WO2023081347A1 - Phosphite antioxidants for fuels and related methods - Google Patents

Phosphite antioxidants for fuels and related methods Download PDF

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Publication number
WO2023081347A1
WO2023081347A1 PCT/US2022/048946 US2022048946W WO2023081347A1 WO 2023081347 A1 WO2023081347 A1 WO 2023081347A1 US 2022048946 W US2022048946 W US 2022048946W WO 2023081347 A1 WO2023081347 A1 WO 2023081347A1
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composition
alkyl
phosphite
compound
moiety
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PCT/US2022/048946
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French (fr)
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Michael Jakupca
Jacob LANCE
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Dover Chemical Corporation
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    • 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
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/08—Inhibitors
    • C10L2230/081—Anti-oxidants
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

  • Combustion engines use these carbon-based fuels, and in doing so, yield unwanted combustionengine emissions such as: i) nitric oxide, ii) nitrogen dioxide, iii) carbon monoxide, and iv) residual hydrocarbons and particulates. These remains a need to reduce these unwanted combustion-engine emissions.
  • Embodiments are directed to a fluid mixture having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component.
  • Petroleum-based diesel, biodiesel, gasoline, and aviation fuels are known.
  • Phosphite compounds are also known, and any known phosphite compound can be employed as an antioxidant in the above identified fuels.
  • Useful phosphites include alkyl phosphites and aryl phosphites having the structure:
  • R 2 o R r O-P-O-R 3 wherein each R is an independently selected moiety that is an alkyl, aryl, alkyl-aryl, or hindered aryl moiety.
  • a hindered aryl moiety is an aryl moiety having attached thereto a branched-carbon-chain moiety that has three or more carbon atoms; nonlimiting examples of a hindered aryl moiety include: 1) an aryl moiety having attached thereto a tert butyl moiety, and 2) an aryl moiety having attached thereto a cumyl moiety.
  • phosphites having the following chemical structure are useful: wherein each R 1 , R 2 , R 3 , R 4 and R 5 is independently selected and is a Cio-Cis alkyl moiety; n is an integer ranging from 3 to 11; and the sum of Xi + X2 is an integer ranging from 1-500.
  • the compound has a weight ranging from 1000 to 30000 Daltons. In some other phosphorus-containing copolymer compound embodiments, such as those having the immediately above chemical structure, the compound has a weight ranging from 400 to 30000 Daltons. In some other phosphorus-containing copolymer compound embodiments, such as those having the immediately above chemical structure, the compound has a weight ranging from 500 to 30000 Daltons.
  • phosphite compounds having the following chemical structure are also useful: wherein each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000.
  • each Y is independently selected and is an ethyl, propyl, cyclohexane dimethanol, or caprylactone moiety.
  • each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000, the compound has a weight ranging from 1000 to 30000 Daltons.
  • the compound has a weight ranging from 400 to 30000 Daltons. In some polyhydrogen-phosphite embodiments, such as those having the immediately above chemical structure, the compound has a weight ranging from 500 to 30000 Daltons.
  • Useful amounts of phosphite antioxidants range from 0.01 to 5.0% by volume of the fluid mixture. Persons of ordinary skill in the art will be able to determine useful amounts of phosphite antioxidants without having to exercise undue experimentation.
  • Other embodiments include using additional antioxidants, in addition to a phosphite, such as a hindered phenolic or an amine compound.
  • a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component having the following chemical structure:
  • each R 1 , R 2 , R 3 , R 4 and R 5 is independently selected and is a Cio-Cis alkyl moiety; n is an integer ranging from 3 to 11; and the sum of Xi + X2 is an integer ranging from 1-500, yields reduced unwanted combustion-engine emissions relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
