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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
  • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
  • C07D251/34—Cyanuric or isocyanuric esters
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • 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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
  • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
• • 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
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2443—Organic compounds containing sulfur, selenium and/or tellurium heterocyclic compounds
  • C10L1/245—Organic compounds containing sulfur, selenium and/or tellurium heterocyclic compounds only sulfur as hetero atom

Definitions

• This invention is directed to multifunctional additives comprising ether-type reaction products which improve the low-temperature properties of distillate fuels.
• kerosene dilutes the wax in the fuel, i.e., lowers the overall weight fraction of wax, and thereby lowers the cloud point, filterability temperature, and pour point simultaneously.
• the additives of this invention effectively lower both the cloud point and CFPP (Cold Filter Plugging Point) of distillate fuel without any appreciable dilution of the wax component of the fuel.
• U.S. Patent 4,957,650 discloses that in broad boiling distillate fuels ester, ether, or ester/ether additives are typically employed in conjunction with other flow improver additives.
• U. S. Patent 4,738,686 provides hydrocarbon fuels having an improved cetane number rating which contain cyclic ether additives such as diketene compounds and diketene-carbonyl adducts.
• U. S. Patent 4,682,984 provides an additive particularly designed for vehicular diesel fuel which generally comprises a mixture of aromatic and aliphatic hydrocarbons and a lower aliphatic ether.
• additives are ether or ether/amine products which have core-pendant group (star-like) structures derived from the reaction of a halogen reactive organic "core” with the following “pendant groups”: (1) an aminoalcohol, the product of an amine and an ep ⁇ xide, or (2) a combination of an aminoalcohol and a secondary amine.
• the aminoalcohols may also encompass a combination of two or more different aminoalcohols.
• a primary object of this invention is to improve the low-temperature flow properties of distillate fuels and thereby provide improved fuel compositions.
• These new additives are especially effective in lowering the cloud point of distillate fuels, and thus improve the low-temperature flow properties of such fuels without the use of any light hydrocarbon diluent, such as kerosene.
• the filterability properties are improved as demonstrated by lower CFPP temperatures.
• the additives of this invention demonstrate multifunctional activity in distillate fuels.
• additives in accordance with the invention are unique. Also, additive concentrates and fuel compositions containing such additives are unique. Similarly, the processes for making these additives, additive concentrates, and fuel compositions are unique.
• Hydrocarbyl as defined herein is an organic radical containing at least carbon and hydrogen atoms.
• Suitable organic radicals include hydrocarbon groups. Also suitable are organic radicals comprising a hydrocarbon group and further comprising heteroatoms such as oxygen, nitrogen, sulfur and halogen.
• suitable hydrocarbon groups include cyclic or acyclic hyrocarbon groups, aliphatic (straight or branched) , cycloaliphatic such as cycloalkyl or cycloalkenyl.
• the hydrocarbon group may also be aromatic.
• Organic radicals suitable as hydrocarbyl include the hydrocarbon groups alkyl, alkenyl, alkynyl and aryl.
• Aryl refers to any aromatic hydrocarbon.
• An ether-type reaction product in accordance with the invention may be prepared by a process which comprises the reaction of (1) reactive hydrocarbyl halides and (2) aminoalcohols or mixture of aminoalcohols or aminoalcohols/amines with long-chain hydrocarbyl groups attached thereto.
• the reaction is carried out under ether and amine formation conditions in substantially molar, less than molar or more than molar amounts at temperatures varying from 85 to 250°C under pressures varying from ambient to about 690 kPa (100 psi) or autogenous for a time sufficient to obtain the desired ether type additive product of reaction containing the desired core- pendant group structures.
• the additives of this invention have core- pendant group (star-like) structures. These additives are reaction products obtained by combining the core structure and the pendant group(s) in differing ratios using standard techniques for ether/amine formation.
• Suitable pendant groups may be derived from alcohols and amines with some combination of linear hydrocarbyl groups attached.
• the pendant groups include, but are not limited to, (1) aminoalcohols, derived from a secondary fatty amine capped with an epoxide, and (2) combinations of the aminoalcohol from (1) and a long-chain secondary amine.
• the aminoalcohol, above, may include one or more different aminoalcohols.
• a generalized preparation of the aminoalcohols from an epoxide and a secondary amine is illustrated below:
• H / C CH 2 relieve. + H-NI-R1. > HO-CJH-CH_-NI-R1.
