WO2024091146A1 - Composition de carburant pour essence sans éthanol pour aviation - Google Patents

Composition de carburant pour essence sans éthanol pour aviation Download PDF

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Publication number
WO2024091146A1
WO2024091146A1 PCT/RU2023/050250 RU2023050250W WO2024091146A1 WO 2024091146 A1 WO2024091146 A1 WO 2024091146A1 RU 2023050250 W RU2023050250 W RU 2023050250W WO 2024091146 A1 WO2024091146 A1 WO 2024091146A1
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WO
WIPO (PCT)
Prior art keywords
gasoline
isomerate
hydrocarbons
fuel composition
composition
Prior art date
Application number
PCT/RU2023/050250
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English (en)
Russian (ru)
Inventor
Михаил Александрович ЕРШОВ
Всеволод Дмитриевич САВЕЛЕНКО
Никита Александрович КЛИМОВ
Никита Олегович БУРОВ
Кирилл Александрович ОВЧИННИКОВ
Екатерина Витальевна ПОДЛЕСНОВА
Original Assignee
Публичное акционерное общество "Газпром нефть"
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from RU2022127882A external-priority patent/RU2802183C1/ru
Application filed by Публичное акционерное общество "Газпром нефть" filed Critical Публичное акционерное общество "Газпром нефть"
Publication of WO2024091146A1 publication Critical patent/WO2024091146A1/fr

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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
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • C10L1/16—Hydrocarbons
    • 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
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom

Definitions

  • the invention relates to oil refining and petrochemistry, namely to commercial products of oil refining production, in particular to the composition of aviation gasoline.
  • GOST 1012 contains only the B-91/115 and B-92 brands that are relevant and in demand by the current fleet
  • GOST 55493 has been developed, identical to the foreign ASTM D 910 or DEF STAN 91-90 for Avgas brand aviation gasoline 100LL, which is the most popular in the world and is approved for almost all piston aircraft.
  • grades B-91/115 are produced in accordance with GOST 1012 and Avgas 100LL in accordance with GOST 55493.
  • the production of both brands requires thermal power plant, which is produced in small quantities by a number of foreign companies.
  • a known fuel composition is high-octane unleaded aviation gasoline, which contains as a base component an alkylate with a wide boiling range, as well as from 0.1 to 40% vol. alkyl tert-butyl ether and from 0.1 to 40% vol. aromatic amines.
  • the fuel composition may also contain manganese-based octane-boosting additives at a concentration of 0.1 to 0.5 g of manganese per gallon of fuel [US Patent No. 6258134, 07/10/2001].
  • the main disadvantage of the proposed fuel composition is the combined use of aromatic amines and oxygenates in its composition. It is known that in the presence of oxygenates (especially alcohol impurities in methyl tert-butyl or other ethers), the accumulation of tarry compounds in gasoline is accelerated, and the fuel darkens. In addition, the presence of alkyl tert-butyl ether in the composition, especially in high concentrations, will increase the aggressiveness of the fuel towards non-metallic materials and significantly reduce the calorific value of gasoline.
  • composition of aviation unleaded gasoline which contains catalytic reformed gasoline, alkyl gasoline, toluene and an anti-knock additive, while the composition additionally contains a straight-run gasoline fraction boiling in the range of 62-85°C, and monomethylaniline and methyl as an anti-knock additive -tert-butyl ether with the following ratio of components, wt.%: alkyl benzine 15.0-25.0; toluene 10.0-20.0; gasoline fraction boiling within 62-85°C, 20.0-35.0; monomethylaniline 1.5-3.0; methyl tert-butyl ether 5.0-10.0; catalytic reforming gasoline, the rest [Patent RU No. 2547151, 04/10/2015].
  • the disadvantage of the proposed fuel composition is the combined use of aromatic amines and oxygenates, as well as the presence of methyl tert-butyl ether.
  • the disadvantages include the relatively low detonation resistance of the composition.
  • the fuel composition may contain additives selected from the group: anti-corrosion, antistatic, anti-icing and others permitted by the standard for aviation gasoline.
  • the fuel composition of aviation unleaded gasoline has the necessary detonation resistance, a reduced content of aromatic hydrocarbons, a high calorific value and a low boiling point of no more than 180°C.
  • this composition includes methyl tert-butyl ether, with the disadvantages mentioned above, as well as technical isooctane, which is highly expensive and is not produced on an industrial scale in Russia.
  • the maximum permissible proportion of C4-C5 hydrocarbons in accordance with the proposed proportion of isopentane is at the level of 25 wt.%, due to which aviation gasolines in accordance with the invention may be characterized by increased volatility, which affects the stability of the quality of gasoline during storage and increases the likelihood the appearance of steam locks.
  • the closest analogue known from the prior art is a composition of aviation unleaded gasoline with an octane number of at least 93.0 units, determined by the motor method, [Patent RU No. 2600112, October 20, 2016] which contains alkyl gasoline, aromatic hydrocarbons and monomethylaniline, while in As alkyl benzine, alkyl benzine with a boiling point of up to 200°C is used, as aromatic hydrocarbon composition contains toluene or its mixture with p-xylene at a mass ratio of toluene: p-xylene from 1: 1 to 5: 1 and additionally contains hexane isomerate at the following component ratio, wt.%: toluene or its mixture with p-xylene 30 .0-32.0; hexane isomerate 10.0-37.0; monomethylaniline 1, 0-3.0; alkyl gasoline with Tkk up to 200°C up to 100.
  • the technical result consists in obtaining a fuel composition of aviation
  • the prototype is characterized by narrow permissible limits for the content of aromatic hydrocarbons, as well as the need to include N-methylaniline in the composition, which affects chemical stability and makes the fractional composition heavier.
  • the present invention solves the problems of the prior art.
  • the technical result of the invention is the proposed fuel composition, which has improved storage stability and a reduced risk of vapor lock formation and includes only industrially available hydrocarbon components and pure hydrocarbons.
  • the fuel composition may contain additives: antistatic, antioxidant, dye.
  • the production of the base component - alkylate - is carried out by the catalytic reaction of isobutane with butylenes or propylenebutylene fraction.
  • the catalysts in this process the most common is sulfuric acid (sulfuric acid alkylation process).
  • the product of this process is a wide alkylate fraction with an end boiling point of more than 200 °C.
  • the alkylate obtained in such a process must be subjected to fractionation to isolate a fraction that boils up to 180°C.
  • hydrofluoric acid is used as a catalyst instead of sulfuric acid.
  • the alkylate formed as a result of this process has a lighter fractional composition; its end boiling point is usually up to 180°C.
  • Such alkyl benzine can be used as a component of the present invention without additional fractionation.
  • C7-C9 aromatic hydrocarbons toluene, xylenes, n-propylbenzene, isopropylbenzene, trimethylbenzenes, methylethylbenzenes used in the present invention are produced in catalytic reforming (platforming) installations of narrow hydrocarbon fractions with subsequent extraction of target aromatic hydrocarbons.
  • These compounds have higher anti-knock properties compared to alkyl gasoline, therefore, in order to increase knock resistance, their share in the fuel composition should be maximum.
  • the composition contains the maximum amount of aromatic hydrocarbons, which ensures compliance with such standardized characteristics of aviation gasoline as specific lower heating value and 50% distillation temperature.
  • the isomerate is formed at the isomerization unit for C5+ paraffin hydrocarbons.
  • the presence of light isoparaffin hydrocarbons in any fuel composition of aviation gasoline is necessary to increase volatility, which is characterized by such standardized indicators as saturated vapor pressure and 10% distillation temperature.
  • the isomerate used in the present invention is distinguished by the fact that it contains a weight limit of up to 5%. the amount of C4-C5 hydrocarbons. This limitation was made to increase the stability of the resulting aviation gasoline during storage and reduce the risk of vapor locks forming in the fuel systems of aircraft during its use. This limitation can be achieved by isolating fractions up to C5 from the wide isomerizate fraction.
  • the process can be implemented in industry, for example, in Isomalk-2 units equipped with a depentanization unit.
  • the most preferred fraction of the isomerate is the fraction rich in C6 isoparaffins, since they have the greatest detonation resistance of all hydrocarbons present in significant quantities in the isomerate.
  • the proposed composition contains the optimal amount of isomerate, which ensures an increase in the DNP and the temperature of the 10% distillation to the required standards.
  • mesitylene produced by Sigma Aldrich with a main substance content of 99.0%.
  • Table 1 presents the main characteristics of the components used to prepare samples of aviation unleaded gasoline.
  • Samples No. 1 and No. 2 are composed of traditionally used industrial components for the production of aviation gasoline. They include an alkylate fraction obtained in the process of hydrofluoric alkylation, a narrow isomerate fraction rich in C6 isoparaffins, obtained from the deisohexanizer unit of the Isomalk-2 installation, as well as toluene isolated from the platforming catalyzate. Samples No. 3 and No. 4 include a heavy isomerate fraction rich in C7+ isoparaffins. This fraction is characterized by low anti-knock properties (RNM is 60.0 units), therefore, to meet the standard for ROM, at least 94.0 units.
  • the composition includes higher octane aromatic hydrocarbons - mesitylene (1,3,5 - trimethylbenzene) and p-xylene.
  • the samples fully comply with the requirements of GOST 1012, with the exception of grade, which is not standardized for unleaded aviation gasoline.
  • grade which is not standardized for unleaded aviation gasoline.
  • the samples In terms of the specific lower heat of combustion and the content of actual resins, the samples have a significant margin of quality compared to the standards established for leaded aviation gasoline B-92 and B-91/115.
  • the specific lower heat of combustion is no less than 43.5 MJ/kg, and the concentration of actual and potential resins is no more than 2 mg/100 cm 3 . Samples do not interact with water.

