ALCOHOL AND ETHER FUEL ADDITIVES FOR UNLEADED GASOLINE

Description

BACKGROUND

[0001] This application relates to fuel additives for a gasoline, a gasoline comprising the additives, and methods of making the gasoline.

[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 performance and the stability of gasoline, for example octane boosters...

[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] Besides that, EP1199296 A1 discloses a process for preparing methyl tert-butyl ether (MTBE) and a substantially isobutene-free C4-hydrocarbon mixture, which are suitable for increasing the octane number. US2015 / 240179 A1 discloses a method for simultaneously dimerizing and hydrating a mixed butenes feedstock to produce butene oligomers and butanols. EP745576 A1 refers to a process for the joint production of ethers and hydrocarbons with a high-octane number. Rankovic Nikola et al. ("Understanding octane number evolution for enabling alternative low RON refinery streams and octane boosters as transportation fuels", Fuel, IPC Science and Technology Press, Guildford, GB, vol. 150, 16 February, 2015, pages 41-45) is directed to a study where a spark ignition engine was operated using fuel with adjustable octane quality.

[0005] Preferred compounds in present use for formulating octane boosters include C 4 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. There is a need for a fuel additive or fuel that has an octane rating that is comparable to gasoline and that has increased combustion efficiency.

[0006] In view of the foregoing, there remains a need to provide cost-effective octane-enhancing compositions, and gasoline compositions including the octane-enhancing compositions.BRIEF DESCRIPTION

[0007] Disclosed, in various embodiments, are octane-enhancing additives, gasoline compositions comprising the octane-enhancing additives, and methods of making the gasoline compositions.

[0008] An octane-enhancing additive includes a mixed butanol composition, sec-butyl ether, methanol, methyl tert-butyl ether, and a C4-dimer, the mixed butanol composition comprising sec-butanol and tert-butanol, and the C4-dimer comprising di-isobutylene, 2,2,4 trimethylpentane, 2,3,3 trimethylpentane, wherein methanol is present in an amount of 0.55 to 0.80 volume percent of the octane- enhancing composition; wherein methyl tert-butyl ether is present in an amount of 70 to 95 volume percent of the octane-enhancing composition; wherein the mixed butanol composition is present in an amount of 3 to 29 volume percent of the octane-enhancing composition; and wherein sec-butyl ether is present in the range of 0.4 to 4 volume percent of the octane-enhancing composition.

[0009] A gasoline composition includes a base gasoline and an octane-enhancing composition disclosed herein.

[0010] A method for preparing the gasoline composition includes combining a base gasoline and an octane-enhancing composition disclosed herein to form a gasoline composition.

[0011] A method for preparing a gasoline composition includes combining a base gasoline with a mixed butanol composition, sec-butyl ether, methanol, methyl tert-butyl ether, and a C4-dimer, the mixed butanol composition comprising sec-butanol and tert-butanol, and the C4-dimer comprising di-isobutylene, 2,2,4 trimethylpentane, 2,3,3 wherein methanol is present in an amount of 0.55 to 0.80 volume percent of the octane- enhancing composition; wherein methyl tert-butyl ether is present in an amount of 70 to 95 volume percent of the octane-enhancing composition; wherein the mixed butanol composition is present in an amount of 3 to 29 volume percent of the octane-enhancing composition; and wherein sec-butyl ether is present in the range of 0.4 to 4 volume percent of the octane-enhancing composition.

[0012] The above described and other features are exemplified by the following detailed description.DETAILED DESCRIPTION

[0013] Described herein are a novel combination of oxygenate additives, octane-enhancing compositions comprising the novel combination of oxygenate additives, and gasoline compositions comprising the novel octane-enhancing composition. It has been found by the inventors that a gasoline composition comprising the novel octane-enhancing composition disclosed herein is characterized by increased octane number, providing better combustion and improved performance in internal combustion engines, particularly for the automotive market. In particular, the gasoline compositions comprising the novel combination of oxygenate additives can provide better performance properties compared to gasoline compositions containing ethanol, MTBE, or butanol as the sole oxygenate additive.