• R. and R are C_ to C_ 4 and R relieve is preferably C_ 2 to C ..
• Amines suitable for use herein should have at least one long-chain hydrocarbyl group containing preferably twelve or more carbon atoms.
• Highly useful secondary amines include but are not limited to di(hydrogenated tallow) amine, ditallow amine, dioctadecylamine, methyloctadecylamine and the like.
• Suitable core structures include hydrocarbon molecules containing at least two or more reactive halide groups (Cl, Br, I) , pseudo-halide groups such as methyl sulfonates, tolyl sulfonates, etc., or low- molecular weight ethers such as methyl or ethyl ether which are susceptible to substitution reactions by reactive nucleophiles.
• These core structures include, but are not limited to, aromatic, cyclic or alicyclic, aralkyl, alkylaryl, and alkyl hydrocarbons, as well as their corresponding heteroatom-containing analogues. Generally speaking there are at least two reactive groups in the core structure precursor.
• the additives of this invention are the reaction products of the "core” and “pendant group” precursors, and a range of reactant stoichiometries may be used.
• each additive requires one "core” derivatized with at least one aminoalcohol "pendant group”; any additional pendant groups may be either aminoalcohols or amines which may be optionally added up to the limit of available reactive groups in the core structure. Residual, unreacted halogen (or other reactive groups) in the reaction product may be removed or reduced by hydrolysis, hydrogenolysis, reduction, or substitution with suitable chemical reagents.
• the aminoalcohol is produced in situ by the reaction of the amine and the epoxide.
• the aminoalcohol may be prepared independently if desired.
• the same "core" reacted with a suitable secondary amine gives a tertiary amine additive product with an analogous release of HCl as by ⁇ product.
• additives may function alone or in the presence of an added pour point additive with additional improvements in cloud point and CFPP activity.
• Cyanuric chloride is a very good example of a halogen containing reactive hydrocarbon "core” which can react with the disclosed aminoalcohols/amines to give product ethers/amines (Table 1, entries 2-7) .
• ether/amine additives and pour point additive demonstrates improved cloud point and CFPP activity- (Table 1, entries 2, 5-7).
• suitable core structure include but are not limited to esters and ethers of cyanuric acid, halogenated alkanes (e.g. dichloromethane, trichloropropane, di- and tri-chloroadamantane) , halogenated aromatics (e.g. trichlorobenzene, dichloroanthracene, dichlorophenol, tetrachloropyrimidine, dichlorothiophene, trichlorofluorenone, and dichloropyridine) .
• halogenated alkanes e.g. dichloromethane, trichloropropane, di- and tri-chloroadamantane
• halogenated aromatics e.g. trichlorobenzene, dichloroanthracene, dichlorophenol, tetrachloropyrimidine, dichlorothiophene, trichlorofluorenone, and dichloropyridine
• the reactions can be carried out under widely varying conditions which are not believed to be critical.
• the reaction temperatures can vary from 100 to 250°C or reflux, preferably 120 to 200°C, under ambient or autogenous pressure. However slightly higher pressures may be used if desired.
• the temperatures chosen will depend upon for the most part on the particular reactants and on whether or not a solvent is used.
• Solvents used will typically be hydrocarbon solvents such as xylene, but any non- polar, unreactive solvent can be used including benzene and toluene and/or mixtures thereof.
• By ⁇ products, such as HC1 may be removed from the reaction mixture via a suitable gas purge (such as nitrogen) or via in-situ scavenging of acidic by ⁇ products with added base (such as sodium hydroxide or sodium carbonate) .
• the molar ratios of the reactants will vary widely dependent upon such variables as temperature, pressure, the specific reactants and the like and accordingly may vary from less than molar to more than molar to equimolar ratios.
• a molar ratio of 1:1 to 10:1 of amine to epoxide is chosen and the preferred ratio of amine/epoxide/reactive halide may vary from 1/1/1 to 1/0.1/1, i.e. for each of the two or more reactive halides in the core group precursor.
• the cloud point of the additized distillate fuel was determined using an automatic cloud point test based on the commercially available Herzog cloud point tester; test cooling rate is approximately 1°C/min. Results of this test protocol correlate well with ASTM D2500 methods.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Liquid Carbonaceous Fuels (AREA)

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Citations (5)

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• 1993
  • 1993-12-22 WO PCT/US1993/012496 patent/WO1994016040A1/en not_active Application Discontinuation
  • 1993-12-22 EP EP94905489A patent/EP0677095A4/en not_active Withdrawn
  • 1993-12-22 CA CA 2148496 patent/CA2148496A1/en not_active Abandoned
  • 1993-12-22 JP JP6516042A patent/JPH08505620A/ja active Pending
• 1995
  • 1995-06-29 FI FI953227A patent/FI953227A/fi not_active Application Discontinuation

Patent Citations (5)

Non-Patent Citations (1)

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