cooled product mixture. The cooled product mixture was further purified to obtain the lubricity additive.
The purification of the cooled product mixture was carried out by adding ethyl acetate (second fluid medium) followed by adding water to obtain a biphasic mixture comprising an organic layer and an aqueous layer. The organic layer was separated followed by treating the organic layer with 200 ml of 5% HCl to obtain a treated organic layer. The treated organic layer was washed with 200 ml of 5% sodium bicarbonate solution to obtain a washed organic layer. Ethyl acetate present in the washed organic layer was separated by using rotary evaporator to obtain the lubricity additive.
The so obtained lubricity additive was further used for the experiments.
Examples 2-23 (LI 2 to LI 23): Preparation of lubricity additives
The same procedure of Example 1 was repeated by varying the components and their amounts as summarized in Table 1 to obtain the lubricity additive.
Table 1: Components and amounts (molar ratio) of the components used in the preparation of a lubricity additive in accordance with the present disclosure
LI-Name Anhydride Organic acid Alcohol Amine Ratio Yield (%)
LI 1 Furan-2,5-dione Acid 1
2-Ethyl hexanoic acid Diol
Ethylene glycol Amine 1
2-Ethyl hexylamine 1:1:1:1 66
LI 2 Amine 2
Diethyl amine 1:1:1:1 65
LI 3 Amine 3
Diethanolamine 1:1:1:1 63
LI 4 Amine 4
Octylamine 1:1:1:1 64
LI 5 Furan-2,5-dione Acid 1
2-Ethyl hexanoic acid Diol
Ethylene glycol Amine 1
2-Ethyl hexylamine 1:1:1:1 66
LI 6 Acid 2
Oleic acid 1:1:1:1 65
LI 7 Acid 3
Stearic acid 1:1:1:1 65
LI 8 Furan-2,5-dione Acid 1
2-Ethyl hexanoic acid Triol
Glycerol Amine 1
2-Ethyl hexylamine 1:1:1:1 69
LI 9 Acid 2
Oleic acid 1:1:1:1 72
LI 10 Acid 3
Stearic acid 1:1:1:1 68
LI 11 Furan-2,5-dione Acid 1
2-Ethyl hexanoic acid Triol
Glycerol Amine 1
2-Ethyl hexylamine 1:1:2:1 65
LI 12 1:2:1:1 68
LI 13 1:2:2:1 69
LI 14 0.5:1:0.5:1 58
LI 15 0.5:2:0.5:1 60
LI 16 2:1:1:1 64
LI 17 1:1:1:2 66
LI 18 Furan-2,5-dione Acid 2
Oleic acid Triol
Glycerol Amine 1
2-Ethyl hexylamine 1:1:2:1 67
LI 19 1:2:1:1 73
LI 20 1:2:2:1 72
LI 21 1:0.5:1:1 67
LI 22 1:0.4:1:1 62
LI 23 1:0.25:1:1 55
From Table 1 it is observed that the product yield of LI 9, LI 19 and LI 20 are good as compared to others (Anhydride 1, Acid 2, Triol 1 and Amine 1 in the ratio of LI 9-1:1:1:1, LI 19-1:2:1:1 and LI 20-1:2:2:1 respectively).
Comparative examples:
Commercially available lubricity additive-1 and additive-2: mixture of higher fatty acids and their simple esters derived from the non-edible oils (such as oleic acid, linoleic acid, methyl oleate, methyl lenoleate and the like).
Experiment 2: Effect of the lubricity additive prepared in Examples 1-23 and comparative examples 1 and 2
The lubricity additives as prepared in Examples 1 to 23 and comparative examples 1 and 2 were tested for lubrication performance of ULSD by using high frequency reciprocating rig (HFRR). HFRR was used for the measurement on the basis of ASTM D 6079-18 standard method (i.e. a vibrator with 50 Hz frequency, 1 mm 1mm stroke length, 200g weight load, 2 mL sample, 60° C temperature and duration of test is 75 minutes). The length (as µm) of the scar in X and Y direction of the wear scar formed on the ball’s surface was measured and the wear scar diameter (WSD) was calculated using the equation WSD = (X+Y)/2 µm. The neat ULSD (having 6 ppm (wt/vol) sulfur) was used as a control. The prepared lubricity additives were added in two different concentrations to ULSD and the WSD value was determined. The size of the wear scar is directly related to the lubrication property of the sample.
The maximum allowed limit for the lubricity value of BS VI ULSD is 460 µm. Therefore, the WSD of LI added ULSD less than or equal to 450 µm at 60° C is considered as acceptable.
The lubricity analysis data of the neat ULSD (control) and the LI (1-23) added ULSD at two different concentrations are tabulated in Table 2.
