WO2014193314A2 - Additive for cetane number increase of diesel fuels and bio-diesel fuels and its use - Google Patents

Additive for cetane number increase of diesel fuels and bio-diesel fuels and its use Download PDF

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WO2014193314A2
WO2014193314A2 PCT/SK2014/050015 SK2014050015W WO2014193314A2 WO 2014193314 A2 WO2014193314 A2 WO 2014193314A2 SK 2014050015 W SK2014050015 W SK 2014050015W WO 2014193314 A2 WO2014193314 A2 WO 2014193314A2
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glycerol
additive
isomers
ester
dinitrate
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PCT/SK2014/050015
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French (fr)
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WO2014193314A3 (en
WO2014193314A4 (en
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Pavol DAUČÍK
Elena HÁJEKOVÁ
Lukáš BUČINSKÝ
Marcela HADVINOVÁ
Tibor JAKUBÍK
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Slovenská Technická Univerzita V Bratislave
Centrum Vedecko-Technických Informácií Sr
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Priority to EP14727092.0A priority Critical patent/EP3004293A2/en
Publication of WO2014193314A2 publication Critical patent/WO2014193314A2/en
Publication of WO2014193314A3 publication Critical patent/WO2014193314A3/en
Publication of WO2014193314A4 publication Critical patent/WO2014193314A4/en

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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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • 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
    • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane 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
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • 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

  • the additive for cetane number increase of diesel fuels and bio-diesel Fuels and its use is related to the area of high-class engine fuels production.
  • the additive is based on the use of glycerol ester mono- and dinitrates constituted by the isomers of glycerol dialkyl ester mononitrate and/or of glycerol monoalkyl ester dinitrate.
  • the diesel fuels contain complicated mixture of hydrocarbon molecules with various configurations of carbon and hydrogen atoms. They may contain various additives, including surfactants, low-temperature agents, emulgators, corrosion inhibitors, sedimentation modifiers and non-hydrocarbon components such as oxygenates and nitrogen compounds. Each of these additives improves the fuel quality parameters. Cetane number is an inportant index of the diesel fuel quality. This number is related to the ignition delay after the fuel injection into the combustion chamber. If the ignition delay is too great, the fuel quantity in the chamber increases and the ignition results in engine hard running and increase smoke generation. Short ignition delay causes engine smooth running and reduced smoke generation.
  • the US Patent 4,420,311 describes the diesel fuels composition and introduces the preparation of the additive of cyclododecyl nitrate from cyclododecanol by the mean of either nitrating mixture of nitric and sulfuric acid or by stirring the the acetic anhydride nitrate.
  • the diesel fuel cetane number has been increased by the addition of small amounts of cyclododecyl nitrate.
  • US Patent 5, 162,048 protects an additive for hydrocarbon fuels, which contains ethanolamine nitrates reducing the smoke quantity and improving the combustion efficiency.
  • the invention includes also the additive production method and fuels improvement by the addition thereof.
  • polynitrate esters selected from the group containing the ethylene glycol dinitrate (EGD), diethylene glycol dinitrate (DEGN), triethylene glycol dinitrate (TEGN) and 2-methyl-2 [(nitroxy)methyl]-l,3- propanediol dinitrate (PDN). These nitrates can be used also in mixtures. Another applicable nitrates are nitroglycerine, cellulose tri-, di- and mononitrates and mixtures thereof.
  • a diesel fuel containing the nitric acid ester with 1 -phenyl ethanol as an additive is described in the US Patent 5,258,049.
  • the diesel mixture prepared under this invention includes at least 85 vol. % of the diesel fuel hydrocarbons and between 0.01 and 3 vol. % of the additive, preferably between 0.1 and 2 vol. %.
  • the US Patent 4,457,763 deals with the cetane number increase by the mean of addition of dioxane nitrates such as m-dioxan-5-ol nitrate or l,3-dioxolane-4-methanol nitrate.
