WO2017093913A1

WO2017093913A1 - Process for enhancing gasoline octane boosters, gasoline boosters, and gasolines

Info

Publication number: WO2017093913A1
Application number: PCT/IB2016/057225
Authority: WO
Inventors: Vinodkumar Vasudevan; Guillermo LEAL; Somak PAUL
Original assignee: Sabic Global Technologies B.V.
Priority date: 2015-11-30
Filing date: 2016-11-30
Publication date: 2017-06-08
Also published as: US20180320098A1; EP3383977A1; CN108291160A

Abstract

A gasoline additive composition includes an oxygenate gasoline additive; and an optical brightener. The gasoline additive composition can be used in a gasoline blend.

Description

PROCESS FOR ENHANCING GASOLINE OCTANE BOOSTERS, GASOLINE BOOSTERS, AND GASOLINES

BACKGROUND

[0001] This disclosure is directed to a process for improving octane boosters for gasoline, the improved boosters, and gasolines containing the boosters.

[0002] Commercial gasoline, which is fuel for internal combustion engines, is a refined petroleum product that is typically a mixture of hydrocarbons (base gasoline), additives, and blending agents. Additives and blending agents are added to the base gasoline to enhance the perfonnance and the stability of gasoline, and can include anti-knock agents, anti-oxidants, metal deactivators, lead scavengers, anti-rust agents, anti-icing agents, upper- cylinder lubricants, detergents, and dyes.

[0003] When used in high compression internal combustion engines, gasoline has the tendency to "knock." Knocking occurs when combustion of the air/fuel mixture in the cylinder does not start off correctly in response to ignition because one or more pockets of air/fuel mixture pre-ignite outside the envelope of the normal combustion front. Anti- knocking agents, also known as octane boosters, reduce the engine knocking phenomenon, and increase the octane rating of the gasoline. Prior octane boosters such as tetraethyl lead and methylcyclopentadienyl manganese tricarbonyl (MMT) have been or are being phased out for environmental, health, or other reasons.

[0004] Preferred compounds in present use for formulating octane boosters include G* oxygenate compounds such as methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and n-butanol and its isomers. However, the production and storage of the large quantities of these materials at oil refineries can be costly. In addition, limitations on the use of high concentrations of additives by regulatory mandate increase the difficulty and expense of refining operations that produce high-octane fuels.

[0005] In view of the foregoing, there remains a need to provide cost-effective methods for producing octane-boosting compositions, including processes for modifying or improving the properties of existing octane boosters and compositions that are made by the processes. BRIEF DESCRIPTION

[0006] Described herein is an octane boosting, gasoline additive composition comprising an oxygenate and an optical brightener.

[0007] A method for the manufacture of the octane boosting, gasoline additive composition comprises combining the oxygenate and the optical brightener.

[0008] Also described herein is a gasoline blend comprising a base gasoline and the octane boosting, gasoline additive composition described above.

[0009] The above described and other features are exemplified by the following figures and detailed description.

DETAILED DESCRIPTION

[0010] Described herein is a process and composition for improving the quality and octane boosting properties of octane boosting compositions. It has been found by the inventors that the quality of any oxygenate can be significantly improved by treatment with an optical brightener. Oxygenates treated with an optical brightener can have improved physical and chemical properties such as color, odor, volatility, density, and chemical composition. The octane boosting compositions can then be blended with gasoline.

[0011] The terms "fuel oxygenates," "gasoline oxygenates" and simply "oxygenates" refer to a class of gasoline additives that contain one or more oxygen atoms and are designed to improve the octane rating of gasoline increasing the oxygen content of the gasoline. Most oxygenates are either alcohols or ethers, for example methanol (MeOH), ethanol (EtOH), isopropyl alcohol (IPA), n-propyl alcohol (NPrOH), isobutanol (IBA), n-butanol (BuOH), sec-butyl alcohol (SB A), tert-butyl alcohol (TB A) or gasoline grade tert-butyl alcohol (GTBA), tert-amyl alcohol (TAA) or tert-pentanol, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), tert-amyl ethyl ether (TAEE), tert- hexyl methyl ether (THEME), and diisopropyl ether (D1PE). These oxygenates can be produced by any known and acceptable chemical and biological reactions that are known in the ait, for example, chemical reaction between isobutylene and methanol or ethanol to produce MTBE or ETBE respectively, microbial fermentation of sugars to produce bio- ethanol, and the like. Production processes can further include purification, distillation, or dehydration steps to increase purity and to remove water. In an embodiment, as further described below, the oxygenate, in particular MTBE or ETBE, is produced without a distillation step to purify the MTBE or ETBE. [0012] Optical brighteners are known in the art, being previously used in various polymers, paper, textiles, textile treatment compositions, detergents, rinses, and the like. An optical brightener may be defined as a chemical that absorbs light and then emits light in a visible region. Optical brighteners can be nonionic or anionic. A large number of brighteners are known and can be used. Examples of such brighteners are described in U.S. Patent Nos. 3201481, 3646015, 4400294, 4483780, 4790856, 6120714, and 8740997.

