Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
  • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1857—Aldehydes; Ketones
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)

Definitions

• This invention relates generally to novel fuel compositions for spark ignition internal combustion engines. More pa ticula ly, it relates to a novel additive combination for "nonleaded" gasoline compositions .
• TEL tetraethyl lead
• organomanganese compounds such as cyclomatic mang ane se tr icarbonyl s , par t ic ul arly methylcyclopentadienyl manganese tricarbonyl ("MMT"), were once accepted alternatives to TEL.
• MMT par t ic ul arly methylcyclopentadienyl manganese tricarbonyl
• these o compounds produced another set of environmental problems. Their use tends to steadily increase the amount of unoxidized and/or partially oxidized hydrocarbons. Fuels containing such organomanganese compounds gradually cause the emission of substantially 5 - higher levels of hydrocarbons than are permitted under law.
• the 195 patent teaches that a positive synergism in the antiknock properties of leaded gasoline/alcohol fuel compositions can be obtained by adding a cyclomatic manganese tr icarbonyl such as MMT to leaded gasoline compositions.
• a cyclomatic manganese tr icarbonyl such as MMT
• Blending octane value is the arithmetic average of the research octane value and the motor octane value and is typically expressed as (R + M)/2.
• methanol/gasoline blends have been reported to be 2 to 3 Motor Octane Number and as high as 16 Research Octane Number above the reported values for the base gasol ine .
• f inished methanol/gasoline fuels normally are 1.5 to 3 octane points (R+M)/2 higher than the base fuel itself.
• methanol by itself is not widely used as a gasoline additive due to the number of serious technical and legal problems associated with its use.
• the presence of even small amounts of water can cause serious operational problems.
• Methanol when used by itself tends to phase-separate from gasoline in the presence of water and/or when exposed to cold weather conditions. This tendency to phase-separate has been an obstacle to the use of such alcohols as octane enhancers and gasoline extenders.
• methanol, particularly when it has phase-separated from gasoline is known to have harmful corrosive tendencies to certain fuel delivery and engine components.
• Section 211(f) (a) of the Clean Air Act, as amended (42 USC 7445), governs the usage and introduction of additives in unleaded gasolines and specifically provides that no fuel or fuel additive may be first introduced into commerce that is not "substantially similar” to any fuel or fuel additive used in the certification of any 1974 or later model year vehicle.
• EPA defined "substantially similar” to include fuels with up to 2.0 wt. percent oxygen. Ethers or alcohols (except methanol) are acceptable additives if they otherwise meet these oxygen limitations.
• Methanol can be used as a de-icer when used up to 0.3 volume percent or be used for this purpose up to 2.75 volume percent when introduced with an equal volume of butanol or a higher molecular weight alcohol.
• the fuel must conform to the characteristics of an unleaded gasoline as specified by ASTM D 439.
• This definition of “substantially similar” provides a general rule for the inclusion of oxygenates in unleaded gasolines.
• Methyl tertiary butyl ether (MTBE) qualifies under the general 2% oxygen rule. This is equivalent to about 11% MTBE by volume, depending on the specific gravity of the gasoline.
• the Clean Air Act under Section 211(f)(4) provides that the EPA Administrator may waive the prohibition on new fuels or fuel additives.
• the concentration of oxygen in the finished fuel cannot exceed 3.5 weight percent.
• the 3.5% oxygen limit translates into about 9.6% by volume.
• the 3.5 weight percent oxygen is equivalent to about 16 volume percent GTBA.
• a gasoline contains excessive concentrations of oxygenated components such as methanol
• the air (oxygen) to fuel ratio is significantly changed from the predetermined ratio. Signification deviations from the predetermined ratio causes poor ignition and combustion properties of the fuel. A high air (oxygen) to fuel ratio produced in this manner will cause the engine to run lean. If an engine's air (oxygen) to fuel ratio becomes too high or lean, the engine will fail to start and/or continue to run.
• Technical enleanment An attribute of enleanment which heretofore has not been distinguished by those skilled in the art is called “technical enleanment”.
• Technical enleanment is that unexpected phenomena which exhibits symptoms of enleanment occurring when the total air (oxygen) content of the finished fuel is not stoichiometrically or chemically lean. Such behavior is very similar to enleanment and includes engine stalling, lack of power.
• alcohols typically increase Reid vapor pressure, depress the initial fraction of the distillation curve, together tending to increase evaporative emissions.
• methanol at 5 to 10 volume percent concentrations increases the blended fuel's vapor pressure from 1.5 to 3.5 p.s.i. over the base fuel itself.
• This negative characteristic is known in the art as a nonideal positive vapor pressure increase, because heat methanol has a vapor pressure lower than that of the base gasoline to which it is blended.
• other lower molecular weight alcohols tend to exhibit similar nonideal vapor pressure attributes.
• cyclomatic manganese tricarbonyls such as MMT are directly traceable to the associative build-up of unoxidized or partially oxidized hydrocarbons and oxides of manganese (believed to be "Mn3 ⁇ 4") .