[0014] 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 effective to improve the octane rating of gasoline by 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 (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). These oxygenates can be produced by any known and acceptable chemical and biological reactions that are known in the art, 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.

[0015] The novel combination of oxygenate additives comprises a mixed butanol composition, sec-butyl ether, methanol, methyl tert-butyl ether, and a C4-dimer.

[0016] The mixed butanol composition comprises sec-butanol and tert-butanol. The relative ratio of sec-butanol to tert-butanol can vary widely, for example a volume ratio of sec-butanol:tert-butanol of 1:99 to 99:1, or 10:90 to 90:10, or 20:80 or 80:20, or 30:70 to 70:30. In an embodiment, the volume ratio of sec-butanol:tert-butanol is 2:1 to 3:1. The preferred volume ratio is 2.4:1. The mixed butanol composition can further comprise n-butanol, isobutanol, or a combination thereof. The amount of n-butanol, isobutanol, or combination thereof can be 1 to 90 volume percent (vol. %), 1 to 80 vol. % or 1 to 70 vol. %, or 1 to 60 vol. %, or 1 to 50 vol. %, or 1 to 40 vol. %, or 1 to 30 vol. %, or 1 to 20 vol. %. In in an embodiment, the amount of n-butanol, isobutanol, or combination thereof is 84 vol. %

[0017] The C4-dimer comprises di-isobutylene; 2,2,4 trimethylpentane; 2,3,3 trimethylpentane; or a combination comprising at least one of the foregoing. There is no particular restriction on the relative amounts of each of the foregoing components in the C4-dimer composition.

[0018] The mixed butanol composition, sec-butyl ether, methanol, methyl tert-butyl ether, and C4-dimer can be added to a base gasoline to form a gasoline composition. The mixed butanol composition, sec-butyl ether, methanol, methyl tert-butyl ether, and C4-dimer can each be added individually to the base gasoline.

[0019] Alternatively, at least two of the mixed butanol composition, sec-butyl ether, methanol, methyl tert-butyl ether, and C4-dimer can be blended to form a premixed octane-enhancing additive. In some embodiments, the mixed butanol composition, sec-butyl ether, methanol, methyl tert-butyl ether, and C4-dimer are blended in a single octane-enhancing composition. The octane-enhancing composition can subsequently be added to a base gasoline to obtain a gasoline composition.

[0020] Accordingly, the octane-enhancing composition comprises a mixed butanol composition, sec-butyl ether, methanol, methyl tert-butyl ether, and a C4-dimer. The mixed butanol composition is present in the octane-enhancing composition in an amount of 3 to 29 vol. %, The C-4 dimer can be present in the octane-enhancing composition in the range of 0.1 to 3 vol. % or 0.19 to 2 vol. %. Methanol is present in the octane-enhancing composition in an amount of 0.55 vol. % to 0.80 vol. %. MTBE is present in the octane-enhancing composition an amount of 70 to 95 vol. %. Each of the foregoing amounts is based on the total volume of the octane-enhancing composition, i.e., the total volume of the mixed butanol composition, sec-butyl ether, methanol, methyl tert-butyl ether, and C4-dimer.

[0021] The octane-enhancing composition or components thereof can be added directly to the base gasoline. However, the octane-enhancing composition or components thereof can be diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene, or xylene, to form an additive concentrate. These concentrates can comprise 0.1 to 80% by weight, or about 1% to 80% by weight, or 10% to 80% by weight, of the octane-enhancing composition and can contain, in addition, one or more other additives known in the art as described below. Concentrations such as 15%, 20%, 30% or 50% or higher can be used. The concentrates can be prepared by combining the desired components in any order at any temperature, for example at 23 to 70°C.