  • a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component having the following chemical structure: wherein each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000, yields reduced unwanted combustion-engine emissions relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component
  • a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component having the following chemical structure:
  • each R 1 , R 2 , R 3 , R 4 and R 5 is independently selected and is a Cio-Cis alkyl moiety; n is an integer ranging from 3 to 11; and the sum of Xi + X2 is an integer ranging from 1-500, has inhibited fuel degradation relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
  • a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component having the following chemical structure: wherein each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000, has inhibited fuel degradation relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
  • a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component having the following chemical structure: wherein each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000, has reduced water content relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
  • Figure 1 shows the reaction of alkyl phosphites with hydroperoxides and water.
  • R is an aryl or hindered aryl
  • Alkyl phosphites are generally quicker to react with hydroperoxides and water compared to aryl phosphites.
  • hydroperoxides are both a result of thermal degradation and also promote further degradation of hydrocarbons. Removing hydroperoxides improves fuel quality and thermal stability.
  • Aryl and hindered aryl phosphites do not readily react with hydroperoxides at ambient temperatures (less than 50°C). Hindered aryl phosphites are particularly resistant towards reaction with water.
  • Peroxide Value is a measurement of the level of hydroperoxides in the sample.
  • Table 1 displays the peroxide values of a soybean based fatty acid methyl ester and isooctane at ambient conditions (temperatures less than 50°C).
  • the methyl ester is used as an example of biodiesel and the isooctane was used as an example of a hydrocarbon based fuel such as diesel.
  • the initial peroxide value of the methyl ester and isooctane were 6.0 and 18.8 respectively.
  • the addition of an alkyl phosphite DOVERPHOS LGP-11) scavenged hydroperoxides that were present and reduced the peroxide value to less than 0.5 in both the methyl ester and the isooctane.
  • DOVERNOX 76 is an example of a hindered phenolic stabilizer. They are used to protect hydrocarbons from oxidation, however they cannot remove any hydroperoxides that are initially present.
  • DOVERPHOS S-480 is an example of a hindered aryl phosphite. Neither the DOVERNOX 76 nor the DOVERPHOS S-480 were capable of significantly decreasing the peroxide value, thus indicating their lack of reactivity towards hydroperoxides at ambient conditions.
  • the methyl ester was then heated at 50°C for 48 hours. The peroxide value of the methyl ester increased both with and without the DOVERNOX 76, although the peroxide value was smaller after aging with DOVERNOX 76.
  • the peroxide value of the formulation that contained DOVERPHOS LGP-11 remained less than 0.5.
  • the addition of an alkyl phosphite improved the quality of the methyl ester/isooctane, and prevented its degradation upon heating.
  • Table 3 includes data on phosphites in the presence of anhydrous and 95% ethanol. Without any water present, neither the trioctyl phosphite (TOP) nor the hindered aryl phosphite (DOVERPHOS S-480) reacted. Once water was added, the trioctyl phosphite reacted to form the phosphonate. The presence of the phosphonate is an indication of a stoichiometric reaction of the phosphite and water. The hindered aryl phosphite did not react with water and the amount of the phosphite remained constant. Thus the use of an alkyl phosphite to fuel can remove water at ambient conditions and mitigate potential corrosion issues due to the presence of water.
  • Table 2 Peroxide Values measurements of soybean based fatty acid methyl ester after aging at 50° for 48 hours.
  • Table 3 Alkyl and hindered aryl phosphites in ethanol and ethanol/water. Phosphites were exposed to the solvents for 1 hour.