• the oxide of manganese is the oxidation product of the cyclomatic manganese tricarbonyls.
• HGM tends to attract other unoxidized or partially oxidized hydrocarbons and Mn3U4 which together tend to plug catalysts, foul spark plugs and form combustion chamber deposits. It is also believed, especially when the quantities of MMT are in excess of about 1/16 grams per gallon, that the presence of HGM causes a certain type of Mn3 ⁇ 4 deposit in the catalytic converter system which ultimately causes it to plug.
• Figure 1 plots temperature versus percentage of distillate recovered for various fuel blends and graphically depicts the improved distillation characteristics of Applicant's novel fuel composition.
• Figure 2 plots hydrocarbon emissions (gr/mi) versus manganese concentration (gr/gal.) in various fuel blends .
• the defined operational range of proportions over wh i c h the g asol ine bases , the Ci to C 6 aliphatic alcohol component, the cyclopentadienyl manganese tricarbonyl component and the aromatic hydrocarbon component may be employed to reduce hydrocarbon and evaporative emissions, correct technical enleanment and improve RVP, control initial and mid-range distillation depression and control end boiling point temperatures is:
• the higher the total concentration of the lower boiling point alcohols the higher the preferred concentrations of manganese.
• the beneficial hydrocarbon emission and other ameliorative effects of this invention do not generally begin to occur until approximately 1.0% oxygen by weight of the Ci to C5 alcohol component is introduced into the fuel composition.
• methanol is used as the sole aliphatic alcohol without the benefit of any cosolvent(s) it should be limited to a concentration of about 5 volume percent or less of the fuel composition.
• a cosolvent or group of cosolvents selected from the group consisting of C2 to C12 aliphatic alcohols, C3 to C 12 k e tones and/or C2 to C 12 ethers in concentrations from about 1 to about 20 volume percent should also be employed.
• the combined methanol and cosolvent concentration should, however, not exceed 30 volume percent of the entire fuel composition.
• the cosolvent alcohol(s) is selected from the group consisting of C2 to C8 aliphatic alcohols
• the preferred aliphatic alcohol is a saturated aliphatic alcohol(s).
• one or more C ]_ to Cg al iphatic alcohols preferably, Ci to C ⁇ saturated aliphatic alcohols, must be employed in the fuel composition.
• the alcohol component maybe any individual alcohol or any combination or mixture thereof. Mixed alcohol combinations may be desirable for enhancing blending octane values and controlling RVP increases. It is contemplated in the practice of this invention that mixed alcohols produced from the modification of known methanol catalysts, use of alkali metal oxide catalysts, use of rhodium catalysts, isosynthesis using alkalized Th ⁇ 2 catalysts, use of modified
• Fischer-Tropsch catalysts modified turgi catalysts, and/or pr od uc ed f rom c er ta in isomer ization/dehydrogenation processes, olefinic/hydration processes, "OXO" processes and the like, are acceptable.
• Alcohol mixtures generally having methanol, ethanol, propanols, butanols, pentanols and hexanols in the composition; which by weight percent of the composition decline as the individual molecular weight of the alcohol increases, are desirable.
• An example of a mixed alcohol composition wherein the lower molecular weight alcohols have a higher relative proportion of the composition by volume percent than do the higher molecular alcohols include: methanol at app o imately 50 weight percent of the alcohol component, ethanol at approximately 25 weight percent, propanols at approximately 13 weight percent, butanols at approximately 6 weight percent, pentanols at approximately 3 weight percent, with hexanols and other higher alcohols generally representing the balance of the alcohol component.
• Another example of a desirable alcohol mixture would include a composition wherein the higher molecular weight alcohols have higher relative proportions by volume percent of the composition than do the lower molecular weight alcohols. Still another exa ple would include a mixed alcohol composition wherein similar proportions of each alcohol exist by volume percent in the composition.
• Mixed alcohol compositions generally include methanol to higher alcohol ratios generally varying from 4:1 to 1:4 weight percent of the alcohol compositions. Those other combinations of alcohol mixtures which positively effect RVP, octane, distillation characteristics, end boiling point temperatures, and/or emissions are particularly desirable.
• Suitable alcohols for use include methanol, ethanol, N-propanol, isopropanol, N-butanol, secondar y-butanol , isobutanol, tertiary butanol, pentanols, hexanols and the like.
• aliphatic alcohols in ranges from up to about 30.0% by volume with about up to 14.2% oxygen by weight give excellent hydrocarbon emission results when used in unleaded gasolines.
• the composition should have at least 0.001 grams manganese and generally no more than one gram manganese of a cyclomatic manganese tricarbonyl compound per gallon.
• the alcohol employed should be anhydrous, but alcohols containing small amounts of water can also be used. Within the preferred concentration range most of the C ⁇ to CQ aliphatic alcohols are completely miscible with petroleum hydrocarbons and it is preferred that such alcohols be used in amounts within their solubility limits. However, if desirable, an amount of alcohol in excess of its solubility can be incorporated in the fuel by such means, as for example, by use of mutual solvents.