Table 2: Lubrication performance of the lubricity additives of Examples 1 to 23 and comparative examples 1 and 2
HFRR 60°C, ASTM D 6079-18
Example No. Concn.
ppm Wear scar (µm) Concn.
ppm Wear scar (µm)
Ball, X Ball, Y WSD,
(X+Y)/2 Ball X Ball Y WSD,
(X+Y)/2
Neat, ULSD (Control) NA 539 513 526 NA NA NA NA
Commercial Additive 1 100 452 502 477 150 374 430 402
Commercial Additive 2 100 447 489 468 150 354 428 391
LI 1 100 488 416 452 150 440 380 410
LI 2 100 478 454 466 150 432 414 423
LI 3 100 481 439 460 150 445 405 425
LI 4 100 494 450 472 150 458 418 438
LI 5 100 468 442 455 150 425 395 410
LI 6 100 455 429 442 150 411 399 405
LI 7 100 492 458 475 150 439 405 422
LI 8 100 474 430 452 150 421 389 405
LI 9 100 453 417 435 150 402 368 385
LI 10 100 465 431 448 150 436 364 400
LI 11 100 493 459 476 150 456 414 435
LI 12 100 484 432 458 150 434 386 410
LI 13 100 472 428 450 150 422 388 405
LI 14 100 464 420 442 150 416 380 398
LI 15 100 464 414 439 150 410 366 388
LI 16 100 456 424 440 150 419 375 397
LI 17 100 471 429 451 150 431 349 390
LI 18 100 476 442 459 150 425 387 406
LI 19 100 463 415 439 150 404 366 385
LI 20 100 447 423 435 150 395 357 376
LI 21 100 467 429 448 150 414 374 394
LI 22 100 473 431 452 150 422 386 404
LI 23 100 475 449 462 150 445 403 424
The results of Table 2 clearly indicated that the lubricity additives prepared in examples 1 to 23 showed good lubrication performance in ULSD as compared to the control. It is observed from Table 2 that amongst 4 amines, amine-1 is selected as one of the reactant as LI 1 is showing better lubricity value than LI 2, LI 3 and LI 4. LIs derived from Acid 1 and 2 (LI 5 and LI 6) showing better lubricity than Acid 3 (LI 7). LIs derived from Triol-1 gave comparatively good yield than Diol-1. Further, amongst Acid 1 and 2, Acid-2 is gave better yields (LI 8 and 9). LI 9, LI 19 and LI 20 are synthesized in good yield and also they showed good lubricity property both in 100 ppm and 150 ppm dosage levels. LIs prepared from anhydride 1, acid 2, triol 1 and amine 1, in the ratio of 1:1:1:1, 1:2:1:1 and 1:2:2:1 are promising synthetic lubricity improvers for the large scale preparation.
At 100 ppm dosage, all the additives i.e. LI 1 to LI 23 showed better WSD than commercial additive 1. Except LI 4, LI 7, and LI 11, all other additives showed better WSD values than commercial additive 2.
At 150 ppm dosage, LI 9, LI 14 – 17 and LI 19– 21 showed better WSD values than commercial additive 1. LI 9, LI 15, LI 17 and LI 20 showed better WSD values than commercial additive 2.
TECHNICAL ADVANCEMENTS
The present disclosure described hereinabove has several technical advantages including, but not limited to, the realization of:
? a lubricity additive that is:
• used for improving the lubricity of ULSD; and
• cheaper as compared to the commercially known additives,
? and a process for preparing a lubricity additive that is:
• simple;
• economic due to the use of easily available raw materials; and
• easily scalable.
Throughout this specification the word “comprise”, or variations such as “comprises” or “comprising, will be understood to imply the inclusion of a stated element, integer or step,” or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the invention to achieve one or more of the desired objects or results. While certain embodiments of the inventions have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Variations or modifications to the formulation of this invention, within the scope of the invention, may occur to those skilled in the art upon reviewing the disclosure herein. Such variations or modifications are well within the spirit of this invention.
The numerical values given for various physical parameters, dimensions and quantities are only approximate values and it is envisaged that the values higher than the numerical value assigned to the physical parameters, dimensions and quantities fall within the scope of the invention unless there is a statement in the specification to the contrary.
While considerable emphasis has been placed herein on the specific features of the preferred embodiment, it will be appreciated that many additional features can be added and that many changes can be made in the preferred embodiment without departing from the principles of the disclosure. These and other changes in the preferred embodiment of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.
,CLAIMS:WE CLAIM:
1. A lubricity additive, being a reaction product of
a. at least one organic acid in an amount in the range of 20 mass% to 40 mass%;
b. at least one anhydride in an amount in the range of 10 mass% to 30 mass%;
c. at least one alcohol in an amount in the range of 10 mass% to 20 mass%;
d. a catalyst in an amount in the range of 0.05 mass% to 0.15 mass%;
e. at least one fluid medium in an amount in the range of 10 mass% to 20 mass%; and
f. at least one amine in an amount in the range of 15 mass% to 35 mass%,
wherein the mass% of each component is with respect to the total mass of said additive.
2. The additive as claimed in claim 1, wherein said organic acid is at least one selected from the group consisting of octanoic acid, 2-ethylhexanoic acid, myristic acid, lauric acid, oleic acid and stearic acid.