Abstract

A composition having a fluid mixture having a liquid fuel component and an antioxidant component; the liquid fuel component being petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and the antioxidant component being a phosphite compound.

Description

TITLE OF THE INVENTION
Phosphite Antioxidants for Fuels and Related Methods
CROSS-REFERENCE TO RELATED APPLICATIONS
This PCT patent application claims priority to U.S. provisional patent application 63/275,746 having a filing date of November 4, 2021. The subject matter of U.S. provisional patent application 63275746 is incorporated by reference into this application in its entirety.
BACKGROUND OF THE INVENTION
It is well known that carbon-based fuels such as petroleum-based diesel, biodiesel, gasoline, and aviation fuel degrade over time at ambient and higher temperatures. This can lead to increased engine deposits, negative effects on fuel systems, and increased emissions. Water is a potential source of fuel corrosion. Because of this, a need remains to inhibit fuel degradation and to remove water from liquid fuels.
Combustion engines use these carbon-based fuels, and in doing so, yield unwanted combustionengine emissions such as: i) nitric oxide, ii) nitrogen dioxide, iii) carbon monoxide, and iv) residual hydrocarbons and particulates. These remains a need to reduce these unwanted combustion-engine emissions.
BRIEF SUMMARY OF THE INVENTION
A composition having a fluid mixture having a liquid fuel component and an antioxidant component; the liquid fuel component being petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and the antioxidant component being a phosphite compound.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING Figure 1 shows two reaction mechanisms; the first reaction mechanism is a peroxide-scavenging reaction mechanism, and the second reaction mechanism is a water-scavenging reaction mechanism.
DETAILED DESCRIPTION OF THE INVENTION
Embodiments are directed to a fluid mixture having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component.
Petroleum-based diesel, biodiesel, gasoline, and aviation fuels are known.
Phosphite compounds are also known, and any known phosphite compound can be employed as an antioxidant in the above identified fuels. Useful phosphites include alkyl phosphites and aryl phosphites having the structure:
R2 o RrO-P-O-R3 wherein each R is an independently selected moiety that is an alkyl, aryl, alkyl-aryl, or hindered aryl moiety. In embodiments, a hindered aryl moiety is an aryl moiety having attached thereto a branched-carbon-chain moiety that has three or more carbon atoms; nonlimiting examples of a hindered aryl moiety include: 1) an aryl moiety having attached thereto a tert butyl moiety, and 2) an aryl moiety having attached thereto a cumyl moiety.
In embodiments, phosphites having the following chemical structure are useful:
Figure imgf000004_0001
wherein each R1, R2, R3, R4 and R5 is independently selected and is a Cio-Cis alkyl moiety; n is an integer ranging from 3 to 11; and the sum of Xi + X2 is an integer ranging from 1-500.
In some phosphorus-containing copolymer compound embodiments, such as those having the immediately above chemical structure, the compound has a weight ranging from 1000 to 30000 Daltons. In some other phosphorus-containing copolymer compound embodiments, such as those having the immediately above chemical structure, the compound has a weight ranging from 400 to 30000 Daltons. In some other phosphorus-containing copolymer compound embodiments, such as those having the immediately above chemical structure, the compound has a weight ranging from 500 to 30000 Daltons.
A chemical compound having the structure:
Figure imgf000004_0002
wherein each R1, R2, R3, R4 and R5 is independently selected and is a Cio-Cis alkyl moiety; n is an integer ranging from 3 to 11; and the sum of X1 + X2 is an integer ranging from 1-1000, can be obtained commercially. Or, it can be manufactured using a known method. In embodiments, phosphite compounds having the following chemical structure are also useful:
Figure imgf000005_0001
wherein each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000.
In some polyhydrogen-phosphite embodiments, such as those having the immediately above chemical structure, each Y is independently selected and is an ethyl, propyl, cyclohexane dimethanol, or caprylactone moiety.
In some polyhydrogen-phosphite embodiments, such as those having the chemical structure:
Figure imgf000005_0002
wherein each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000, the compound has a weight ranging from 1000 to 30000 Daltons. In some polyhydrogenphosphite embodiments, such as those having the immediately above chemical structure, the compound has a weight ranging from 400 to 30000 Daltons. In some polyhydrogen-phosphite embodiments, such as those having the immediately above chemical structure, the compound has a weight ranging from 500 to 30000 Daltons.
A chemical compound having the structure:
Figure imgf000006_0001
wherein each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000, can be obtained commercially from Dover Chemical under the trademark Doverphos LGP-11
Or, it can be manufactured using a known method.
Useful amounts of phosphite antioxidants range from 0.01 to 5.0% by volume of the fluid mixture. Persons of ordinary skill in the art will be able to determine useful amounts of phosphite antioxidants without having to exercise undue experimentation.
Other embodiments include using additional antioxidants, in addition to a phosphite, such as a hindered phenolic or an amine compound.
In embodiments, a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component, yields reduced unwanted combustion-engine emissions relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
In embodiments, a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component having the following chemical structure:
Figure imgf000008_0001
wherein each R1, R2, R3, R4 and R5 is independently selected and is a Cio-Cis alkyl moiety; n is an integer ranging from 3 to 11; and the sum of Xi + X2 is an integer ranging from 1-500, yields reduced unwanted combustion-engine emissions relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
