WO2017127071A1 - Methods of increasing the heating value of fuel - Google Patents

Methods of increasing the heating value of fuel Download PDF

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Publication number
WO2017127071A1
WO2017127071A1 PCT/US2016/014129 US2016014129W WO2017127071A1 WO 2017127071 A1 WO2017127071 A1 WO 2017127071A1 US 2016014129 W US2016014129 W US 2016014129W WO 2017127071 A1 WO2017127071 A1 WO 2017127071A1
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Prior art keywords
fuel
liquid hydrocarbon
polymer
hydrocarbon fuel
heating value
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PCT/US2016/014129
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French (fr)
Inventor
Jerry TRIPPE
Preston WAHL
Michael ANFINSON
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Viscon Usa Llc
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Priority to PCT/US2016/014129 priority Critical patent/WO2017127071A1/en
Publication of WO2017127071A1 publication Critical patent/WO2017127071A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • C10L1/1625Hydrocarbons macromolecular compounds
    • C10L1/1633Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L2200/00Components of fuel compositions
    • C10L2200/04Organic compounds
    • C10L2200/0407Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415Light distillates, e.g. LPG, naphtha
    • C10L2200/0423Gasoline
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L2200/00Components of fuel compositions
    • C10L2200/04Organic compounds
    • C10L2200/0407Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/043Kerosene, jet fuel
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L2200/00Components of fuel compositions
    • C10L2200/04Organic compounds
    • C10L2200/0407Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446Diesel
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L2230/00Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/22Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency

Definitions

  • Fuel additives are known to enhance fuel performance, for example, if they are fuels themselves, or used to adapt the physical properties of the fuel to enhance engine performance. See, e.g., U.S. Patent Number 5,906,665.
  • low concentrations of high molecular weight polymers, such as high molecular weight polyisobutylene, are known to reduce flow turbulence and have been used as drag-reducing additives. See, e.g., U.S. Pat. Nos.
  • High molecular weight alpha-olefins are known as anti-misting additives for fuels to reduce flammability of fuel sprays occurring during aircraft crashes.
  • U.S. Pat. No. 4,789,383 discloses the use of high molecular weight polymer (e.g., Oppanol® B200
  • polyisobutylene having a molecular weight of about 4 million Daltons polyisobutylene having a molecular weight of about 4 million Daltons
  • very high molecular weight polymers as those above 5 million Daltons.
  • U.S. Patent Number 5,906,665 assigned to the assignee of the present application, is directed to methods of improving the mechanical efficiency of fuel-burning devices, such as gasoline engines, diesel engines, furnaces and burners, by adding an effective amount of a high- molecular weight polymer to the fuel (e.g., ultra-high molecular weight polyisobutylene
  • PIB polyisobutene
  • PIB is a pure hydrocarbon which burns to carbon dioxide and water vapor, or decomposes cleanly to gaseous isobutene which also burns to carbon dioxide and water vapor.
  • U.S. Patent Number 5,906,665 PIB is thought to increase combustion efficiency through its extended molecular length attributed to polymerization of other monomers with isobutene resulting in co-polymers which improve efficiency at high molecular weights and imposing non-Newtonian characteristics on the fuel. See, e.g.. U.S. Pat. No. 4,508,128. U.S. Pat. Nos. 4,573,488 and 5,080,121.
  • the low carbon fuel standard (LCFS) was first enacted in 2007 by the ARB.
  • Other U.S. States, the U.S. Federal Government and other governments are considering similar legislation and rules.
  • the California regulation requires oil refineries and distributors to ensure that fuels meet stringent carbon emissions standards with a goal of reducing California transportation fuel carbon intensity by 10% by the year 2020.
  • the LCFS was enacted to reduce carbon intensity in transportation fuels and to encourage the use of alternatives (e.g., ethanol, compressed natural gas (CNG) or liquefied natural gas (LNG)).
  • alternatives e.g., ethanol, compressed natural gas (CNG) or liquefied natural gas (LNG)
  • alternatives e.g., ethanol, compressed natural gas (CNG) or liquefied natural gas (LNG)
  • alternatives e.g., ethanol, compressed natural gas (CNG) or liquefied natural gas (LNG)
  • Carbon intensity refers to the amount of carbon produced per unit of energy created in combustion of a fuel (gC0 2 /MJ).