  • the EP 2114844A1 patent application describes the use of branched decyl nitrates having the formula Ri R 2 CH-CH 2 -0-N0 2 , where Ri is identified as propyl or isopropyl substituent and and R 2 means either linear or branched alkyl substituent with 5 carbons.
  • Ri is identified as propyl or isopropyl substituent and and R 2 means either linear or branched alkyl substituent with 5 carbons.
  • the mentioned compounds improve the combustion and/or increase the cetane number.
  • Alkyl nitrates such as pentyl nitrate, ethylhexyl nitrate and a mixture of alkyl nitrates were utilized in industrial scale and giving good results.
  • organic nitrates particularly the commercial 2-ethylhexyl nitrate
  • cetane index improvers Another nitrates such as 2-methyl-2-nitropropyl (U.S. Pat. No. 4,536, 190) were suggested as the cetane index improvers, but they were found to be sensitive to shocks. Due to its relatively low price and environmental friendliness (ash-free additives), the number of works aimed to replace 2-ethylhexyl nitrate was limited.
  • Alkyl nitrates and particularly 2-ethylhexyl nitrate, are commercially the most efficient cetane number improvers.
  • a disadvantage of the up-to-date patented additives is both their difficult production and the raw materials price.
  • the additives constituted by isomers of glycerol dialkyl ester mononitrates and/or glycerol monoalkyl ester dinitrates are able to compete with 2-etylhexyl nitrate since the cetane number increase has been proven for their use in diesel and bio-diesel fuels.
  • the essence of the additive increasing the diesel and bio-diesel fuels cetane number according to the invention consists in the additive constituted by isomers of glycerol monoalkyl ester dinitrate with between 1 and 20 carbons in the ester alkyl group and/or isomers of glycerol dialkyl ester mononitrate with between 1 and 20 carbons in the ester alkyls groups.
  • Isomers of glycerol monoalkyl ester dinitrate and/or isomers of glycerol dialkyl ester mononitrate belong to the family of nitrates and/or dinitrates of the partially esterified glycerol.
  • the isomers of glycerol dialkyl ester mononitrate and/or of glycerol monoalkyl ester dinitrate having from 1 to 20 carbons in the ester alkyl group are added in concentrations from 1 to 5000 mg/kg of the fuel total amount.
  • the glycerol dialkyl ester mononitrate isomers are constituted by l,3-dialkanoyl-glycerol-2- nitrate (Al) and l,2-dialkanoyl-glycerol-3 -nitrate (A2), and the glycerol monoalkylester dinitrate isomers by l,3-dinitro-2-alkanoyl-glycerol (Bl) and l,2-dinitro-3-alkanoyl-glycerol (B2).
  • Nitrates and/or dinitrates of the partially esterified glycerol can be prepared by the mean of nitration of the corresponding glycerol esters.
  • Ri is the hydrocarbon chain having between 1 and 20 atoms of carbon, preferably between 1 and 5 carbons.
  • kerosen refined by hydrogenation (distillation range from 143 °C to 257 °C) and gas oil refined by hydrogenation (distillation range from 175 °C to 353 °C) were used.
  • the fuel contained 33 m/m % of kerosene and 67 m/m % of gas oil.
  • the cetane number (CeN) value of the basic diesel fuel DF determined according to EN ISO 5165/01 was 50.3.
  • the fuel with biocomponent (BDF) was prepared from the basic diesel fuel (DF) by adding a mixture of rapeseed oil methyl esters.
  • the resulting content of the rapeseed oil methyl esters in the BDF fuel was 6.32 m/m %.
  • the cetane number value of the fuel with biocomponent BDF determined according to EN ISO 5165/01 was 51.1.
  • the diesel fuels DF and BDF were used as base for the determination of the impact of the compounds Al, A2 and/or B l, B2 on the cetane number.
  • the additive l,3-dialkanoyl-glycerol-2-nitrate (Al) in form of l,3-diacetyl-glycerol-2-nitrate has been diluted in diesel fuel DF.