In embodiments, a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component having the following chemical structure:
Figure imgf000008_0002
wherein each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000, yields reduced unwanted combustion-engine emissions relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
In embodiments, a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component, has inhibited fuel degradation relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
In embodiments, a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component having the following chemical structure:
Figure imgf000010_0001
wherein each R1, R2, R3, R4 and R5 is independently selected and is a Cio-Cis alkyl moiety; n is an integer ranging from 3 to 11; and the sum of Xi + X2 is an integer ranging from 1-500, has inhibited fuel degradation relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
In embodiments, a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component having the following chemical structure:
Figure imgf000010_0002
wherein each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000, has inhibited fuel degradation relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
In embodiments, a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component, has reduced water content relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
In embodiments, a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component having the following chemical structure:
Figure imgf000011_0001
each R1, R2, R3, R4 and R5 is independently selected and is a Cio-Cis alkyl moiety; n is an integer ranging from 3 to 11; and the sum of Xi + X2 is an integer ranging from 1-500, has reduced water content relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
In embodiments, a composition having: i) a liquid fuel component that is petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and ii) a phosphite antioxidant component having the following chemical structure:
Figure imgf000012_0001
wherein each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000, has reduced water content relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
It is believed that at least one of the reaction schemes shown in Figure 1 causes the compositional embodiments to:
1) yield reduced unwanted combustion-engine emissions relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component; 2) have inhibited fuel degradation relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component; or
3) have reduced water content relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
EXPERIMENTAL
Figure 1 shows the reaction of alkyl phosphites with hydroperoxides and water. At ambient conditions, if R is an aryl or hindered aryl, a significant amount of reaction with hydroperoxides will not occur. Alkyl phosphites are generally quicker to react with hydroperoxides and water compared to aryl phosphites. It is known that hydroperoxides are both a result of thermal degradation and also promote further degradation of hydrocarbons. Removing hydroperoxides improves fuel quality and thermal stability. Aryl and hindered aryl phosphites do not readily react with hydroperoxides at ambient temperatures (less than 50°C). Hindered aryl phosphites are particularly resistant towards reaction with water. Peroxide Value (PV) is a measurement of the level of hydroperoxides in the sample.
Table 1 displays the peroxide values of a soybean based fatty acid methyl ester and isooctane at ambient conditions (temperatures less than 50°C). The methyl ester is used as an example of biodiesel and the isooctane was used as an example of a hydrocarbon based fuel such as diesel. The initial peroxide value of the methyl ester and isooctane were 6.0 and 18.8 respectively. The addition of an alkyl phosphite (DOVERPHOS LGP-11) scavenged hydroperoxides that were present and reduced the peroxide value to less than 0.5 in both the methyl ester and the isooctane. DOVERNOX 76 is an example of a hindered phenolic stabilizer. They are used to protect hydrocarbons from oxidation, however they cannot remove any hydroperoxides that are initially present. DOVERPHOS S-480 is an example of a hindered aryl phosphite. Neither the DOVERNOX 76 nor the DOVERPHOS S-480 were capable of significantly decreasing the peroxide value, thus indicating their lack of reactivity towards hydroperoxides at ambient conditions. The methyl ester was then heated at 50°C for 48 hours. The peroxide value of the methyl ester increased both with and without the DOVERNOX 76, although the peroxide value was smaller after aging with DOVERNOX 76. The peroxide value of the formulation that contained DOVERPHOS LGP-11 remained less than 0.5. Thus, the addition of an alkyl phosphite improved the quality of the methyl ester/isooctane, and prevented its degradation upon heating.
Table 3 includes data on phosphites in the presence of anhydrous and 95% ethanol. Without any water present, neither the trioctyl phosphite (TOP) nor the hindered aryl phosphite (DOVERPHOS S-480) reacted. Once water was added, the trioctyl phosphite reacted to form the phosphonate. The presence of the phosphonate is an indication of a stoichiometric reaction of the phosphite and water. The hindered aryl phosphite did not react with water and the amount of the phosphite remained constant. Thus the use of an alkyl phosphite to fuel can remove water at ambient conditions and mitigate potential corrosion issues due to the presence of water.
Figure imgf000014_0001
TABLE 1 : Peroxide Values measurements of soybean based fatty acid methyl ester (example of biodiesel) and isooctane (simulant for fuel) mixed at 50°C for 15 minutes. DOVERNOX 76 (common primary hindered phenolic stabilizer). DOVERPHOS S-480 Hindered Aryl Phosphite (tris-2, 4-di-t-butylphenol phosphite). DOVERPHOS LGP-11 Polymeric alkyl phosphite.
Figure imgf000015_0001
Table 2: Peroxide Values measurements of soybean based fatty acid methyl ester after aging at 50° for 48 hours.
Figure imgf000015_0002
Table 3: Alkyl and hindered aryl phosphites in ethanol and ethanol/water. Phosphites were exposed to the solvents for 1 hour.