  • C0 2 is calculated from the carbon content of the fuel.
  • the energy component (MJ) is the fuel's heat of combustion or "heating value.”
  • the heating value of a fuel refers to the amount of heat released during combustion of a defined amount of fuel using a bomb calorimeter.
  • aspects herein provide methods of increasing the heating value of liquid hydrocarbon fuel by adding an effective amount of a high molecular weight polymer.
  • high molecular weight polymer fuel additives were used to increase combustion efficiency in fuel burning devices. In these applications, atomization of the fuel formed fuel droplets resulting in faster heat release and increased combustion efficiency. Thus, it was believed that the beneficial effects of the high molecular weight polymer additives could only be achieved through atomization of the fuel.
  • aspects described herein provide methods of increasing the heating value of a liquid hydrocarbon fuel by adding an effective amount of a polymer having a molecular weight greater than about 2 million Daltons to the liquid hydrocarbon fuel.
  • the heating value of the liquid carbon fuel is increased by at least about 2% compared to a liquid hydrocarbon fuel without the added polymer when the liquid hydrocarbon fuel is burned to completion.
  • the heating value of the liquid carbon fuel can be increased from about 2% to about 8%, for example, by increasing the molecular weight of the polymer added to the liquid hydrocarbon fuel.
  • the polymer is selected from polyisobutylenes (PIB) with a relative mass ranging from about 2 million Daltons to about 6 million Daltons.
  • PIB polyisobutylenes
  • Examples of PIB s suitable for use in aspects described herein include, but are not limited to, Oppanol ® B 100, Oppanol ® B 150, and Oppanol ® B 200 (BASF).
  • the liquid hydrocarbon fuel is selected from the group consisting of gasoline, heating oil, jet fuel, kerosene, diesel fuel, and residual fuel oil.
  • the molecular weight of the polymer is greater than about 4 million Daltons or greater than about 6 million Daltons.
  • the PIBs have a concentration range of about 0.1 ppm to about 100 ppm by weight in the liquid hydrocarbon fuel. In another aspect, the PIBs are in a concentration range of about 1 to about 20 ppm by weight in the liquid hydrocarbon fuel.
  • FIG. 1 Further aspects provide methods of increasing the heating value of a liquid hydrocarbon fuel by adding an effective amount of a polymer having a molecular weight of about 2 million to 7 million Daltons to the liquid hydrocarbon fuel.
  • the heating value of the liquid hydrocarbon fuel is increased by about 2% to 8% compared to liquid hydrocarbon fuel without the added polymer.
  • Yet another aspect provides methods of increasing the heating value of gasoline comprising adding an effective amount of a polymer having a molecular weight greater than about 2 million Daltons to the liquid hydrocarbon fuel wherein the heating value of the gasoline is greater than about 20,000 BTU per pound of gasoline when the gasoline is burned to completion.
  • ExxonMobil was weighed in a small mixing pot.
  • the solvent was heated to 140 °F and the polymer was added.
  • the polymer and solvent mixed at a speed sufficient to keep the PIB moving in the solvent without falling to the bottom. For example, 50 RPM for the first 30 minutes and then 23 RPM for 11.5 hours. The solution was mixed until no particles could be observed.
  • the enthalpies of the reactants cannot be determined from the enthalpies of formation of the reactant species because the reactant species and their amounts are not precisely known. Heywood, "Internal Combustion Engine Fundamentals", (McGraw Hill International Edition, 1988) pages 78-79. Therefore, the heating value or heat of combustion is measured directly. Id.
  • the heating value QHV or calorific value of a fuel is the magnitude of the heat of reaction at constant pressure or at a constant volume at a standard temperature. Id.
  • the heating value is typically expressed in joules per kilogram and measured in a calorimeter. In this aspect, the fuel is burned with oxygen under pressure at a constant volume in a bomb calorimeter. Id. At 79.
  • the heat of combustion is determined by burning a weighed sample in an oxygen bomb calorimeter under controlled conditions. Temperature observations are made before, during, and after combustion while making thermochemical and heat transfer adjustments and corrections. Id.
  • carbon intensity values can be generated using the California- modified GREET (CA-GREET) model.
  • Vehicles generate greenhouse gases including C0 2 and CO and hydrocarbon emissions.