  • This fuel (DF-A1) contained a mixture of basic fuel DF and additive Al .
  • the content of additive Al in the fuel (DF-A1) was 2,054 mg.kg "1 .
  • the fuel DF-A1 cetane number value determined according to EN ISO 5165/01 was 52.6.
  • the additive Al in form of l,3-diacetyl-glycerol-2-nitrate increased the basic diesel fuel DF cetane number from 50.3 to 52.6.
  • the additive l,2-dialkanoyl-glycerol-3 -nitrate (A2) in form of l,2-diacetyl-glycerol-3 -nitrate has been diluted in the mixture of rapeseed oil methyl esters.
  • a solution (S2) (additive A2 in the mixture of rapeseed oil methyl esters) contained 2.52 m/m % of l,2-diacetyl-glycerol-3- nitrate.
  • fuel (BDF-A2) containing the mixture of basic fuel, rapeseed oil methyl esters and additive A2 was prepared.
  • the additive A2 content in fuel (BDF- A2) was 2,515 mg.kg "1 .
  • the fuel BDF-A2 cetane number value determined according to EN ISO 5165/01 was 52.9.
  • the additive A2 in form of l,2-diacetyl-glycerol-3 -nitrate increased the basic diesel fuel BDF cetane number from 51.1 to 52.9.
  • cetane number values of the diesel fuels DF and BDF were used.
  • the additive l,3-dinitro-2-alkanoyl-glycerol (B l) in form of l,3-dinitro-2-acetyl-glycerol has been diluted in the mixture of rapeseed oil methyl esters.
  • a solution (S3) of the mentioned additive in the mixture of rapeseed oil methyl esters contained 1.28 m/m % of l,3-dinitro-2- acetyl-glycerol.
  • fuel (BDF-Bl) containing the mixture of basic fuel, rapeseed oil methyl esters and additive Bl was prepared.
  • the additive B l content in fuel (BDF-Bl) was 1, 171 mg.kg "1 .
  • the fuel BDF-Bl cetane number value determined according to EN ISO 5165/01 was 52.6.
  • the additive B l in form of l,3-dinitro-2-acetyl-glycerol increased the diesel fuel cetane number from 51.1 to 52.6.
  • cetane number values of the diesel fuels DF and BDF were used.
  • the additive l,2-dinitro-3-alkanoyl-glycerol (B2) in form of l,2-dinitro-3 -acetyl-glycerol has been diluted in the mixture of rapeseed oil methyl esters.
  • a solution (S4) of the mentioned additive in the mixture of rapeseed oil methyl esters contained 1.63 m/m % of l,2-dinitro-3- acetyl-glycerol.
  • fuel (BDF-B2) containing the mixture of basic fuel, rapeseed oil methyl esters and additive B2 was prepared.
  • the additive B2 content in fuel (BDF-B2) was 1,054 mg.kg "1 .
  • the fuel BDF-B2 cetane number value determined according to EN ISO 5165/01 was 52.9.
  • the additive B2 in form of l,2-dinitro-3 -acetyl-glycerol increased the diesel fuel cetane number from 51.1 to 52.9.
  • cetane number values of the diesel fuels DF and BDF were used.
  • the additive l,3-dialkanoyl-glycerol-2-nitrate (Al) in form of l,3-diacetyl-glycerol-2-nitrate and the additive l,2-dinitro-3-alkanoyl-glycerol (B2) in form of l,2-dinitro-3 -acetyl-glycerol were diluted in the mixture of rapeseed oil methyl esters.
  • a solution (S5) of the mentioned additives Al and B2 in the mixture of rapeseed oil methyl esters contained 0.63 m/m % of l,3-diacetyl-glycerol-2-nitrate and 1.35 m/m % of l,2-dinitro-3-acetyl-glycerol.
  • fuel (BDF-A1B2) containing the mixture of basic fuel, rapeseed oil methyl esters and additives Al and B2 was prepared.