[0013] Types of optical brighteners that can be used include, without limitation, azole derivatives, benzoxazole derivatives such as bis-benzoxazolylstyrenes, biphenyl derivatives, certain carboxylic acid derivatives, coumarin derivatives, dibenzotbiophene-5,5-dioxide derivatives, diphenyl styryl derivatives, methinecyanine derivatives, oxazole derivatives, phenyloxazole derivatives, pyrazoline derivatives, and stilbene derivatives. Examples of these types of brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, published by John Wiley & Sons, New York (1982) and in the Kirk-Othmer Encyclopedia of Chemical Technology, Volume 3, (1962) under the heading "Brighteners, Optical". Combinations of two or more different optical brighteners can be used.

[0014] Azoles, which are derivatives of 5-membered ring heterocycles, can be further subcategorized into monoazoles and bisazoles.

[0015] Specific examples of biphenyl derivatives include 4,4'-bis-(styryl)-bisphenyls such as l,l'-biphenyl-4,4'-bis{2-(methoxyphenyl)ethenyl} (CAS #40470-68-6), 1,1'- biphenyl-4,4'-bis[2-(methoxyphenyl)ethenyl], benzene-4,4'-bis(2-(cyano-phenyl)ethenyl), and l,l'-biphenyl-4,4'-bis[2-(sodium sulfonate phenyl)ethenyl].

[0016] Carboxylic acid derivatives that can be used include fumaric acid derivatives; benzoic acid derivatives; p-phenylene-bis-acrylic acid derivatives; naphthalenedicarboxylic acid derivatives; heterocyclic acid derivatives; and cinnamic acid derivatives. Cinnamic acid derivatives that can be used can be further subclassif ied into groups which include styryltriazoles and styrylpolyphenyls,. Styrylazoles can be further subclassified into styrylbenzoxazoles, styiylimidazoles, and styrylthiazoles. It will be understood that these three identified subclasses may not necessarily reflect an exhaustive list of the subgroups into which styrylazoles may be subclassified. Cinnamic acid derivatives also include 2-styryl- benzimidazole derivatives, styrylbenzofuran derivatives, styryloxadiazole derivatives, and styrylpolyphenyl derivatives. [0017] Coumarin derivatives that can be used include derivatives substituted in the 3- position, in the 7-position such as 4-methyl-7-diethyl-amino coumarin, and in both the 3- and 7-positions.

[0018] Derivatives of dibenzothiophene-5,5-dioxide include 3,7- diaminodibenzotbiophene-2,8-disulfonic acid 5,5 dioxide.

[0019] Examples of diphenyl styryl derivatives include alkali metal salts of 4,4'-bis- (2-sulfostyryl)-diphenyl, 4,4'-bis-(4-chloro-2-sulfostyryl)-diphenyl or 4-(4-chlorostyryl)-4'- (2-sulfostyryl)-diphenyl,

[0020] Examples of metmnecyanine derivatives that can be used include

oxamethinecyanines and thiamethinecyanines.

[0021] Specific examples of oxazole derivatives include 2,2'-(l,2-ethenediyl-di-4,l- phenylene) bisbenzoazole (CAS # 1533-45-5), 2,2'-(2,5-miophenydiyl)-bis[5-(1,1'-dimethyl) benzoxazole (CAS # 7128-64-5), 2,5-bis-(benzoxazole-2-) thiophene (CAS # 2866-43-5), and

2.2- (l,4-naphthalenediyl)bis-benzoxazole.