• An acceptable cyclomatic manganese tricarbonyl concentration range is from about 0.001 to about 1.0 grams manganese per gallon of fuel composition. A more acceptable range is from about 1/64 to about 1/2 grams manganese per gallon of composition. A more
• SUBSTITUTE SHE desirable and preferred range is from about 1/64 to about 1/4 grams manganese per gallon of composition. An even more preferred range is from about 1/64 to about 1/8 grams manganese per gallon of composition. 5
• the preferred cyclomatic manganese tricarbonyl used in the composition is methyl cyclopentadienyl manganese tricarbonyl (MMT).
• the acceptable oxygen by weight in the fuel composition is up to about 14.2 weight percent.
• a 0 more desirable range would be from about 1.0 to about 8.0 weight percent.
• a preferred range would be from about 1.0 to about 5.0 weight percent.
• the most preferred range is from about 2.0 to about 3.5 weight percent of the fuel composition.
• An acceptable range of aromatic hydrocarbons is up to about 45 percent.
• a desirable range is from about 1.0 to about 20 volume percent of the composition.
• a preferred range would be from about 1.0 to about 10.0 volume percent of the composition.
• a more preferred o range would be from about 1.0 to about 5.0 volume percent of the composition.
• An acceptable boiling range of the aromatic hydrocarbons including streams or fractions containing aromatic hydrocarbons is up to about 700°F.
• a more 5 acceptable range is from about 200°F to about 550 °F.
• a preferred range is from about 200°F to about 500°F, and a more preferred range is from 250°F to about 450 °F.
• Preferred end point boiling ranges are from approximately 400°F to 550 °F. 0 It is contemplated that in order to maximize the benefits of this invention that the fuel composition is to be constructed within the scope of the Table of Ingredient Ranges above.
• Desirable individual alcohol compositions would 5 contain from about up to about 5 volume percent methanol, or up to about 15 volume percent ethanol, or up to about 18 volume percent isopropanol, or up to about 18 volume percent normal propanol, or up to about 20 volume percent tertiary butanol, or up to about 20 volume percent secondary butanol, or up to about 20 volume percent isobutanol, or up to about 20 volume percent normal butanol, or kup to about 25 volume percent pentanols, or up to about 30 volume percent hexanols and aromatic hydrocarbons from up to about 20 volume percent together with MMT as the cyclopentadienyl manganese in a concentration of up to about 1/4 gram of manganese per gallon of fuel composition.
• a more preferred composition would contain aromatic hydrocarbons from about 1.0 to about 10 volume percent and a MMT concentration from about 1/64 to about 1/8 grams of manganese per gallon of fuel composition.
• a desirable alcohol/gasoline fuel composition includes a Ci - C6 alcohol component from about 2 to 30 volume percent, plus about 1/64 to 1 gram manganese of MMT per gallon of the composition with about 1 to about 45 volume percent aromatic hydrocarbons together with unleaded gasoline.
• a more desirable composition would contain aromatic hydrocarbons from about 1 to about 20 volume percent together with MMT from about 1/64 to 1/4 gram manganese of MMT per gallon of the composition.
• a desirable alcohol ( cosolvent) /gasol ine fuel compo s i tion includes a Cj - Cg alcohol component from about 2 to 25 volume percent of the composition plus a cosolvent or group of cosolvents selected from the group consisting of C2 - C12 aliphatic alcohols, C3 - C12 ketones ' and/or C2 to C12 ethers in concent ations from about 1 to 20 volume percent, so that the combined alcohol and cosolvent concentration in the composition is not more than 30 volume percent.
• This fuel composition includes a Cj - Cg alcohol component from about 2 to 25 volume percent of the composition plus a cosolvent or group of cosolvents selected from the group consisting of C2 - C12 aliphatic alcohols, C3 - C12 ketones ' and/or C2 to C12 ethers in concent ations from about 1 to 20 volume percent, so that the combined alcohol and cosolvent concentration in the composition is not more than 30 volume percent.
• SUBSTITUT would be combined with about 1/64 to 1 gram manganese of MMT per gallon of the composition with about 1 to about 40 volume percent aromatic hydrocarbons in the composition together with an unleaded gasoline base.
• a more desirable composition would contain aromatic hydrocarbons from about 1 to about 20 volume percent together with MMT from about 1/64 to about 1/4 grams manganese per gallon of composition.
• a preferred composition would contain aromatic hydrocarbons from about 1 to 10 volume percent together with MMT from about 1/64 to 1/8 grams manganese per gallon of the composition.
• An even more preferred composition would contain aromatic hydrocarbons in a concentration range up to about 6 volume percent of the composition.