  • the total content of additives Al and B2 in fuel (BDF-A1B2) was 994 mg.kg "1 .
  • the fuel BDF-A1B2 cetane number value determined according to EN ISO 5165/01 was 52.3.
  • the fuel cetane number increase from 51.1 to 52.3 has been proven for the mixture of additives Al in form of l,3-diacetyl-glycerol-2-nitrate and B2 in form of l,2-dinitro-3 -acetyl- glycerol.
  • the diesel and bio-diesel fuels cetane number improver under the invention can be used in the automotive industry.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Additive for Cetane Number Increase of Diesel Fuels or Bio-Diesel Fuels The essence of the additive increasing the diesel or bio-diesel fuels cetane number consists in the additive constituted glycerol mono- and diesters nitrates containing the isomers of glycerol dialkyl ester mononitrate and/or isomers of glycerol monoalkyl ester dinitrate with between 1 and 20 carbons in the ester alkyl group and their addition in concentrations between 1 and 5,000 mg/kg to the total fuel amount. The additive is added either directly or diluted in fatty acids alkyl esters having from 1 to 20 carbons in the acid and/or alcohol relevant group contained in the esters.

Description

Additive for Cetane Number Increase of Diesel Fuels and Bio-Diesel Fuels and Its Use
Technical Field
The additive for cetane number increase of diesel fuels and bio-diesel Fuels and its use is related to the area of high-class engine fuels production. The additive is based on the use of glycerol ester mono- and dinitrates constituted by the isomers of glycerol dialkyl ester mononitrate and/or of glycerol monoalkyl ester dinitrate.
Background Art
The diesel fuels contain complicated mixture of hydrocarbon molecules with various configurations of carbon and hydrogen atoms. They may contain various additives, including surfactants, low-temperature agents, emulgators, corrosion inhibitors, sedimentation modifiers and non-hydrocarbon components such as oxygenates and nitrogen compounds. Each of these additives improves the fuel quality parameters. Cetane number is an inportant index of the diesel fuel quality. This number is related to the ignition delay after the fuel injection into the combustion chamber. If the ignition delay is too great, the fuel quantity in the chamber increases and the ignition results in engine hard running and increase smoke generation. Short ignition delay causes engine smooth running and reduced smoke generation.
Generally the commercially available oil-based diesel fuels are required to be with the cetane number equal or greater than 51. In order to improve the cetane number, organic nitrates and nitro compounds were and are added to diesel fuels more years already. From 1930, organic nitrates are used in diesel fuels for the cetane number increase, achieving thereby the appropriate self-ignition allowing the diesel engine smooth running.
Throughout the years, many types of additives were used for the cetane number increase of the diesel fuels. However, only additives based on peroxides, nitrites, nitroso carbamates and, first of all, various types of nitrates, are described in the patent files, as can be seen in the following references:
The US Patent 4,420,311 describes the diesel fuels composition and introduces the preparation of the additive of cyclododecyl nitrate from cyclododecanol by the mean of either nitrating mixture of nitric and sulfuric acid or by stirring the the acetic anhydride nitrate. The diesel fuel cetane number has been increased by the addition of small amounts of cyclododecyl nitrate.
US Patent 5, 162,048 protects an additive for hydrocarbon fuels, which contains ethanolamine nitrates reducing the smoke quantity and improving the combustion efficiency. The invention includes also the additive production method and fuels improvement by the addition thereof.
The US Patent 4,705,534 specifies the following additive components: polynitrate esters selected from the group containing the ethylene glycol dinitrate (EGD), diethylene glycol dinitrate (DEGN), triethylene glycol dinitrate (TEGN) and 2-methyl-2 [(nitroxy)methyl]-l,3- propanediol dinitrate (PDN). These nitrates can be used also in mixtures. Another applicable nitrates are nitroglycerine, cellulose tri-, di- and mononitrates and mixtures thereof.