[0022] Stilbene derivatives that can be used include derivatives of

bis(triazmyl)amino-stilbene; bisacylamino derivatives of stilbene; triazole derivatives of stilbene such as 4,4'-bis(l,2,3-triazol-2-yl)-stilbenes and 2-(stilbene-4-yl)2H-naphth-[l,2- d]triazole; oxadiazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene. Other examples include diaminostilbene disulfonic acid and alkali metal salts thereof, for example, derivatives of 4,4'-cUamino-2,2'-stilbene disulfonic acid (flavonic acid), such the salts of 4,4'-bis-(2-anilmo-4-moφholmo-l,3,5-triazmyl-6-amino)- stillbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, contain a diethanolamino group, a methylamino group, an anilino group, or a 2-methoxyethylamino group.

[0023] An additional class of brighteners that can be used are the derivatives of 6- membered-ring hetero-cycles, for example brighteners derived from pyrazine and brighteners derived from 4-aminonaphthalamide. Miscellaneous agents that can also be useful as brighteners include l-hydroxy-3,6,8-pyrenemsulfonic acid; 2,4-dimethoxy-l,3,5-triazin-6-yl- pyrene; 4,5-di-phenylimidazolonedisulfonic acid; derivatives of pyrazoline-quinoline; the 2- (4-styryl-phenyl)-2H-naphthol-[l,2-d]triazoles; methyl umbelliferone; dihydroquinolinone,

1.3- diaryl pyrazoline; 1,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenylphrazolines; 2,5- bis(benzoxazol-2-yl)tbiophene; and 2-styryl-naphth-[l,2-d]oxazole. [0024] In an embodiment, the optical brightener comprises a compound of the formula

wherein R^a and R^b are each independently a C_1-60 hydrocarbyl group optionally containing 1 to 20 heteroatoms, a halide, a nitro group, a C_1-5 alkyl giOup, or a sulfonic acid group, and preferably wherein R^a and R^b are each independently a halide, a nitro group, a C_1-5 alkyl group, or a sulfonic acid group.

[0025] In an embodiment, the optical brightener comprises a compound of the formula

wherein R¹, R², R³, and R⁴ are each independently a halide, a nitro group, a C_1-5 alkyl group, a C_1-5 alkoxy group, a sulfonic acid group, a phosphoric acid group, or a phosphonic acid group.

[0026] In an embodiment, the optical brightener comprises a compound of the formula

wherein R₁ is carbonyl or sulfonyl; R3 is hydroxyl,— 0^"M⁺ wherein M⁺ is a positively charged counterion, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C_1-10 alkyl) ammonium group, tri(C₁- ₁₀)alkoxysilyl group, or carboxy (C_1-10 alkyl), or ether; R4 and R5 are each independently hydrogen, hydroxy, amino, (C_1-10alkoxy)amino, (C_1-10alkyOamino, (C_6-12 aryl)amino, hydroxy(C_1-10 alkyl)amino, morpholino, aniline, (C_1-10 alkyl)anilino, (C_1-10alkylene)sulfonic acid, piperazinyl, piperidinyl, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C_1-10 alkyl) ammonium group, tri(C_1-10)alkoxysilyl group, carboxy (C_1-10 alkyl), or ether.

[0027] In an embodiment, the optical brightener comprises a compound of the formula

wherein R₁ is carbonyl or sulfonyl; R3 is hydroxyl,— 0^~M⁺ wherein M⁺ is a positively charged counterion, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C_1-10 alkyl)ammonium group, tri(C₁- !o)alkoxysilyl group, carboxy(C_1-10 alkyl), or ether, and R4 and R5 are each independently hydrogen, hydroxy, amino, (C_1-10alkoxy)amino, (C_1-10alkytyamino, (C_6-12 aryl)amino, hydroxyiC_1-10 alkyl)amino, morpholino, aniline, (C_1-10alkyl)anilino, (C_1-10alkylene)sulfonie acid, piperazinyl, piperidinyl, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C_1-10 alkyl) ammonium group, tti(C₁-!o)alkoxysilyl group, carboxy (C_1-10 alkyl), ether; and R₅₀is— R₁— R3 or— OR₁₀ wherein R₁₀ is a C_1-200 hydrocarbyl substituent comprising at least one of an ether, a carbonyl, a secondary amine, or a quaternized amine.