• Another desirable fuel composition contains methanol from about 1 to about 15 volume percent of the composition, C2 to C12 aliphatic alcohols, C 2 - C 12 e ther s and/or C3 -C 12 ketones in concentration from about 1 to about 15 volume percent of the composition and a MMT concentration from about 1/64 to about 1/2 gram of manganese per gallon of fuel composition together with about 1.0 to about 20 volume percent aromatic hydrocarbons.
• a preferred MMT concentration would be from about 1/64 to about 1/4 grams manganese per gallon of the composition together with about 1.0 to about 10 volume percent aromatic hydrocarbons.
• 1 concentration would be from about 1/64 to 1/8 grams manganese per gallon of the fuel composition with about 1.0 to about 5 volume percent aromatic hydrocarbons.
• a preferred fuel composition contains methanol from about 1 percent to about 9 volume percent of the composition, C2 to C12 aliphatic alcohols in concentrations from about 1 to about 10 volume percent of the composition, a MMT concentration from about 1/64 to about 1/4 gram manganese per gallon of fuel composition with aromatic hydrocarbons from about 1.0 to about 20 volume percent and a more preferred MMT concentration from about 1/32 to 1/8 gram per gallons with aromatic hydrocarbons from about 1.0 to about 10 volume percent of the fuel composition.
• a more preferred fuel composition contains methanol from about 2 to about 6 volume percent with C2 to Ci2 saturated aliphatic alcohols in concentration from about 1 percent to about 10 volume percent of the composition and a MMT concentration from about 1/64 to about 1/4 gram manganese per gallon of fuel composition together with about 1.0 to about 20 percent aromatic hydrocarbons in the composition and an even more preferred MMT concentration is from about 1/64 to 1/8 gram per gallon together with about 1.0 to about 10 volume percent aromatic hydrocarbons in the composition.
• Another highly preferred fuel composition would contain methanol from about 2 to.6 volume percent with C4 to C12 saturated aliphatic alcohols in concentrations from about 1 percent to about 10 volume percent of the composition, particularly those having boiling points higher than tertiary butanol and a MMT concentration from about 1/64 to about 1/4 grams manganese per gallon of fuel composition together with about 1.0 to about 20 percent aromatic hydrocarbons in the composition.
• a more preferred MMT concentration would be from about 1/64 to 1/8 gram per gallon together with about 1.0 to about 10 volume percent aromatic hydrocarbons in the composition.
• Aromatic hydrocarbons often are the resultant product of the reformer. Fluid Catalyst Cracker Unit (FCC), Riser Cracker Unit or Coker Unit using napthas, gas oils, resid, coal liquids, shale oils, asphalt and/or other similar feed stocks. Aromatic hydrocarbons may also be the product of other reaction processing units within a petrochemical complex or refinery. These aromatic hydrocarbons may be streams themselves.
• FCC Fluid Catalyst Cracker Unit
• Riser Cracker Unit or Coker Unit using napthas, gas oils, resid, coal liquids, shale oils, asphalt and/or other similar feed stocks.
• Aromatic hydrocarbons may also be the product of other reaction processing units within a petrochemical complex or refinery. These aromatic hydrocarbons may be streams themselves.
• Nonlimiting examples of Applicant's contemplated aromatic hydrocarbons include reformates, raffinates, pi a t f o rmate s , alkalates, napthas, distillates, isomerates, polymerates, light cycle oils, coal liquids, biomass liquids, wood liquids and the like.
• aromatic hydrocarbons or aromatic based hydrocarbon streams normally boil in ranges which include temperatures inside and/or outside normal gasoline boiling temperatures. They often are components of streams which themselves can not readily be added to gasoline or streams which can not be economically processed into gasoline for various reasons. Often these streams contain significant quantities of olefins and paraffins. Higher octane components are preferred, especially branched chain, condensed ring and iso-par af f ins and olefins. In certain cases these streams are exclusive of aromatic hydrocarbons.
• light cycle oils which are generally known to be fluid catalytic cracker (FCC) recycle oils and which are produced by the FCC from heavy gas oils, have boiling ranges normally varying from about 300°F to about 650°F and in certain cases boiling at temperatures outside these ranges.
• Light cycle oils are generally recycled through the FCC to produce additional gasoline material until the economics of recycling diminish and they become a component of distillate, diesel fuel oils, or other fuels.
• SUBSTITUTE SHEET Acceptable aromatic hydrocarbons are those having boiling ranges from approximately 200 °F to 700 °F and in certain cases boiling temperatures outside these ranges.
• Applicant's aromatic hydrocarbons, or streams or fractions containing aromatic hydrocarbons thereof are those with a carbon molecular content up to generally C-25, more preferred are those up to C-15, with the most preferred being those between C-5 to C-15.
• Applicant's aromatic hydrocarbons can be added to or processed into gasoline only at additional expense to the refiner because of the nature of the process stream itself. Often this additional expense if prohibitive.
• SUBSTITUTE SHEET alcohols at 10% by volume.
• the alcohols used therein are methanol and pentanol in equal parts.