A diesel fuel containing the nitric acid ester with 1 -phenyl ethanol as an additive is described in the US Patent 5,258,049. The diesel mixture prepared under this invention includes at least 85 vol. % of the diesel fuel hydrocarbons and between 0.01 and 3 vol. % of the additive, preferably between 0.1 and 2 vol. %.
The US Patent 4,457,763 deals with the cetane number increase by the mean of addition of dioxane nitrates such as m-dioxan-5-ol nitrate or l,3-dioxolane-4-methanol nitrate.
The US Patent 4,328,005 specifies that the family of additives for hydrocarbon fuels known as polynitro alkyls having the general formula Ri-C(N02)2-R2 enhance the overall combustion characteristics of motor fuels by increasing the combustion efficiency and reducing the undesirable combustion by-products.
The EP 2114844A1 patent application describes the use of branched decyl nitrates having the formula Ri R2 CH-CH2-0-N02, where Ri is identified as propyl or isopropyl substituent and and R2 means either linear or branched alkyl substituent with 5 carbons. The mentioned compounds improve the combustion and/or increase the cetane number.
Alkyl nitrates such as pentyl nitrate, ethylhexyl nitrate and a mixture of alkyl nitrates were utilized in industrial scale and giving good results. However, it is generally accepted that the organic nitrates, particularly the commercial 2-ethylhexyl nitrate, are the most economic cetane number improvers. Another nitrates such as 2-methyl-2-nitropropyl (U.S. Pat. No. 4,536, 190) were suggested as the cetane index improvers, but they were found to be sensitive to shocks. Due to its relatively low price and environmental friendliness (ash-free additives), the number of works aimed to replace 2-ethylhexyl nitrate was limited.
In the found publications and patents, no additives constituted by glycerol monoalkyl ester dinitrates and/or glycerol dialkyl ester nitrates were found.
Alkyl nitrates, and particularly 2-ethylhexyl nitrate, are comercially the most efficient cetane number improvers. A disadvantage of the up-to-date patented additives is both their difficult production and the raw materials price.
Taking into account the above mentioned, the additives constituted by isomers of glycerol dialkyl ester mononitrates and/or glycerol monoalkyl ester dinitrates are able to compete with 2-etylhexyl nitrate since the cetane number increase has been proven for their use in diesel and bio-diesel fuels.
Disclosure of Invention
The essence of the additive increasing the diesel and bio-diesel fuels cetane number according to the invention consists in the additive constituted by isomers of glycerol monoalkyl ester dinitrate with between 1 and 20 carbons in the ester alkyl group and/or isomers of glycerol dialkyl ester mononitrate with between 1 and 20 carbons in the ester alkyls groups. Isomers of glycerol monoalkyl ester dinitrate and/or isomers of glycerol dialkyl ester mononitrate belong to the family of nitrates and/or dinitrates of the partially esterified glycerol.
The isomers of glycerol dialkyl ester mononitrate and/or of glycerol monoalkyl ester dinitrate having from 1 to 20 carbons in the ester alkyl group are added in concentrations from 1 to 5000 mg/kg of the fuel total amount.
The glycerol dialkyl ester mononitrate isomers are constituted by l,3-dialkanoyl-glycerol-2- nitrate (Al) and l,2-dialkanoyl-glycerol-3 -nitrate (A2), and the glycerol monoalkylester dinitrate isomers by l,3-dinitro-2-alkanoyl-glycerol (Bl) and l,2-dinitro-3-alkanoyl-glycerol (B2).
It was found out that it is advantageous when the isomers of glycerol dialkyl ester mononitrate and/or of glycerol monoalkyl ester dinitrate have in their molecule from 1 to 5 carbon atoms in the ester alkyl group.
Furthermore, it was found out to be advantageous to add the additive into the diesel fuel diluted in fatty acids alkyl esters having from 1 to 20 carbons in the acid and/or alcohol relevant group, and for the bio-diesel fuel, the best results were achieved when this fuel contained fatty acids esters.