[0028] In an embodiment, the optical brightener comprises a compound of the formula

wherein R^a and R^b are each independently a C_1-60 hydrocarbyl group optionally containing up 1 to 20 heteroatoms, a halide, a nitro group, a C_1-5 alkyl group, or a sulfonic acid group, and M is H, an alkali metal, ammonium, or magnesium; preferably wherein R^a and R^b are each independently a halide, a nitro group, a C_1-5 alkyl group, a C1-5 alkoxy group, or a sulfonic acid group.

[0029] In an embodiment, the optical brightener comprises a compound of the formula

wherein each R^c is independently H or ( C_1-6)alkyl; A=N or C; and X is a bond via 1,4- naphthyl, 2,5-thiophene, 2,5-furan, 1,4-phenyl, ethylene, stilbene, styrene or imidazolyl units.

[0030] In an embodiment, the optical brightener comprises a compound of the formula

wherein X is manganese, cobalt, iron, zinc, or lead.

[0031] In some embodiments the octane boosting, gasoline additive composition comprises 0.01 to 5.0 wt. % of the optical brightener and 95 to 99.99 wt. % of a gasoline oxygenate comprising methanol (MeOH), ethanol (EtOH), isopropyl alcohol (IPA), n-propyl alcohol (NPrOH), isobutanol (IBA), n-butanol (BuOH), sec-butyl alcohol (SBA), tert-butyl alcohol (TBA) or gasoline grade tert butyl alcohol (GTBA), tert-amyl alcohol (TAA) or tert pentanol, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), tert-amyl ethyl ether (TAEE), tert-hexyl methyl ether (THEME) and diisopropyl ether (DIPE), or a combination of two or more of the foregoing. Within this range the optical brightener can be present in an amount of 0.1 to 2.5 wt%, or 0.01 to 3 wt%, or 1 to 5 wt%, and the oxygenate can be present in an amount of 97.5 to 99.9 wt%, or 95 to 99.9 wt.%, based on the total weight of the optical brightener and the oxygenate.

[0032] Other gasoline additive compounds can be present in the compositions in amounts known in the art.

[0033] A process for preparing an octane boosting, gasoline additive composition comprises combining an optical brightener with the oxygenate. In some embodiments, addition of an optical brightener can improve the quality of the oxygenate sufficiently so that distillation to purify the oxygenate can be eliminated, resulting in a time and cost saving.

[0034] Addition of an optical brightener can provide a gasoline additive composition having improved color. Saybolt color scale is used for grading light colored petroleum products including aviation fuels, kerosene, naphthas, white mineral oils, hydrocarbon solvents, and the like. ASTM D156 describes a standard test method for Saybolt color of petroleum products. A Saybolt number of +30 indicates that the product has no color or is completely clear, while the strongest evaluable Saybolt coloration value (the darkest) is -16. The untreated composition comprising the oxygenate can have a dark to light brown color with a Saybolt value of +4 to +10. Addition of an optical brightener can provide the oxygenate with a Saybolt number of +12, +15, +20, or +25. In some embodiments, untreated composition comprising the oxygenate can have an improvement in Saybolt number of at least 1 unit, for example 1 to 40 units, at least 5 units, for example 5 to 35 units, or 5 to 30 units, or 5 to 20 units compared to the original Saybolt number of the untreated composition comprising the oxygenate.

[0035] The chemical composition of the untreated composition comprising the oxygenate can be altered, leading to an overall increase of the oxygen content of the additive composition and improvement in other physical properties. In an embodiment, addition of an optical brightener can result in an increase in at least one of blending octane value (i.e., RON or MON), lightening of liquid color (e.g., to less brown or yellow to nearly colorless), decrease in odor, or decrease in density.

[0036] Blending octane value (BOV) can be used to characterize the octane value of octane boosting gasoline additives oxygenates. The BOV is calculated from the difference between the octane value of a base gasoline with a known amount of the gasoline additive (i.e., the gasoline blend) and the base gasoline without the gasoline additive. The formula for BOV calculation is given below:

RON (research octane number) can be determined according to DIN EN ISO 5164 (ASTM D

2699) and describes the knocking behavior at a low engine load and low rotational speeds. MON (motor octane number) can be determined according to DIN EN ISO 5163 (ASTM D

2700) and describes the behavior at a high engine load and under high thermal stress.