• Figure 1 shows that the "uncorrected base fuel”, (an alcohol gasoline composition without the balance of Applicant' s MMT and aromatic hydrocarbon ingredients) , has the expected initial and mid-range distillation fraction depression when compared to the base gasoline. Note that the "corrected fuel” (containing Applicant' s defined ingredients) substantially improves the initial and mid-range distillation depression as well as improving the end boiling point characteristics of the "uncorrected base fuel with aromatic hydrocarbons" (without the benefit of Applicant's other ingredients).
• aromatic based hydrocarbon streams or fractions thereof are acceptable.
• generally acceptable aromatic hydrocarbons streams are those which have at least 10% by weight aromatic hydrocarbons, but those having an aromatic content in excess of 50% or more by weight are more preferred.
• the hydrocarbon streams or fractions thereof have, an octane (R + M)/2 rating in excess of 50, a more preferred octane rating would be in excess of 70, an even more preferred octane rating would be in excess of 85 (generally, the higher the octane rating the better).
• the initial lighter, lower boiling point hydrocarbon based fractions boiling between 200°F to 450°F are preferred over those fractions boiling between 200°F to 550 °F over those fractions boiling from 200°F to 700°F.
• aromatic hydrocarbons which are typically found in normal boiling range gasolines it is also within the scope and teachings of this invention to utilize aromatic hydrocarbons streams or fractions thereof and/or any other aromatic based hydrocarbon streams or fractions thereof which would not normally be used in normal boiling range gasolines in significant quantities, if any. It is within the teachings and scope of this invention to substitute an individual aromatic hydrocarbon with other aromatic hydrocarbons, with aromatic hydrocarbon streams or fractions thereof, with aromatic based hydrocarbon streams or fractions thereof. Aromatic hydrocarbon substitution may also be made with acceptable non-aromatic hydrocarbon streams or fractions thereof.
• aromatic hydrocarbon streams or fractions thereof may be the product of iso erization units, crude distillation units, cokers, vacuum distillation units, hy rocracking units, catalytic cracking units, riser cracking units, reforming units, akylation units, polymerization units, hydrodesulf ur ization units, pyrolsis units, gasification units and the like, and/or produced from any combination of these units using crude oil, natural gasolines, natural gas, natural gas liquids, heavy gas oils, coal, coal liquids, shale oil, biomass, wood, lignate, peat moss, tar sands and the like, at a refinery, petrochemical complex and/or other production complex.
• volume percentages of aromatic hydrocarbons up to 45% as taught in the Table of Ingredient Ranges and elsewhere in this invention are in addition to the aromatic content percentage of the unleaded gasoline bases as taught in Section 6 below.
• Applicant contemplates that it may be necessary in certain circumstances to tailor the boiling characters and the distillation characteristics of these aromatic hydrocarbon streams or fractions thereof. Tailoring, for example, may include cutting the aromatic hydrocarbon so that its ending boiling point would be between 400 °F to about 550 °F. This may be desirable in order to conform to Applicant's blended fuel with ASTM D 439 standards. In certain instances it may be desirable to separate one or more components within the aromatic based hydrocarbon stream from other components of the stream. Other tailoring would include mixing various noncut or cut aromatic hydrocarbon fractions together.
• SUBSTIT is likely to occur it may be desirable to reduce the concentrations of gum forming hydrocarbons in the composition, increase usage of other solvent ingredients of this invention and/or use appropriate gum inhibitors, such as antioxidants, and/or other antigumming agents.
• Applicant's invention Applicants can effectively improve the end boiling point and emission cha acte istics of the fuel composition which would normally be expected by the addition of the contemplated aromatic hydrocarbon. Applicant's may also control distillation depression and increased RVP which would normally occur with the addition of lower molecular weight alcohols. Applicant also corrects the excessive hydrocarbon emissions occurring with the addition of MMT to unleaded gasoline. These attributes of Applicant's invention represent a very significant departure from the prior art and in view of the prior art literature is quite unexpected and novel.
• Figure 2 illustrates the range of hydrocarbon emissions on the basis of engine out hydrocarbons (EOHC) improvement expected at 5,000 miles using the defined proportions of C to
• the preferred cyclomatic manganese tricarbonyl used in our composition is methyl cyclopentadienyl manganese tricarbonyl (MMT) but the composition can contain a homologue or such other substituents as, for example, alkenyl, aralkyl, aralkenyl, cycloalkyi, cycloalkenyl , aryl and alkenyl groups.
• Illustrative, but nonl imiting examples of such substituted and un s bst i tuted cyclomatic manganese tricarbonyl antiknock compounds are: cyclopentadienyl manganese tricarbonyl; me thyl eye 1 open tad ienyl manganese ben zyl eyel open tad ienyl manganese tricarbonyl;
• concentrations of the methyl cyclomatic manganese tricarbonyl compound concentrations (expressed as grams of manganese metal per gallon of the resulting fuel composition) as low as 1/64 grams manganese per gallon are sufficient in many cases.