  • CARBOB California Reformulated Gasoline Blendstock for Oxygenate Blending
  • CO and hydrocarbon emissions are converted to C0 2 in the atmosphere within a few days.
  • CA-GREET values include only the C0 2 emissions from vehicles on a per-mile bases using "tank to wheel” calculations. Id.
  • the carbon in the fuel is calculated from the carbon content and fuel density.
  • the average carbon ratio for CARBOB is 85.9% by weight or 76,921 grams of C0 2 per mmBtu of fuel or 79.21 g C0 2 /MJ. Id.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Methods of increasing the heating value of liquid hydrocarbon fuels are provided. Aspects include adding an effective amount of a high molecular weight polymer to the fuel wherein the heating value of the fuel is increased.

Description

METHODS OF INCREASING THE HEATING VALUE OF FUEL
[0001] All references cited herein, including but not limited to patents and patent applications, are incorporated by reference in their entirety.
BACKGROUND
[0002] Carbon emissions resulting from burning fossil fuels is increasingly a worldwide concern. The Paris climate change agreement negotiated in December 2015 further demonstrates that additional and significant steps will be taken to limit carbon emissions. Carbon emitted from fuel burning devices, such as cars, are a significant source of pollution.
[0003] The energy efficiency of gasoline engines (e.g., spark ignition engines) is notoriously poor. Only about 14-30% of the energy from fuel put in a conventional vehicle is used to move the vehicle down the road. U.S. Department of Energy (www.fueleconomy.gov). Energy loss can be attributed to thermal loss (e.g., combustion, exhaust heat, radiator), power to wheels (e.g., wind resistance, braking, rolling resistance), drivetrain losses, and idling losses. Id.
[0004] The impact of carbon emissions on pollution and climate change has led to dramatic changes in fuel burning technologies along with more stringent legal requirements to reduce and minimize carbon emissions. For example, the California Air Resources Board (ARB), a part of the California Environmental Protection Agency, has enacted rules and regulations to reduce air pollution in California. According to the ARB, 30 million vehicles traverse California roads per day accounting for 40% of greenhouse gas emissions. In response, California enacted the low carbon fuel standard (LCFS) to encourage development of alternative fuels with lower carbon intensity in an effort to curb C02 emissions resulting from use of transportation fuels.
[0005] Fuel additives are known to enhance fuel performance, for example, if they are fuels themselves, or used to adapt the physical properties of the fuel to enhance engine performance. See, e.g., U.S. Patent Number 5,906,665. In certain applications low concentrations of high molecular weight polymers, such as high molecular weight polyisobutylene, are known to reduce flow turbulence and have been used as drag-reducing additives. See, e.g., U.S. Pat. Nos.
4,546,748 and 4,837,249.
[0006] High molecular weight alpha-olefins are known as anti-misting additives for fuels to reduce flammability of fuel sprays occurring during aircraft crashes. For example, U.S. Pat. No. 4,789,383 discloses the use of high molecular weight polymer (e.g., Oppanol® B200
(polyisobutylene having a molecular weight of about 4 million Daltons)) and very high molecular weight polymers as those above 5 million Daltons.
[0007] U.S. Patent Number 5,906,665, assigned to the assignee of the present application, is directed to methods of improving the mechanical efficiency of fuel-burning devices, such as gasoline engines, diesel engines, furnaces and burners, by adding an effective amount of a high- molecular weight polymer to the fuel (e.g., ultra-high molecular weight polyisobutylene
(polyisobutene)(PIB)). PIB is a pure hydrocarbon which burns to carbon dioxide and water vapor, or decomposes cleanly to gaseous isobutene which also burns to carbon dioxide and water vapor. As discussed in U.S. Patent Number 5,906,665, PIB is thought to increase combustion efficiency through its extended molecular length attributed to polymerization of other monomers with isobutene resulting in co-polymers which improve efficiency at high molecular weights and imposing non-Newtonian characteristics on the fuel. See, e.g.. U.S. Pat. No. 4,508,128. U.S. Pat. Nos. 4,573,488 and 5,080,121.