[0037] In some embodiments, the untreated composition comprising the oxygenate can have an improvement in blending research octane value (BOV based on RON). In some embodiments the improvement in blending research octane value can be 0.5 to 10%, or 1 to 8%, over the original value. In some embodiments, improvement in blending motor octane value (BOV based on MON) can be 0.5 to 10%, or 1 to 8%, over the original value of before addition of optical brightener.

[0038] The gasoline octane boosting composition can have a blending research octane value of 89 to 122 and a blending motor octane value of 82 to 95.

[0039] The gasoline octane boosting composition is blended with a gasoline to provide a gasoline blend. The gasoline blend can comprise 80 to 90 vol. % of a base gasoline and 15 to 20 vol. % of the gasoline octane boosting composition. Within these ranges the gasoline blend can comprise 10 to 20 vol. %, or 15 to 20 vol. %, or 10 to 15 vol. %, of the gasoline octane boosting composition with the balance of the gasoline blend being the base gasoline.

[0040] The gasoline blend can have a RON of 1 to 10 or more units higher than the base gasoline. Within this range the RON is 1 to 2 units higher, or 1 to 3 units higher. The gasoline blend can have an MON of 1 to 10 units higher than the base gasoline. Within this range the MON is 1 to 2 units higher, or 1 to 3 units higher.

[0041] In the United States, under the federal volatility control program, commercial gasoline, especially summer-grade gasoline, has a Reid vapor pressure (RVP) below 9.0 psi at about 7.8 psi. The gasoline blend can have an RVP within 0.2 psi of the RVP of the base gasoline.

[0042] The methods and compositions are further set forth in the Embodiments below, which are not intended to limit the claims.

[0043] Embodiment 1 : An octane boosting, gasoline additive composition, comprising: an oxygenate gasoline additive; and an optical brightener.

[0044] Embodiment 2: The gasoline additive composition of Embodiment 1, wherein the oxygenate comprises methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutanol, n-butanol, sec-butyl alcohol, tert-butyl alcohol, gasoline grade ten butyl alcohol, tert-amyl alcohol, methyl tert-butyl ether, ethyl tert-butyl ether, tert-amyl methyl ether, tert-amyl ethyl ether, tert-hexyl methyl ether, diisopropyl ether, or a combination comprising at least one of the foregoing, preferably wherein the oxygenate comprises methyl tert-butyl ether.

[0045] Embodiment 3: The gasoline additive composition of any one or more of the preceding Embodiments, comprising 99.5 to 99.9 wt.%, or 97.5 to 99.9 wt.%, or 99.9 to 95 wt.% of the oxygenate, and 0.01 to 3 wt.%, or 0.1 to 2.5 wt %, or 1 to 5 wt %, of the optical brightener, each based on the combined amount of oxygenate and optical brightener.

[0046] Embodiment 4: The gasoline additive composition of any one or more of the preceding Embodiments, wherein the optical brightener is an azole derivative, benzoxazole derivative, biphenyl derivative, cinnamic acid derivative, fumaric acid derivative, coumarin derivative, dibenzotbiophene-5,5-dioxide derivative, diphenyl styryl derivative,

methinecyanine derivative, oxazole derivative, phenyloxazole derivative, pyrazoline derivative, stilbene derivative, or a combination comprising at least one of the foregoing; preferably wherein the optical brightener is a cinnamic acid derivative, a diphenyl derivative, or a stilbene derivative.

[0047] Embodiment 5: The gasoline additive composition of any one or more of the preceding Embodiments, wherein the optical brightener comprises a compound of the formula

wherein R^a and R^b are each independently a C_1-60 hydrocarbyl group optionally containing up 1 to 20 heteroatoms, a halide, a nitro group, a C_1-5 alkyl group, or a sulfonic acid group, and preferably wherein R^a and R^b are each independently a halide, a nitro group, a C_1-5 alkyl group, or a sulfonic acid group.

[0048] Embodiment 6: The gasoline additive composition of any one or more of Embodiments 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein R¹, R², R³, and R⁴ are each independently a halide, a nitro group, a C_1-5 alkyl group, a C₁-5 alkoxy group, a sulfonic acid group, a phosphoric acid group, or a phosphonic acid group.