Claims

CLAIMS What is claimed is:
1. A composition comprising: a fluid mixture having a liquid fuel component and an antioxidant component; the liquid fuel component being petroleum-based diesel, biodiesel, gasoline, or aviation fuel; and the antioxidant component being a phosphite compound.
2. The composition of claim 1, wherein the composition yields reduced unwanted combustionengine emissions relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
3. The composition of claim 1, wherein the composition has inhibited fuel degradation relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
4. The composition of claim 1, wherein the composition has reduced water content relative to a different composition having a formulation that is otherwise the same but does not include the phosphite antioxidant component.
5. The composition of claim 1, wherein the phosphite compound is an alkyl phosphite.
6. The composition of claim 1, wherein the phosphite compound is an aryl phosphite.
7. The composition of claim 1, further comprising an additional antioxidant component that is a hindered phenolic or amine.
8. The composition of claim 1, wherein the antioxidant component is present in the fluid mixture in an amount ranging from 0.01% to 0.5% by volume.
9. The composition of claim 1, wherein the phosphite compound has the chemical structure:
R2 o RrO-P- O-R3 wherein each R is an independently selected moiety that is an alkyl, aryl, alkyl-aryl, or hindered aryl.
10. The composition of claim 5, wherein the alkyl phosphite compound is tri-octyl phosphite.
11. The composition of claim 5, wherein the alkyl phosphite has the chemical structure:
Figure imgf000017_0001
wherein each R is an independently selected alkylphenol-free moiety that is a C1-22 alkyl, C6-40 cycloalkyl, C3-20 methoxy alkyl glycol ether, C3-20 alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C2-40 alkyl, C6-40 cycloalkyl, C2-20 alkyl glycol ether, or C3-40 alkyl lactone moiety; wherein each m is an independently selected integer ranging from 1 to 100; and wherein x is an integer ranging from 1 to 1000. 17
12. The composition of claim 11, wherein each Y is an independently selected ethyl, propyl, cyclohexane dimethanol, or caprylactone moiety.
13. The composition of claim 11, wherein the compound has a weight ranging from 1000 to 30000 Daltons.
14. The composition of claim 11, wherein the compound has a weight ranging from 400 to 30000 Daltons.
15. The composition of claim 11, wherein the compound has a weight ranging from 500 to 30000 Daltons.
16. The composition of claim 5, wherein the alkyl phosphite has the chemical structure:
Figure imgf000018_0001
each R1, R2, R3, R4 and R5 is independently selected and is a Cio-Cis alkyl moiety; n is an integer ranging from 3 to 11; and the sum of Xi + X2 is an integer ranging from 1-500. 18
17. The composition of claim 16, wherein the compound has a weight ranging from 1000 to 30000 Daltons.
18. The composition of claim 16, wherein the compound has a weight ranging from 400 to 30000 Daltons.
19. The composition of claim 16, wherein the compound has a weight ranging from 500 to 30000 Daltons.
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Citations (6)

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CN102061203A (en) * 2009-11-16 2011-05-18 济南开发区星火科学技术研究院 High-temperature diesel antioxidant and preparation method thereof
US20110263760A1 (en) * 2010-02-19 2011-10-27 Dover Chemical Corporation Alkylphenol free - liquid polymeric phosphite polymer stabilizers
US20130345346A1 (en) * 2010-02-19 2013-12-26 Dover Chemical Corporation Cycloaliphatic polyphosphite polymer stabilizers
CN109810289A (en) * 2018-12-27 2019-05-28 江苏迈达新材料股份有限公司 A kind of liquid composite antioxidant and preparation method thereof
US20200407513A1 (en) * 2018-02-14 2020-12-31 Dover Chemical Corporation Use of a polymeric polyphosphite as a polymer processing aid

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61225232A (en) * 1985-03-29 1986-10-07 Adeka Argus Chem Co Ltd Polyolefin resin composition
CN102061203A (en) * 2009-11-16 2011-05-18 济南开发区星火科学技术研究院 High-temperature diesel antioxidant and preparation method thereof
US20110263760A1 (en) * 2010-02-19 2011-10-27 Dover Chemical Corporation Alkylphenol free - liquid polymeric phosphite polymer stabilizers
US20130345346A1 (en) * 2010-02-19 2013-12-26 Dover Chemical Corporation Cycloaliphatic polyphosphite polymer stabilizers
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