[0008] According to U.S. Patent Number 5,906,665, the increased mechanical efficiency of fuel-burning is believed to be attributed to suppression in the formation of sub-50-micron diameter droplets as the fuel is sprayed resulting in increased momentary, or extensional, viscosity of the fuel droplets under conditions such as those encountered in engine fuel and combustion systems. The previously described apparatus atomizes the fuel to increase efficiency of fuel burning resulting in, for example, faster heat release resulting from the viscoelasticity of the high molecular weight polymer additive. The PIB, for example, controls the rate of fuel vaporization by providing a more uniform fuel droplet size and suppressing formation of very small droplets. SUMMARY
[0009] The low carbon fuel standard (LCFS) was first enacted in 2007 by the ARB. Other U.S. States, the U.S. Federal Government and other governments are considering similar legislation and rules. The California regulation requires oil refineries and distributors to ensure that fuels meet stringent carbon emissions standards with a goal of reducing California transportation fuel carbon intensity by 10% by the year 2020. The LCFS was enacted to reduce carbon intensity in transportation fuels and to encourage the use of alternatives (e.g., ethanol, compressed natural gas (CNG) or liquefied natural gas (LNG)). However, current efforts with respect to alternative fuels typically do not typically consider reformulating conventional fossil fuels (e.g., gasoline, diesel).
[0010] Carbon intensity refers to the amount of carbon produced per unit of energy created in combustion of a fuel (gC02/MJ). In the formula for carbon intensity, C02 is calculated from the carbon content of the fuel. The energy component (MJ) is the fuel's heat of combustion or "heating value." The heating value of a fuel refers to the amount of heat released during combustion of a defined amount of fuel using a bomb calorimeter.
[0011] Aspects herein provide methods of increasing the heating value of liquid hydrocarbon fuel by adding an effective amount of a high molecular weight polymer. Previously, high molecular weight polymer fuel additives were used to increase combustion efficiency in fuel burning devices. In these applications, atomization of the fuel formed fuel droplets resulting in faster heat release and increased combustion efficiency. Thus, it was believed that the beneficial effects of the high molecular weight polymer additives could only be achieved through atomization of the fuel.
[0012] Unexpectedly, the present inventors discovered that the heating value of liquid hydrocarbon fuel is significantly increased by the high molecular weight polymers in the absence of atomization of the fuel. Methods of the invention permit, for example, the manufacture of liquid hydrocarbon fuels that meet the California LCFS standards. DETAILED DESCRIPTION
[0013] Before describing several exemplary aspects described herein, it is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description. The aspects described herein are capable of being practiced or being carried out in various ways.
[0014] Aspects described herein provide methods of increasing the heating value of a liquid hydrocarbon fuel by adding an effective amount of a polymer having a molecular weight greater than about 2 million Daltons to the liquid hydrocarbon fuel. In this aspect, the heating value of the liquid carbon fuel is increased by at least about 2% compared to a liquid hydrocarbon fuel without the added polymer when the liquid hydrocarbon fuel is burned to completion. In this aspect the heating value of the liquid carbon fuel can be increased from about 2% to about 8%, for example, by increasing the molecular weight of the polymer added to the liquid hydrocarbon fuel.
[0015] In another aspect, the polymer is selected from polyisobutylenes (PIB) with a relative mass ranging from about 2 million Daltons to about 6 million Daltons. Examples of PIB s suitable for use in aspects described herein include, but are not limited to, Oppanol® B 100, Oppanol® B 150, and Oppanol® B 200 (BASF).
[0016] In another aspect, the liquid hydrocarbon fuel is selected from the group consisting of gasoline, heating oil, jet fuel, kerosene, diesel fuel, and residual fuel oil. In yet another aspect, the molecular weight of the polymer is greater than about 4 million Daltons or greater than about 6 million Daltons.
[0017] In further methods, the PIBs have a concentration range of about 0.1 ppm to about 100 ppm by weight in the liquid hydrocarbon fuel. In another aspect, the PIBs are in a concentration range of about 1 to about 20 ppm by weight in the liquid hydrocarbon fuel.
[0018] Further aspects provide methods of increasing the heating value of a liquid hydrocarbon fuel by adding an effective amount of a polymer having a molecular weight of about 2 million to 7 million Daltons to the liquid hydrocarbon fuel. In this aspect, the heating value of the liquid hydrocarbon fuel is increased by about 2% to 8% compared to liquid hydrocarbon fuel without the added polymer.
[0019] Yet another aspect provides methods of increasing the heating value of gasoline comprising adding an effective amount of a polymer having a molecular weight greater than about 2 million Daltons to the liquid hydrocarbon fuel wherein the heating value of the gasoline is greater than about 20,000 BTU per pound of gasoline when the gasoline is burned to completion.