[0049] Embodiment 7: The composition of any one or more of Embodiments 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein R₁ is carbonyl or sulfonyl; R₃ is hydroxyl,— 0^~M⁺ wherein M⁺ is a positively charged counterion, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C_1-10 alkyl)ammonium group, tri(C₁- io)alkoxysilyl group, or carboxy (C_1-10 alkyl), or ether; and R₄ and R₅ are each independently hydrogen, hydroxy, amino, (C_1-ioalkoxy)amino, (C_1-10alkytyamino, (C_6-12 aryl)amino, hydroxy(C_1-10 alkyl)amino, morpholino, aniline, (C_1-10 alkyl)anilino, (C_1-10alkylene)sulfonic acid, piperazinyl, piperidinyl, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C_1-10 alkyl) ammonium group, tri(C_1-10)alkoxysilyl group, carboxy (C_1-10 alkyl), or ether.

[0050] Embodiment 8: The composition of any one or more of Embodiments 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein R₁ is carbonyl or sulfonyl; R₃ is hydroxyl,— 0-M⁺ wherein M⁺ is a positively charged counterion, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C_1-10 alkyl)ammonium group, tri(C₁- io)alkoxysilyl group, carboxy (C_1-10 alkyl), or ether, R₄ and R₅ are each independently hydrogen, hydroxy, amino, (C_1-ioalkoxy)amino, (C_1-10alkytyamino, (Ce-12 aryl)amino, hydroxy(C_1-10 alkyl)amino, morpholino, aniline, (C_1-10 alkyl)anilino, (C_1-10alkylene)sulfonic acid, piperazinyl, piperidinyl, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C_1-10 alkyl)ammonium group, tri(C_1-10)alkoxysilyl group, carboxy (C_1-10 alkyl), ether, R₅₀is— R₁— R₃ or— OR10 wherein R₁₀ is a C_1-200 hydrocarbyl substituent comprising at least one of an ether, a carbonyl, a secondary amine, or a quaternized amine.

[0051] Embodiment 9: The gasoline additive composition of any one or more of Embodiments 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein R^a and R^b are each independently a C_1-60 hydrocarbyl group optionally containing up 1 to 20 heteroatoms, a halide. a nitro group, a C_1-5 alkyl group, or a sulfonic acid group, and M is H, an alkali metal, ammonium, or magnesium; preferably wherein R^a and R^b are each independently a halide, a nitro group, a C_1-5 alkyl group, a C_1-5 alkoxy group, or a sulfonic acid group.

[0052] Embodiment 10: The composition of any one or more of Embodiments 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein each R^c is independently H or (C_1-6)alkyl; A=N or C; and X is a bond via 1 ,4- naphthyl, 2,5-thiophene, 2,5-furan, 1,4-phenyl, ethylene, stilbene, styrene or imidazolyl units.

[0053] Embodiment 11 : The gasoline additive composition of any one or more of Embodiments 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein X is manganese, cobalt, iron, zinc, or lead,

[0054] Embodiment 12: The gasoline additive composition of any one or more of the preceding Embodiments wherein the composition has an improvement in Saybolt number at least 1 unit, 1 to 40 units, or at least 5 units, or at 5 to 35 units, or 5 to 30 units, or 5 to 20 units compared to the original Saybolt number of the composition without the optical brighter. [0055] Embodiment 13: The gasoline additive composition of any one or more of the preceding Embodiments wherein the composition has a Saybolt number of +20 to +35, preferably +25 to +30.

[0056] Embodiment 14: The gasoline additive composition of any one or more of the preceding Embodiments wherein the composition has an improvement in blending research octane value of 0.5 to 10%, or 1 to 8%, compared to composition without the optical brightener; or the composition has an improvement in blending motor octane value of 0.5 to 10%, or 1 to 8%, compared to composition without the optical brightener.

[0057] Embodiment 15: The gasoline additive composition according to any one or more of the preceding Embodiments, wherein the composition, when added to a base gasoline up to a final volume percentage of 15 vol. %, changes the Reid vapor pressure of the base gasoline by 0 to ±0.2 psi.

[0058] Embodiment 16: A process for preparing the octane boosting, gasoline additive composition of any one or more of the preceding Embodiments, the process comprising: combining the oxygenate and the optical brightener.