Nitrates and/or dinitrates of the partially esterified glycerol can be prepared by the mean of nitration of the corresponding glycerol esters.
Glycerol dialkyl ester mononitrate isomers
Figure imgf000004_0001
l,3-dialkanoyl-glycerol-2-nitrate (Al)
Figure imgf000004_0002
1 , 2-di alkanoy 1 -glycerol -3 -nitrate ( A2) where Ri is the hydrocarbon chain having between 1 and 20 atoms of carbon, preferably between 1 and 5 carbons. Glycerol monoalkyl ester dinitrate isomers
Figure imgf000005_0001
1 , 3 -dinitro-2-alkanoyl-gly cerol (B 1 )
Figure imgf000005_0002
l,2-dinitro-3-alkanoyl-gly cerol (B2) where Ri is the hydrocarbon chain having between 1 and 20 atoms of carbon, preferably between 1 and 5 carbons.
Examples of Invention Embodiments
For the preparation of basic diesel fuel (DF), kerosen refined by hydrogenation (distillation range from 143 °C to 257 °C) and gas oil refined by hydrogenation (distillation range from 175 °C to 353 °C) were used. The fuel contained 33 m/m % of kerosene and 67 m/m % of gas oil. The cetane number (CeN) value of the basic diesel fuel DF determined according to EN ISO 5165/01 was 50.3.
The fuel with biocomponent (BDF) was prepared from the basic diesel fuel (DF) by adding a mixture of rapeseed oil methyl esters. The resulting content of the rapeseed oil methyl esters in the BDF fuel was 6.32 m/m %. The cetane number value of the fuel with biocomponent BDF determined according to EN ISO 5165/01 was 51.1.
The diesel fuels DF and BDF were used as base for the determination of the impact of the compounds Al, A2 and/or B l, B2 on the cetane number.
Example 1
The additive l,3-dialkanoyl-glycerol-2-nitrate (Al) in form of l,3-diacetyl-glycerol-2-nitrate has been diluted in diesel fuel DF. This fuel (DF-A1) contained a mixture of basic fuel DF and additive Al . The content of additive Al in the fuel (DF-A1) was 2,054 mg.kg"1. The fuel DF-A1 cetane number value determined according to EN ISO 5165/01 was 52.6. The additive Al in form of l,3-diacetyl-glycerol-2-nitrate increased the basic diesel fuel DF cetane number from 50.3 to 52.6.
Example 2
The additive l,2-dialkanoyl-glycerol-3 -nitrate (A2) in form of l,2-diacetyl-glycerol-3 -nitrate has been diluted in the mixture of rapeseed oil methyl esters. A solution (S2) (additive A2 in the mixture of rapeseed oil methyl esters) contained 2.52 m/m % of l,2-diacetyl-glycerol-3- nitrate.
Using the basic diesel fuel DF and solution S2, fuel (BDF-A2) containing the mixture of basic fuel, rapeseed oil methyl esters and additive A2 was prepared. The additive A2 content in fuel (BDF- A2) was 2,515 mg.kg"1. The fuel BDF-A2 cetane number value determined according to EN ISO 5165/01 was 52.9.
The additive A2 in form of l,2-diacetyl-glycerol-3 -nitrate increased the basic diesel fuel BDF cetane number from 51.1 to 52.9.
Example 3
In order to find out the additive Bl impact, cetane number values of the diesel fuels DF and BDF were used.
The additive l,3-dinitro-2-alkanoyl-glycerol (B l) in form of l,3-dinitro-2-acetyl-glycerol has been diluted in the mixture of rapeseed oil methyl esters. A solution (S3) of the mentioned additive in the mixture of rapeseed oil methyl esters contained 1.28 m/m % of l,3-dinitro-2- acetyl-glycerol.
Using the basic diesel fuel DF and solution S3, fuel (BDF-Bl) containing the mixture of basic fuel, rapeseed oil methyl esters and additive Bl was prepared. The additive B l content in fuel (BDF-Bl) was 1, 171 mg.kg"1. The fuel BDF-Bl cetane number value determined according to EN ISO 5165/01 was 52.6.