[0020] Further aspects provide methods of manufacturing a hydrocarbon fuel by adding an effective amount of a polymer having a molecular weight greater than about 2 million Daltons to the liquid hydrocarbon fuel. In this aspect, the heating value of the liquid carbon fuel is increased by at least about 2% compared to a liquid hydrocarbon fuel without the added polymer when the liquid hydrocarbon fuel is burned to completion.
EXAMPLES
[0021] The following non-limiting examples illustrate aspects described herein. [0022] Example 1
[0023] Preparation of PIB and PIB/Gasoline Solutions
[0024] Two gallons of Solvent 142 (Exxsol D60™, 47.5 API at the time of use,
ExxonMobil) was weighed in a small mixing pot. The solvent was heated to 140 °F and the polymer was added. The polymer and solvent mixed at a speed sufficient to keep the PIB moving in the solvent without falling to the bottom. For example, 50 RPM for the first 30 minutes and then 23 RPM for 11.5 hours. The solution was mixed until no particles could be observed.
[0025] For each blend shown in Table 1, three gallons of gasoline (Chevron, 87 Octane) was poured into a mixing pot and dosed (1 ounce to 10 gallons (781.25 ppm)) with the indicated PIB blend and mixed for 30 minutes. Eight ounces of the resulting mixture was used for heating value measurements discussed above.
[0026] Example 2
[0027] Measuring the Heat of Combustion of Liquid Hydrocarbon Fuels
[0028] For mixed-component fuels, the enthalpies of the reactants cannot be determined from the enthalpies of formation of the reactant species because the reactant species and their amounts are not precisely known. Heywood, "Internal Combustion Engine Fundamentals", (McGraw Hill International Edition, 1988) pages 78-79. Therefore, the heating value or heat of combustion is measured directly. Id. The heating value QHV or calorific value of a fuel is the magnitude of the heat of reaction at constant pressure or at a constant volume at a standard temperature. Id. The heating value is typically expressed in joules per kilogram and measured in a calorimeter. In this aspect, the fuel is burned with oxygen under pressure at a constant volume in a bomb calorimeter. Id. At 79.
[0029] The standard test for measuring the heat of combustion for liquid hydrocarbon fuels is provided in ASTM (American Society for Testing and Materials) International D240
(www.astm.org/Standards/D240). In one aspect, the heat of combustion is determined by burning a weighed sample in an oxygen bomb calorimeter under controlled conditions. Temperature observations are made before, during, and after combustion while making thermochemical and heat transfer adjustments and corrections. Id.
[0030] By way of example, carbon intensity values can be generated using the California- modified GREET (CA-GREET) model. Vehicles generate greenhouse gases including C02 and CO and hydrocarbon emissions. See., Detailed CA-GREET Pathway for California Reformulated Gasoline Blendstock for Oxygenate Blending (CARBOB) from Average Crude Refined in California (California Environmental Protection Agency, Air Resources Board, Stationary Source Division, February 27, 2009, Version 2.1). CO and hydrocarbon emissions are converted to C02 in the atmosphere within a few days. Id. However, the CA-GREET values include only the C02 emissions from vehicles on a per-mile bases using "tank to wheel" calculations. Id. The carbon in the fuel is calculated from the carbon content and fuel density. Id. In the CA-GREET model, for example, the average carbon ratio for CARBOB is 85.9% by weight or 76,921 grams of C02 per mmBtu of fuel or 79.21 g C02/MJ. Id.
[0031] Example 3
[0032] Heating Values for Gasoline/PIB Blends
[0033] The table below provides the Gross Heat of Combustion for gasoline, PIB/Gasoline blend G2105B150110, PIB gasoline blend G2105B250110, and PIB/gasoline blend
G2105S150110. The PIB concentration in the gasoline for each sample was 15.6 ppm. Heating Values were measured using ASTM International D240 (www.astm.org/Standards/D240) which is incorporated by reference herein in its entirety.
[0034] Table 1
Fuel Sample PIB Gross Heat of Percent increase
Combustion j/kg) vs. Gasoline
Gasoline NA 45.525 NA
G2105B 150110 Oppanol B 150 (mol. 47.150 3.5 %
wt 2.6 million
Daltons.)