[0059] Embodiment 17: The process of claim 16, further comprising manufacturing the oxygenate; and combining the oxygenate and the brightener without distilling the oxygenate to purify the oxygenate.

[0060] EmbcKtiment 18: A gasoline blend comprising: 80 to 90 vol. %, preferably 80 to 85 vol. %, more preferably 85 to 90 vol. % of a fuel-grade base gasoline; and 10 to 20 vol. %, preferably 15 to 20 vol. %, or 10 to 15 vol.% of the gasoline additive composition according to any one or more of Embc»diments 1 to 15, or the gasoline additive composition made by the process of any one or more of Embodiments 16 to 17.

[0061] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate components or steps herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any steps, components, materials, ingredients, adjuvants, or species that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0062] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of "up to 25 wt.%, or, more specifically, 5 wt.% to 20 wt.%," is inclusive of the endpoints and all intermediate values of the ranges of "5 wt.% to 25 wt.%," etc.). "Combinations" is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms "first," "second," and the like, do not denote any order, quantity, or importance, but rather are used to denote one element from another. The terms "a" and "an" and "the" do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. "Or" means "and/or" unless clearly stated otherwise.

Reference throughout the specification to "some embodiments," "an embodiment," and so forth, means that a particular element described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.

[0063] Unless defined otherwise, technical and scientific terms have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0064] While particular embodiments have been described, alternatives,

modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

1. An octane boosting, gasoline additive composition, comprising:

an oxygenate gasoline additive; and

an optical brightener.

2. The gasoline additive composition of claim 1, wherein the oxygenate comprises methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutanol, n-butanol, sec- butyl alcohol, tert-butyl alcohol, gasoline grade tert butyl alcohol, tert-amyl alcohol, methyl tert-butyl ether, ethyl tert-butyl ether, tert-amyl methyl ether, tert-amyl ethyl ether, tert-hexyl methyl ether, diisopropyl ether or a combination comprising at least one of the foregoing, preferably wherein the oxygenate comprises methyl tert-butyl ether.

3. The gasoline additive composition of any one or more of the preceding claims, comprising

99.5 to 99.9 wt%, or 97.5 to 99.9 wt%, or 99.9 to 95 wt% of the oxygenate, and 0.01 to 3 wt%, or 0.1 to 2.5 wt%, or 1 to 5 wt%, of the optical brightener, each based on the combined amount of oxygenate and optical brightener.

4. The gasoline additive composition of any one or more of the preceding claims, wherein the optical brightener is an azole derivative, benzoxazole derivative, biphenyl derivative, cinnamic acid derivative, fumaric acid derivative, coumarin derivative, dibenzothiophene-5,5-dioxide derivative, diphenyl styryl derivative, methinecyanine derivative, oxazole derivative, phenyloxazole derivative, pyrazoline derivative, stilbene derivative, or a combination comprising at least one of the foregoing;

preferably wherein the optical brightener is a cinnamic acid derivative, a diphenyl derivative, or a stilbene derivative.

5. The gasoline additive composition of any one or more of the preceding claims, wherein the optical brightener comprises a compound of the formula

wherein

R^a and R^b are each independently a C_1-60 hydrocarbyl group optionally containing up 1 to 20 heteroatoms, a halide, a nitro group, a C_1-5 alkyl group, or a sulfonic acid group, and preferably wherein R^a and R^b are each independently a halide, a nitro group, a C_1-5 alkyl group, or a sulfonic acid group.

6. The gasoline additive composition of any one or more of claims 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein

R¹, R², R³, and R⁴ are each independently a halide, a nitro group, a C_1-5 alkyl group, a C₁-5 alkoxy group, a sulfonic acid group, a phosphoric acid group, or a phosphonic acid group.

7. The composition of any one or more of claims 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein

R₁ is carbonyl or sulfonyl;

R₃ is hydroxyl,— 0-M⁺ wherein M⁺is a positively charged counterfoil, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C_1-10 alkyl)ammonium group, tri(C_1-10)alkoxysilyl group, or carboxy (C₁- 10 alkyl), or ether; and

R4 and R5 are each independently hydrogen, hydroxy, amino, (C_1-1oalkoxy)amino, (C₁- ₁₀alkyl)amino, (C_6-12 aryl)amino, hydroxy(C_1-10 alkyl)amino, morpholino, aniline, (C_1-10 alkyl)anilino, (C_1-10alkylene^ulfonic acid, piperazinyl, piperidinyl, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C_1-10 alkyl) ammonium group, tri(C_1-10)alkoxysilyl group, carboxy (C_1-10 alkyl), or ether.