[0022] Also disclosed is a gasoline composition comprising a base gasoline and an octane-enhancing composition disclosed herein. In the gasoline composition, the base gasoline is present in an amount of 60 to 97 vol. % preferably 65 to 95 vol. %, more preferably 70 to 90 vol. %. The octane-enhancing composition can be present in the gasoline composition in an amount of 3 to 40 vol. %, preferably 5 to 35 vol. %, preferably 10 to 30 vol. %, each based on the total volume of the gasoline composition.

[0023] The gasoline composition can be prepared by combining a base gasoline and the components of an octane-enhancing composition disclosed herein, either separately or in any combination.

[0024] The mixed butanol composition can be present in the gasoline composition in a total amount of 0.5 to 20 vol. %, preferably 0.7 to 10 vol. %, more preferably 0.8 to 5 vol. %, each based on the total volume of the gasoline composition.

[0025] The methanol can be present in the gasoline composition in a total amount of 0.02 to 0.3 vol. %, preferably 0.04 to 0.25 vol. %, more preferably 0.08 to 0.20 vol. %, each based on the total volume of the gasoline composition.

[0026] The sec butyl ether and the methyl tert-butyl ether can be present in the gasoline composition in a total amount of 0.02 to 30 vol. %, preferably 0.06 to 26 vol. %, each based on the total volume of the gasoline composition.

[0027] The C4-dimer can be present in the gasoline composition in an amount of 0.01 to 2 vol. %, preferably 0.04 vol. % to 1 vol. %, each based on the total volume of the gasoline composition.

[0028] The octane-enhancing composition can further comprise other additives known in the art, for example anti-foam agents, anti-icing agents, additional anti-knock agents, anti-oxidants, anti-wear agents, color stabilizers, corrosion inhibitors, detergents, dispersants, dyes, extreme pressure agents, lead scavengers, metal deactivators, pour point depressing agents, upper-cylinder lubricants, viscosity improvers, and the like. The amounts of such additives depend on the particular additive, and can be readily determined by one of ordinary skill in the art.

[0029] Anti-foam agents used to reduce or prevent the formation of stable foam include silicones or organic polymers. Anti-oxidants, corrosion inhibitors, and extreme pressure agents are exemplified by chlorinated aliphatic hydrocarbons, organic sulfides and polysulfides, phosphorus esters including dihydrocarbon and trihydrocarbon phosphites, molybdenum compounds, and the like. Other anti-oxidants alkylated diphenyl amines, hindered phenols, especially those having tertiary alkyl groups such as tertiary butyl groups in the position ortho to the phenolic -OH group, and the like.

[0030] Detergents and dispersants can be of the ash-producing or ashless type. The ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, phenols, or organic phosphorus acids characterized by a least one direct carbon-to-phosphorus linkage. Ashless detergents and dispersants can yield a nonvolatile residue such as boric oxide or phosphorus pentoxide upon combustion, but do not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion. Examples include reaction products of carboxylic acids (or derivatives thereof) containing 34 to 54 carbon atoms with nitrogen containing compounds such as amine, organic hydroxy compounds such as phenols and alcohols, and / or basic inorganic materials.

[0031] Viscosity improvers are usually polymers, for example polyisobutenes, poly(methacrylic acid esters), hydrogenated diene polymers, polyalkyl styrenes, esterified styrene-maleic anhydride copolymers, hydrogenated alkenylarene-conjugated diene copolymers, and polyolefins.

[0032] In particular, the octane-enhancing composition can further comprise other oxygenate compounds, for example other alcohol, esters, or ether oxygenates. Examples of other alcohols that can be included are ethanol, isopropyl alcohol, n-propyl alcohol, tert-amyl alcohol, or a combination comprising at least one of the foregoing, Examples of other ethers that can be included are 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. Examples of esters that can be included are isoamyl acetate, amyl acetate, isoamyl propionate, isoamyl nonanoate, isobutyl acetate, methyl butyrate, methyl caproate, methyl caprylate, or a combination comprising at least one of the foregoing. These additional oxygenate compounds can be present in an amount of 0.02 to 20 vol. %, or 0.1 to 10 vol. %, each based on the total volume of the gasoline composition.