• concentrations up to and including 1.0 grams manganese per gallon can be employed, but are less preferred.
• amounts outside of the above-recited range can also be employed, but such concentrations tend to be less satisfactory.
• concentrations of cyclomatic manganese tricarbonyl in the range of from about 1/64 grams to about 1/4 grams manganese/gallon give good results, and concentrations from 1/64 to 1/8 grams manganese/gallon give better results and are preferred.
• This invention also contemplates the use of other additives, such as gum and corrosion inhibitors, multipurpose additives and scavengers, made uecessary or desirable to maintain fuel system cleanliness and control exhaust emissions due to the presence of alcohol, organo-manganese compounds * and aromatic hydrocarbons in the fuel.
• additives such as gum and corrosion inhibitors, multipurpose additives and scavengers, made uecessary or desirable to maintain fuel system cleanliness and control exhaust emissions due to the presence of alcohol, organo-manganese compounds * and aromatic hydrocarbons in the fuel.
• the methods of incorporation of such additives into fuel blends are well known to the art.
• Applicant believes that there is some sort of a three way synergism between aromatic hydrocarbons, MMT and lower molecular alcohols which together in unleaded gasoline, controls the emissions of the resultant fuel composition.
• a cosolvent should also be employed to insure phase stability of the fuel composition to the extent that the fuel composition containing methanol and approximately 500 parts per million water will not phase separate at 15°F, or the lowest probable temperature to which the fuel composition will be exposed.
• the methanol to cosolvent ratio should not exceed about 5 parts methanol to 1 part cosolvent depending upon the nature of the base fuel and the cosolvent(s) used. There does not appear to be any minimum ratio of methanol to cosolvent, except as required by economics or the desired
• the cosolvent(s) can be selected from the group consisting of C2 to C12 aliphatic alcohols, C3 to C12 ke tones and/or C2 to C12 ethers. Within the scope of this invention it is contemplated that these cosolvents may also be used with any C ⁇ _ - CQ aliphatic alcohol, especially in cases where corrosion, phase stability or vapor pressure become an issue. It is also within the scope and teaching of this invention to employ one or more alcohols, ketones or ethers within a particular class of cosolvents and/or to employ any one or more cosolvents classes of this invention simultaneously.
• mixed cosolvents including mixed alcohols, ethers and/or ketones
• mixed cosolvent alcohols particularly tho se in the C2 to C g r ang e have a particularly ameleorative effect on both RVP and octane blending values.
• the preferred cosolvent class rankings would be alcohols first, ketones second, and ethers last.
• the alcohol cosolvents will have from two to twelve carbon atoms.
• the preferred cosolvent alcohols are saturates having high water tolerances and high boiling points.
• Representative alcohol cosolvents include ethanol, isopropanol, n-propanol, tertiary butanol, 2-butanol , isobutanol, n-butanol, pentanols, amyl alcohol, cyclohexanol , 2-ethylhexanol , furfuryl alcohol, iso amyl alcohol, methyl amyl alcohol, te tr ahyd rof ur f uryl alcohol, hexanols, cyclohexanols , septanols, octanols and the like.
• the alcohol cosolvents in reverse order of their preference, are propanols, butanols, pentanols, hexanols and the other higher boiling point alcohols.
• the more preferred alcohol cosolvents include isobutanol, n-butanol, pentanol and the other higher boiling point alcohols.
• the ketones used as cosolvents in fuel compositions taught herein will have from three to about twelve carbon atoms. Lower alkenyl ketones are, however, slightly preferred.
• Representative lower alkenyl ketones would include diethyl ketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, ethyl butyl ketone, butyl isobutyl ketone and ethyl propyl ketone and the like.
• Other ketones include acetone, diacetone alcohol, diisobutyl ketone, isophorone, methyl amyl ketone, methyl isa yl ketone, methyl propyl ketone and the like.
• a representative cyclic ketone would be ethyl phenyl ketone.
• Representative ethers which can be used as cosolvents in fuel compositions taught herein will have from 2 to about 12 carbon atoms and would include the preferred methyl alkyl t-butyl ethers such as methyl tert-butyl ether, ethyl tertiary butyl ether, also preferred tertiary amyl methyl ether, dialkyl ether, isopropyl ether, diisopropyl ether, diethyl ether, ethyl n-butyl ether, ethyl idenedimethyl ether, butyl ether, and ethyl ene glycol dibutyl ether and the like.
• the representative straight ethers which can be used in the fuel blends of this invention would include straight chain ethers such as those presented ' above, as well as cyclic ethers wherein the ether's oxygen molecule is in a ring with carbon atoms.
• straight chain ethers such as those presented ' above, as well as cyclic ethers wherein the ether's oxygen molecule is in a ring with carbon atoms.