8. The composition of any one or more of claims 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein

R₁ is carbonyl or sulfonyl;

R₃ is hydroxyl,— 0^~M⁺ wherein M⁺is a positively charged counterion, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C₁-10 alkyl)ammonium group, tri(C_1-20)alkoxysilyl group, carboxy (C₁-₁₀ alkyl), or ether,

R₄ and R₅ are each independently hydrogen, hydroxy, amino, (C_1-1oalkoxy)amino, (C₁- ₁₀alkyl)amino, (C_6-12 aryl)amino, hydroxy(C_1-10 alkyl)amino, morpholino, aniline, (C_1-10 alkyl) anilino, (C_1-10alkylene)sulfonic acid, piperazinyl, piperidinyl, or a C_6-200 substituent further containing at least one primary, secondary, tertiary, or quaternary amino group, ether group, ketone group, and at least one hydroxyl, primary or secondary amino group, quaternized (C₁- 10 alkyl)ammonium group, tri(C_1-10)alkoxysilyl group, carboxy (C_1-10 alkyl), or ether,

R₅₀ is— R₁— R₃ or— OR₁₀ wherein R₁₀ is a C_1-200 hydrocarbyl substituent comprising at least one of an ether, a carbonyl, a secondary amine, or a quaternized amine.

9. The gasoline additive composition of any one or more of claims 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein R^a and R^b are each independently a C_1-60 hydrocarbyl group optionally containing up 1 to 20 heteroatoms, a halide, a nitro group, a C_1-5 alkyl group, or a sulfonic acid group, and M is H, an alkali metal, ammonium, or magnesium;

preferably wherein R^a and R^b are each independently a halide, a nitro group, a C_1-5 alkyl group, a C₁-5 alkoxy group, or a sulfonic acid group.

10. The composition of any one or more of claims 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein

each R^c is independently H or (C_1-6)alkyl;

A=N or C; and

X is a bond via 1,4-naphthyl, 2,5-thiophene, 2,5-furan, 1,4-phenyl, ethylene, stilbene, styrene or imidazolyl units.

11. The gasoline additive composition of any one or more of claims 1 to 4, wherein the optical brightener comprises a compound of the formula

wherein X is manganese, cobalt, iron, zinc, or lead.

12. The gasoline additive composition of any one or more of the preceding claims wherein the composition has an improvement in Saybolt number at least 1 unit, 1 to 40 units, or at least 5 units, or at 5 to 35 units, or 5 to 30 units, or 5 to 20 units compared to the original Saybolt number of the composition without the optical brighter.

13. The gasoline additive composition of any one or more of the preceding claims wherein the composition has a Saybolt number of +20 to +35, preferably +25 to +30.

14. The gasoline additive composition of any one or more of the preceding claims wherein

the composition has an improvement in blending research octane value of 0.5 to 10%, or 1 to 8%, compared to composition without the optical brightener; or

the composition has an improvement in blending motor octane value of 0.5 to 10%, or 1 to 8%, compared to composition without the optical brightener.

15. The gasoline additive composition according to any one or more of the preceding claims, wherein the composition, when added to a base gasoline up to a final volume percentage of 15 vol. %, changes the Reid vapor pressure of the base gasoline by 0 to +0.2 psi.

16. A process for preparing the octane boosting, gasoline additive composition of any one or more of the preceding claims, the process comprising:

combining the oxygenate and the optical brightener.

17. The process of claim 16, further comprising manufacturing the oxygenate; and combining the oxygenate and the brightener without distilling the oxygenate to purify the oxygenate.

18. A gasoline blend comprising:

80 to 90 vol. %, preferably 80 to 85 vol. %, more preferably 85 to 90 vol. % of a fuel- grade base gasoline; and

10 to 20 vol. %, preferably 15 to 20 vol. %, or 10 to 15 vol.% of the gasoline additive composition according to any one or more of claims 1 to 15, or the gasoline additive composition made by the process of any one or more of claims 16 to 17.