[0033] Other anti-knock additives include xylene, benzene, toluene, aniline, and the like.

[0034] The gasoline composition can be characterized as having a Reid vapor pressure (RVP) of 6.0 to 8.0 psi, preferably 6.5 to 7.8. The gasoline composition can also be characterized as having a research octane number (RON) higher than the RON of the base gasoline and a motor octane number (MON) higher than the MON of the base gasoline. For example, the gasoline composition can have a RON of 88 to 110, preferably 90 to 105, and a MON of 82 to 105.

[0035] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLESExample 1 Gasoline blends with fuel additives

[0036] Various potential additives selected from alcohols, ethers, or C4-dimers are added to a base gasoline which has the properties shown in Table 1 below. The composition of each gasoline blend is provided in Tables 2 and 3. Table 1. Typical Physical Properties of Base gasolineTestMethodResultDensity @15.0°C(kg / L)ASTM D40520.7580RVPASTM D3236.39 psiDoctor TestASTM D4952+iveOxygenatesASTM D4815Not DetectedTotal Aromatics (FIA)ASTM D131936.0 vol. %Total Aromatics (GC)ASTM D558035.68 vol. %Olefins (FIA)ASTM D13197.98 vol. %RONASTM D269989.5

[0037] Reid Vapor Pressure (RvP), research octane number (RON), and motor octane number (MON) are measured for each blend.

[0038] RvP is a measure of the volatility of gasoline. It is defined as the absolute vapor pressure exerted by a liquid (e.g., gasoline) at 100 °F (37.8 °C) as determined by test method ASTM D 323.

[0039] RON describes the knocking behavior at a low engine load and low rotational speeds and is determined according to DIN EN ISO 5164 (ASTM D 2699).

[0040] MON describes the behavior at a high engine load and under high thermal stress and is determined according to DIN EN ISO 5163 (ASTM D 2700).

[0041] Results of the tests for the base gasoline and each of the blends are tabulated in Tables 2 and 3 below. Table 2. RvP, RON and MON of gasoline blendsAlcoholsEthersHydrocarbonSec-Butyl AlcoholTer.-Butyl AlcoholMethanolDi-Sec-Butyl EtherMethyl-Tertiary-Butyl EtherDi-isoButyleneBase GasolineRvPRONMON0000001006.3989.581.50.000.000.040.004.960.00956.3991.384.10.000.000.080.009.930.00906.5992.684.30.000.000.110.0014.890.00856.679484.70.000.000.150.0019.850.00806.7495.185.32.921.220.000.600.000.26956.2890.3825.842.440.001.210.000.52906.2490.982.68.763.650.001.810.000.78856.2391.983.411.684.870.002.420.001.04805.979384 Table 3. RvP, RON and MON of gasoline blends AlcoholsEthersHydrocarbonSec-Butyl AlcoholTer.-Butyl AlcoholMethanolDi-Sec-Butyl EtherMethyl-TertiaryButyl EtherDi-isoButyleneBase GasolineRvPRONMON0000001006.3989.581.5000.0809.930906.5992.684.30.580.240.080.129.930.05896.6592.684.31.750.730.080.369.930.16876.5692.884.42.921.220.080.609.930.26856.539384.40.000.000.110.0014.890.00856.679484.70.580.240.110.1214.890.05846.6693.784.71.170.490.110.2414.890.10836.6393.884.81.750.730.110.3614.890.16826.6293.984.82.340.970.110.4814.890.21816.5694.184.92.921.220.110.6014.890.26806.5194.384.90.000.000.150.0019.850.00806.7495.185.30.580.240.150.1219.850.05796.795.185.41.170.490.150.2419.850.10786.6795.385.51.750.730.150.3619.850.16776.6595.585.62.340.970.150.4819.850.21766.6595.685.62.921.220.150.6019.850.26756.6295.885.7000.19024.810756.896.786.50.580.240.190.1224.810.05746.896.786.51.750.730.190.3624.810.16726.779786.52.921.220.190.6024.810.26706.7297.286.6

[0042] The compositions and methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0043] 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 "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.