The additive B l in form of l,3-dinitro-2-acetyl-glycerol increased the diesel fuel cetane number from 51.1 to 52.6.
Example 4
In order to find out the additive B2 impact, cetane number values of the diesel fuels DF and BDF were used.
The additive l,2-dinitro-3-alkanoyl-glycerol (B2) in form of l,2-dinitro-3 -acetyl-glycerol has been diluted in the mixture of rapeseed oil methyl esters. A solution (S4) of the mentioned additive in the mixture of rapeseed oil methyl esters contained 1.63 m/m % of l,2-dinitro-3- acetyl-glycerol.
Using the basic diesel fuel DF and solution S4, fuel (BDF-B2) containing the mixture of basic fuel, rapeseed oil methyl esters and additive B2 was prepared. The additive B2 content in fuel (BDF-B2) was 1,054 mg.kg"1. The fuel BDF-B2 cetane number value determined according to EN ISO 5165/01 was 52.9. The additive B2 in form of l,2-dinitro-3 -acetyl-glycerol increased the diesel fuel cetane number from 51.1 to 52.9.
Example 5
In order to find out the impact of the mixture of the additives Al and B2, cetane number values of the diesel fuels DF and BDF were used.
The additive l,3-dialkanoyl-glycerol-2-nitrate (Al) in form of l,3-diacetyl-glycerol-2-nitrate and the additive l,2-dinitro-3-alkanoyl-glycerol (B2) in form of l,2-dinitro-3 -acetyl-glycerol were diluted in the mixture of rapeseed oil methyl esters. A solution (S5) of the mentioned additives Al and B2 in the mixture of rapeseed oil methyl esters contained 0.63 m/m % of l,3-diacetyl-glycerol-2-nitrate and 1.35 m/m % of l,2-dinitro-3-acetyl-glycerol.
Using the basic diesel fuel DF and solution S5, fuel (BDF-A1B2) containing the mixture of basic fuel, rapeseed oil methyl esters and additives Al and B2 was prepared. The total content of additives Al and B2 in fuel (BDF-A1B2) was 994 mg.kg"1. The fuel BDF-A1B2 cetane number value determined according to EN ISO 5165/01 was 52.3.
The fuel cetane number increase from 51.1 to 52.3 has been proven for the mixture of additives Al in form of l,3-diacetyl-glycerol-2-nitrate and B2 in form of l,2-dinitro-3 -acetyl- glycerol.
Industrial Applicability
The diesel and bio-diesel fuels cetane number improver under the invention can be used in the automotive industry.

Claims

1. The additive for increase of the diesel or bio-diesel fuel cetane numbers characterized in that the additive is constituted by glycerol nitrate mono- and diesters consisting of the isomers of glycerol dialkyl ester mononitrate and/or of glycerol monoalkyl ester dinitrate having from 1 to 20 carbons in the ester alkyl group.
2. The additive under claim 1 characterized in that the glycerol mononitrate dialkyl ester isomers are constituted by l,3-dialkanoyl-glycerol-2-nitrate (Al) and 1,2- dialkanoyl-glycerol-3 -nitrate (A2) and glycerol monoalkyl ester dinitrate isomers are constituted by l,3-dinitro-2-alkanoyl-glycerol (Bl) and l,2-dinitro-3-alkanoyl- glycerol (B2).
3. The additive under claims 1 and 2 characterized in that the isomers of glycerol dialkyl ester mononitrate and/or isomers of glycerol monoalkyl ester dinitrate have in their chains from 1 to 5 carbon atoms in the ester alkyl group.
4. The additive under claims 1 to 3 characterized in that the isomers of glycerol dialkyl ester mononitrate and/or isomers of glycerol monoalkyl ester dinitrate are added in concentrations not exceeding 5,000 mg/kg of total fuel amount.