3. The additive as claimed in claim 1, wherein said anhydride is at least one selected from the group consisting of furan-2,5-dione and succinic anhydride.
4. The additive as claimed in claim 1, wherein said alcohol is at least one selected from the group consisting of ethylene glycol, glycerol, trimethylolpropane, 1,3-propanediol and 1,4-butanediol.
5. The additive as claimed in claim 1, wherein said catalyst is selected from the group consisting of p-toluene sulfonic acid (PTSA), sulfuric acid and phosphoric acid.
6. The additive as claimed in claim 1, wherein said fluid medium is at least one selected from the group consisting of tetrahydrofuran, cyclopentyl methyl ether (CPME) and 1,4-dioxne.
7. The additive as claimed in claim 1, wherein said amine is at least one selected from the group consisting of 2-ethyl hexylamine, diethanolamine, diethyl amine, ethanolamine, octylamine and hexylamine.
8. A process for the preparation of a lubricity additive, said process comprising the following steps:
(i) mixing predetermined amounts of at least one anhydride and a catalyst in a predetermined amount of at least one first fluid medium under stirring at a speed in the range of 300 rpm to 400 rpm to obtain a first mixture followed by adding a predetermined amount of at least one alcohol to obtain a second mixture;
(ii) refluxing said second mixture at a first predetermined temperature for a first predetermined time period to obtain a homogeneous slurry;
(iii) adding predetermined amount of at least one amine followed by addition of a predetermined amount of at least one organic acid to said homogeneous slurry while refluxing and continuing said refluxing for a second predetermined time period to obtain a product mixture;
(iv) cooling said product mixture at a second predetermined temperature for a third predetermined time period to obtain a cooled product mixture; and
(v) purifying said cooled product mixture to obtain said lubricity additive.
9. The process as claimed in claim 8, wherein said cooled product mixture is purified by the following sub-steps:
a. adding a predetermined amount of a second fluid medium to said cooled product mixture followed by adding water to obtain a biphasic mixture comprising an organic layer and an aqueous layer;
b. separating said organic layer followed by treating said organic layer with hydrochloric acid having a concentration in the range of 2% to 10% to obtain a treated organic layer;
c. washing said treated organic layer with a sodium bicarbonate solution having a concentration in the range of 2% to 10% to obtain a washed organic layer;
d. separating said second fluid medium from said washed organic layer to obtain said lubricity additive.
10. The process as claimed in claim 8, wherein said organic acid is at least one selected from the group consisting of octanoic acid, 2-ethylhexanoic acid, myristic acid, lauric acid, oleic acid and stearic acid; and wherein said predetermined amount of said organic acid is in the range of 20 mass% to 40 mass% with respect to the total mass of said additive.
11. The process as claimed in claim 8, wherein said anhydride is at least one selected from the group consisting of furan-2,5-dione and succinic anhydride; and wherein said predetermined amount of said anhydride is in the range of 10 mass% to 30 mass% with respect to the total mass of said additive.
12. The process as claimed in claim 8, wherein said alcohol is at least one selected from the group consisting of ethylene glycol, glycerol, trimethylolpropane1, 3-propanediol and 1,4-butanediol; and wherein said predetermined amount of said alcohol is in the range of 10 mass% to 20 mass% with respect to the total mass of said additive.
13. The process as claimed in claim 8, wherein said first fluid medium is at least one selected from the group consisting of tetrahydrofuran, cyclopentyl methyl ether (CPME) and 1,4-dioxne; and wherein said predetermined amount of said first fluid medium is in the range of 10 mass% to 20 mass% with respect to the total mass of said additive.
14. The process as claimed in claim 8, wherein said amine is at least one selected from the group consisting of 2-ethyl hexylamine, diethanolamine, diethyl amine, ethanolamine and hexylamine; and wherein said predetermined amount of said amine is in the range of 15 mass% to 35 mass% with respect to the total mass of said additive.
15. The process as claimed in claim 8, wherein said catalyst is selected from the group consisting of p-toluene sulfonic acid (PTSA), sulfuric acid and phosphoric acid; and wherein said predetermined amount of said catalyst is in the range of 0.05 mass% to 0.15 mass% with respect to the total mass of said additive.
16. The process as claimed in claim 8, wherein
• said first predetermined temperature is in the range of 50 ºC to 80 ºC; and
• said second predetermined temperature is in the range of 20 °C to 50 ºC.
17. The process as claimed in claim 8, wherein
• said first predetermined time period is in the range of 30 minutes to 90 minutes;
• said second predetermined time period is in the range of 24 hours to 48 hours; and
• said third predetermined time period is in the range of 30 minutes to 60 minutes.
18. The process as claimed in claim 9, wherein said second fluid medium is selected from the group consisting of ethyl acetate, methyl acetate and diethyl ether.

Dated this 14th day of December, 2022

_______________________________
MOHAN RAJKUMAR DEWAN, IN/PA – 25
of R.K.DEWAN & CO.
Authorized Agent of Applicant

TO,
THE CONTROLLER OF PATENTS
THE PATENT OFFICE, AT CHENNAI