[0044] All test methods cited herein are those in effect as of the priority date of this application.

[0045] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs.

Claims

1. An octane-enhancing composition comprising a mixed butanol composition, sec-butyl ether, methanol, methyl tert-butyl ether, and a C4-dimer, the mixed butanol composition comprising sec-butanol and tert-butanol, and the C4-dimer comprising at least one of di-isobutylene, 2,2,4 trimethylpentane, or 2,3,3 trimethylpentane, wherein methanol is present in an amount of 0.55 to 0.80 volume percent of the octane-enhancing composition; wherein methyl tert-butyl ether is present in an amount of 70 to 95 volume percent of the octane-enhancing composition; wherein the mixed butanol composition is present in an amount of 3 to 29 volume percent of the octane-enhancing composition; and wherein sec-butyl ether is present in the range of 0.4 to 4 volume percent of the octane-enhancing composition.

2. The octane-enhancing composition of claim 1, the mixed butanol composition further comprising n-butanol, or isobutanol, or a combination thereof.

3. The octane-enhancing composition according to any one or more of claims 1 to 2, wherein the C4-dimer is present in the range of 0.1 to 3 volume percent of the octane-enhancing composition.

4. The octane-enhancing composition according to any one or more of claims 1 to 3, wherein the C4-dimer is present in the range of 0.19 to 2 volume percent of the octane-enhancing composition.

5. The octane-enhancing composition according to any one or more of claims 1 to 4, further comprising ethanol, isopropyl alcohol, n-propyl alcohol, tert-amyl alcohol, or a combination comprising at least one of the foregoing.

6. The octane-enhancing composition according to any one or more of claims 1 to 5, further comprising 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.

7. A gasoline composition comprising a base gasoline, and the octane-enhancing composition of any one or more of claims 1 to 6.

8. The gasoline composition of claim 7 having a Reid vapor pressure of 41.4 to 55.2 kilopascals (6.0 to 8.0 pounds per square inch), the Reid vapor pressure determined by test method ASTM D 323; or having a research octane number higher than the research octane number of the base gasoline and a motor octane number higher than the motor octane number of the base gasoline, the research octane number determined according to ASTM D 2699, and the motor octane number determined according to ASTM D 2700.

9. The gasoline composition of any one or more of claims 7 to 8 having a research octane number of 88 to 110 and a motor octane number of 82 to 105, the research octane number determined according to ASTM D 2699, and the motor octane number determined according to ASTM D 2700.

10. The gasoline composition of any one or more of claims 7 to 9 wherein the mixed butanol composition and methanol are present in a total amount of 0.9 to 5 volume percent of the gasoline composition.

11. The gasoline composition of any one or more of claims 7 to 10 wherein the sec butyl ether and the methyl tert-butyl ether are present in a total amount of 0.06 to 26 volume percent of the gasoline composition.

12. The gasoline composition of any one or more of claims 7 to 11 wherein the C4-dimer is present at 0.04 to 1 volume percent of the gasoline composition.

13. The gasoline composition of any one or more of claims 7 to 12 wherein the base gasoline is present at 70 to 90 volume percent of the gasoline composition.

14. A method for preparing a gasoline composition, comprising combining a base gasoline and the components of the octane-enhancing composition as defined in any one or more of claims 1 to 6 to form a gasoline composition.

15. The method of claim 14, wherein the octane-enhancing composition is present in the gasoline composition in an amount of 10 to 30 volume percent of the gasoline composition.