G2105S150110 Laxness SGPPO150B 48.785 7.1%
(mol. wt. about 6
million Daltons)
G2105B250110 Oppanol B 250 (mol. 49.125 7.9%
wt. 7 million Daltons)
[0035] As shown in Table 1, as the molecular weight of the PIB increases, the heating value of the resulting fuel increases.
[0036] Example 4
[0037] PIB Additive Specifications
[0038] Table 2
47.5
API Gravity @ 60°F, 15.6°C
Pounds per Gallon 6.581 lbs
Specific Gravity .78857749
Flash Point °F / °C 144°F / 62.2°C
Viscosity Eta cP @ 90°F, 32.2°C 144 cP
Color Clear to White
[0039] Not every element described herein is required. Indeed, a person of skill in the art will find numerous additional uses of and variations to the methods described herein, which the inventors intend to be limited only by the claims. All references cited herein are incorporated by reference in their entirety.

Claims

CLAIMS What is claimed is:
1. A method of increasing the heating value of a liquid hydrocarbon fuel comprising adding an effective amount of a polymer having a molecular weight greater than about 2 million Daltons to the liquid hydrocarbon fuel, wherein the heating value of the liquid carbon fuel is increased by at least about 2% compared to a liquid hydrocarbon fuel without the added polymer when the liquid hydrocarbon fuel is burned to completion.
2. The method of claim 1, wherein the liquid hydrocarbon fuel is selected from the group consisting of gasoline, heating oil, jet fuel, kerosene, diesel fuel, and residual fuel oil.
3. The method of claim 1, wherein the molecular weight of the polymer is greater than about 4 million Daltons.
4. The method of claim 1, wherein the molecular weight of the polymer is greater than about 6 million Daltons.
5. The method of claim 1, wherein the polymer comprises polyisobutylene in a concentration range of about 0.1 ppm to about 100 ppm by weight in the liquid hydrocarbon fuel.
6. The method of claim 5, wherein the polymer comprises polyisobutylene in a concentration range of about 1 to about 20 ppm by weight in the liquid hydrocarbon fuel.
7. A method of increasing the heating value of a liquid hydrocarbon fuel comprising adding an effective amount of a polymer having a molecular weight of about 2 million to 7 million Daltons to the liquid hydrocarbon fuel wherein the heating value of the liquid hydrocarbon fuel is increased by about 2% to 8% compared to liquid hydrocarbon fuel without the added polymer.
8. The method of claim 7, wherein the liquid hydrocarbon fuel is selected from the group consisting of gasoline, heating oil, jet fuel, kerosene, diesel fuel, and residual fuel oil.
9. A method of increasing the heating value of gasoline comprising adding an effective amount of a polymer having a molecular weight greater than about 2 million Daltons to the liquid hydrocarbon fuel wherein the heating value of the gasoline is greater than about 20,000 BTU per pound of gasoline when the gasoline is burned to completion.
10. The method of claim 9, wherein the molecular weight of the polymer is from about 2.6 million Daltons to about 7 million Daltons.
11. The method of claim 9, wherein the polymer comprises polyisobutylene in a concentration range of about 0.1 ppm to about 100 ppm by weight.
12. The method of claim 11, wherein the polymer comprises polyisobutylene in a concentration range of about 1 to about 20 ppm by weight.
13. A method of making a liquid hydrocarbon fuel comprising adding an effective amount of a polymer having a molecular weight greater than about 2 million Daltons to the liquid hydrocarbon fuel wherein the heating value of the liquid carbon fuel is increased by at least about 2% compared to a liquid hydrocarbon fuel without the added polymer when the liquid hydrocarbon fuel is burned to completion.
14. The method of claim 13, wherein the molecular weight of the polymer is from about 2.6 million Daltons to about 7 million Daltons.
15. The method of claim 13, wherein the polymer comprises polyisobutylene in a concentration range of about 0.1 ppm to about 100 ppm by weight.
16. The method of claim 15, wherein the polymer comprises polyisobutylene in a concentration range of about 1 to about 20 ppm by weight.
PCT/US2016/014129 2016-01-20 2016-01-20 Methods of increasing the heating value of fuel WO2017127071A1 (en)

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US5906665A (en) * 1995-09-26 1999-05-25 General Technology Applications, Inc. High molecular weight fuel additive
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