5. The additive under claims 1 to 4 characterized in that the isomers of glycerol dialkyl ester mononitrate and/or isomers of glycerol monoalkyl ester dinitrate are added to the diesel fuel diluted in fatty acids alkyl esters.
6. The additive under claims 1 to 5 characterized in that the isomers of glycerol dialkyl ester mononitrate and/or isomers of glycerol monoalkyl ester dinitrate are added to the diesel fuel diluted in fatty acids alkyl esters having from 1 to 20 carbons in the acid and/or alcohol relevant group contained in the esters.
7. The additive under claims 1 to 4 characterized in that the additive is added to bio- diesel fuel containing fatty acids esters.
8. Use of additive under claims 1 to 7 to increase the cetane number of fuel containing kerosene refined by hydrogenation, gas oil refined by hydrogenation and/or the mixture of fatty acids methyl esters.
PCT/SK2014/050015 2013-05-31 2014-04-17 Additive for cetane number increase of diesel fuels and bio-diesel fuels and its use WO2014193314A2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022183263A1 (en) * 2021-03-01 2022-09-09 Marco Antonio Falquete Cetane improvers for diesel cycle fuels

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4328005A (en) 1980-10-10 1982-05-04 Rockwell International Corporation Polynitro alkyl additives for liquid hydrocarbon motor fuels
US4420311A (en) 1982-11-09 1983-12-13 Ethyl Corporation Diesel fuel composition
US4457763A (en) 1983-11-07 1984-07-03 Ethyl Corporation Diesel fuel cetane improver
US4536190A (en) 1984-04-02 1985-08-20 Ethyl Corporation Cetane improver composition
US4705534A (en) 1985-11-15 1987-11-10 Mobil Oil Corporation Cetane number of diesel fuel by incorporating polynitrate esters and stabilizers
US5162048A (en) 1989-09-27 1992-11-10 Kirsten, Inc. Additive for hydrocarbon fuels
US5258049A (en) 1993-02-17 1993-11-02 Arco Chemical Technology, L.P. Diesel fuel composition
EP2114844A1 (en) 2007-01-29 2009-11-11 Basf Se Branched decyl nitrates and the use thereof as combustion improvers and/or cetane number improvers in fuels

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2066506A (en) * 1932-10-13 1937-01-05 Du Pont Fuel
US4448587A (en) * 1983-03-28 1984-05-15 Ethyl Corporation Synergistic cetane improver
GB2352239A (en) * 1999-07-03 2001-01-24 Secr Defence Preparation of Glycerol Dinitrates

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4328005A (en) 1980-10-10 1982-05-04 Rockwell International Corporation Polynitro alkyl additives for liquid hydrocarbon motor fuels
US4420311A (en) 1982-11-09 1983-12-13 Ethyl Corporation Diesel fuel composition
US4457763A (en) 1983-11-07 1984-07-03 Ethyl Corporation Diesel fuel cetane improver
US4536190A (en) 1984-04-02 1985-08-20 Ethyl Corporation Cetane improver composition
US4705534A (en) 1985-11-15 1987-11-10 Mobil Oil Corporation Cetane number of diesel fuel by incorporating polynitrate esters and stabilizers
US5162048A (en) 1989-09-27 1992-11-10 Kirsten, Inc. Additive for hydrocarbon fuels
US5258049A (en) 1993-02-17 1993-11-02 Arco Chemical Technology, L.P. Diesel fuel composition
EP2114844A1 (en) 2007-01-29 2009-11-11 Basf Se Branched decyl nitrates and the use thereof as combustion improvers and/or cetane number improvers in fuels

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022183263A1 (en) * 2021-03-01 2022-09-09 Marco Antonio Falquete Cetane improvers for diesel cycle fuels

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SK288302B6 (en) 2015-09-03
WO2014193314A3 (en) 2015-01-22
SK500182013A3 (en) 2014-12-04
EP3004293A2 (en) 2016-04-13
WO2014193314A4 (en) 2015-03-19

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