• tetrahydrofurans such as, f o r ex ample , 2-me thyl te tr ahyd ro f ur an , 2-ethyl te tr ahydrof ur an , and 3 -methy.letetrahydrof u an may also find use in the present invention.
• the most preferred ether would be a branch chained ether. In order to be most advantageously employed, the above ethers should also be readily soluble, either directly or indirectly in gasoline.
• the preferred methanol/cosolvent ratio will range from 0.2 to 3 parts methanol to 1 part cosolvent. Ratios from about 3 to 5 parts methanol to 1 part cosolvent are also preferred in certain circumstances. The ratio of methanol to cosolvent can exceed 5 to 1 or be less than 0.5 to 1. However methanol/cosolvent ratios outside these ranges are normally less desirable unless vapor pressure or technical enleanment are issues in the fuel -36-
• the more desirable the base fuel composition as described hereafter the less restrictive will be the formulation and construction of the Ci to C6 aliphatic alcohol and cosolvent components.
• the more desirable the base gasoline the greater the permissible percentage oxygen by weight that can be in the finished fuel, the better the RVP response and initial and mid-range distillation characteristics.
• the more desirable the base gasoline the greater the flexibility in reducing or increasing the total percent alcohol cosolvents by volume in the finished gasoline.
• the methanol to cosolvent ratios will generally be higher when a higher boiling point aliphatic alcohol up to C8 is the cosolvent and lowest when ethanol is the cosolvent.
• methanol to cosolvent ratios are higher with alcohols, than they are with ketones, than they are with ethers. That is to say, when a comparable higher boiling point or molecular weight alcohol, ketone or ether is compared, the highest ratio (within the general range of 3 to 5 parts methanol to 1 part cosolvent) is permissible when the cosolvent is an alcohol, the second highest ratio when the cosolvent is the ketone and the lowest ratio when the cosolvent is an ether.
• the preferred ratios might be 3 to 5 parts methanol to 1 part N-butanol, 1 to 2 parts methanol to 1 part methyl ethyl ketone, and 1 part methanol to 2 to 3 parts diethyl ether.
• the methanol-cosolvent ratios should be at their highest when higher molecular weight cosolvent molecules (e.g., C4 - C12) are used.
• Hydrocarbon Components example, a lower methanol to cosolvent ratio and a higher average boiling point alcohol and cosolvent components. This same low aromatic gasoline will limit the flexibility of reducing or increasing the total volume of the alcohol component. It is likely that the alcohol component as a percent of volume would be easier to increase then it would be to decrease.
• a methanol to cosolvent ratio of 3 to 1 using isopropanol as the cosolvent, together with the alcohol component representing 7 percent by volume of the fuel would normally be acceptable if the fuel were to be distributed in a dry system averaging 60°F.
• certain adjustments would have to be made. One or more of the following adjustments would be required:
• the age of the vehicular population which consumes the finished fuel also impacts the amount of oxygen which may be contained in the fuel.
• the finished fuel may contain upwards to 5-7 percent total oxygen by weight.
• Those newer automobiles using 3-way catalysts which require more stringent air fuel ratios are limited to generally 4-5 percent total oxygen by weight.
• SUBSTITUTE SHEET containing oxygen sensing devices may use fuels containing upwards of 7 percent oxygen by weight. With the anticipated improvements of oxygen sensing devices in 1985 and future model years, the oxygen content of the finished fuel could approach 12 percent or more by weight.
• cosolvent 1 Another element that must be considered when formulating the cosolvent component, is the cosolvent 1 s effect with the aromatic hydrocarbon component on mid and end range distillation temperatures.
• c 2 " c 4 alcohols up to and including TBA
• C4 (higher than TBA) - C12 alcohols tend to reduce temperatures beyond the mid-range.
• the inclusion of aromatic hydrocarbons into the fuel composition raises end range temperatures and tends to compress the distillation curve with the effect of increasing mid-range temperatures. Therefore, effect must be given to the particular characte istics of ' the aromatic hydrocarbon component (i.e., boiling range, end boiling point and the like) when formulating the cosolvent component.
• the higher the end boiling point of the aromatic hydrocarbon component the higher the average molecular weight of the cosolvent component.
• Aromatic hydrocarbon component of the composition comparison must be made between their octane, RVP, emissions and distillation benefits versus the butane debit of utilizing certain lower molecular weight alcohols in the composition.
• gasoline to which this invention is applied is a lead fuel or substantially lead free
• gasoline bases in Applicants' fuel composition are conventional motor fuels boiling in the general range of about 70° to about 40°F. They include substantially all grades of unleaded gasoline presently being employed in spark ignition internal
• gasolines can be prepared from saturated hydrocarbons, e.g., straight stocks, alkylation
• the base gasoline will be a blend of stocks obtained from several refinery processes.
• the final blend may also contain hydrocarbons made by other procedures such as alkylates made by the reaction of C4 olefins and butanes using an acid catalyst such
• UB as sulfuric acid or hydrofluoric acid, and aromatics made from a reformer.