Landscapes

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

Abstract

L'invention se rapporte au domaine de la transformation du pétrole et de la pétrochimie. L'invention concerne une composition de carburant pour une essence d'aviation ayant un indice d'octane, selon un procédé de test moteur, d'au moins 94,0, une pression de vapeurs insaturées dans une plage de 38,0-49,3 kPa, et une température de point d'ébullition d'au moins 40°C, laquelle comprend un alkylat ayant une température de fin d'ébullition allant jusqu'à 180°C, des hydrocarbures aromatiques C7-C9 et un isomérisat, dans laquelle l'isomérisat comprend une part limitée d'hydrocarbures C4-C5 ne dépassant pas 5% en poids; on utilise en qualité de composants uniquement des fractions hydrocarbures industriellement disponibles et des hydrocarbures purs selon les proportions suivantes en % en poids: alkylat avec Тkk jusqu'à 180°: jusqu'à 100; isomérisat: 8-20; hydrocarbures aromatiques C7-C9: 20-28. Le résultat technique consiste en une amélioration de la stabilité lors du stockage et une diminution du risque de formation de bouchons de vapeurs.
PCT/RU2023/050250 2022-10-27 2023-10-26 Composition de carburant pour essence sans éthanol pour aviation WO2024091146A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2022127882 2022-10-27
RU2022127882A RU2802183C1 (ru) 2022-10-27 Топливная композиция авиационного неэтилированного бензина

Publications (1)

Publication Number Publication Date
WO2024091146A1 true WO2024091146A1 (fr) 2024-05-02

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU2023/050250 WO2024091146A1 (fr) 2022-10-27 2023-10-26 Composition de carburant pour essence sans éthanol pour aviation

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2600112C1 (ru) * 2015-07-08 2016-10-20 Акционерное общество "Газпромнефть-Омский НПЗ" Топливная композиция авиационного неэтилированного бензина
RU2613087C1 (ru) * 2015-12-21 2017-03-15 Акционерное общество "Газпромнефть - Омский НПЗ" Способ получения неэтилированного авиабензина б-92/115

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2600112C1 (ru) * 2015-07-08 2016-10-20 Акционерное общество "Газпромнефть-Омский НПЗ" Топливная композиция авиационного неэтилированного бензина
RU2613087C1 (ru) * 2015-12-21 2017-03-15 Акционерное общество "Газпромнефть - Омский НПЗ" Способ получения неэтилированного авиабензина б-92/115

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