• the olefins are generally formed by using such procedures as thermal cracking and catalytic cracking, Deyhydrogenation of paraffins to olefins can supplement the gaseous olefins occurring in the refinery to produce feed material for either polymerization or alkylation processes.
• the saturated gasoline components comprise paraffins and naphthenates. These saturates are obtained from: (1) virgin gasoline by distillation (straight run gasoline), (2) alkylation processes (alkylates), and (3) isomer ization procedures (conversion of normal paraffins to branched chain paraffins of greater octane quality). Saturated gasoline components also occur in so-called natural gasolines.
• gasoline bases are those having an octane rating of (R + M)/2 ranging from 78-95. It is desirable to blend the gasoline base as contemplated in Applicant's invention so that the minimum aromatic content within a normal gasoline base, to which the balance of Applicant's ingredients are added to, is no less than 5% and preferably greater than 20%. This minimum aromatic content of the base gasoline may be generated and introduced into the gasoline as a compliment to or as a result of the process stream(s) or fractions thereof which are taught as necessary hydrocarbon ingredients of this invention.
• the gasoline base should have an olefinic content ranging from 1% to 30%, and a saturate hydrocarbon content ranging from about 40 to 80 volume percent.
• the motor gasoline bases used in formulating the fuel blends of this invention generally are within the parameters of ASTM D-439 and have initial boiling
• SUBSTITUTE SHEET points ranging from about 70 °F to about 115 °F and final boiling points ranging from about 380 °F to about 440 °F as measured by the standard ASTM distillation procedure (ASTM D-86 ) . Intermediate gasoline fractions boil away at temperatures within these extremes.
• desirable base gasoline compositions would include as many aromatics with Cs or lower carbon molecules as possible in the circumstances.
• the ranking or aromatics in order of their preference would be: benzene, toluene, m-xylene, ethylbenzene, o-xylene, isoproplydenzene, N-propybenzene and the like.
• the next preferred gasoline component in terms of phase stability would be olefins.
• the ranking of preferred olefins in order of their preference would be; 2-methyl-2-butane, 2 methyl-1 butane, 1 pentent, and the like.
• olefinic content must be closely watched.
• the least preferred gasoline component in terms of phase stability would be paraffins.
• the ranking of preferred paraffins in order of their preference would be; cyclopentane, N-pentane, 2,3 dimethylbutane, isohexane, 3-methylpentane and the like.
• aromatics are generally preferred over olefins and olefins are preferred over paraffins.
• olefins are preferred over paraffins.
• the lower molecular weight components are preferred over the higher molecular weight components.
• base gasolines having a low sulfur content as the oxides of sulfur tend to contribute to the irritating and choking characteristics of smog and other forms of atmospheric pollution.
• the base gasolines should contain not more than 0.1 weight percent of sulfur in the form of conventional sulfur-containing impurities. Fuels in which the sulfur content is no more than about 0.02 weight percent are especially preferred for use in this invention.
• the gasoline bases of this invention can also contain other high octane organic blending agents.
• Nonlimiting examples include phenols (e.g., P-cresal, 2, 4 xylenal, 3-methoxyphenal) , esters (e.g., isopropyl acetate, ethyl acrylate) oxides (e.g., 2-methylfuran) , ketones (e.g., acetone, cyclopentanone), alcohols (furon, furfuryl), ethers (e.g., MTBE, TAME, dimethyl, diisopropyl) , aldehydes and the like.
• phenols e.g., P-cresal, 2, 4 xylenal, 3-methoxyphenal
• esters e.g., isopropyl acetate, ethyl acrylate
• oxides e.g., 2-methylfuran
• ketones e.g., ace
• the gasoline bases which this invention employs should be lead-free or substantially lead-free.
• the gasoline may contain antiknock quantities of other agents such as cyclopentadienyl nickel nitrosyl, N-methyl aniline, and the like. Antiknock promoters such as 2.4 pentanedione may also be included.
• the descriptive characteristics of one common base gasoline is given as example 2. Obviously many other standard and specialized gasolines can be used in Applicants' fuel blend.
• the fuel composition of this invention can generally be prepared by adding the cyclopentadienyl manganese antiknock compound, the C ⁇ to C ⁇ alcohols and the cosolvents, if any, together with aromatic hydrocarbons together with the base gasoline with sufficient agitation to give a uniform composition to the finished fuel. It is essential in the practice of this invention only that the novel combination of additives, a cyclopentadienyl manganese tricarbonyl and the Ci to C 6 alcohols and cosolvents, if any, along with aromatic hydrocarbons be present in the defined-proportions with unleaded gasoline bases immediately prior to vaporization and combustion of the fuel in the engine. Accordingly, it is within the scope of this invention to add the components of the composition as herein taught either separately in any sequence, or as a mixture with each other, so long as the foregoing requirement is met.

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• 1986
  • 1986-08-26 DE DE8686906042T patent/DE3682503D1/de not_active Expired - Lifetime
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