WO2023060751A1 - 一种94号无铅航空汽油及其生产方法 - Google Patents

一种94号无铅航空汽油及其生产方法 Download PDF

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Publication number
WO2023060751A1
WO2023060751A1 PCT/CN2021/138428 CN2021138428W WO2023060751A1 WO 2023060751 A1 WO2023060751 A1 WO 2023060751A1 CN 2021138428 W CN2021138428 W CN 2021138428W WO 2023060751 A1 WO2023060751 A1 WO 2023060751A1
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weight
alkanes
boiling point
blending component
aviation gasoline
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English (en)
French (fr)
Inventor
杜文莉
隆建
钱锋
钟伟民
杨明磊
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East China University of Science and Technology
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East China University of Science and Technology
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons

Definitions

  • the invention belongs to the technical field of fuel, and in particular relates to No. 94 unleaded aviation gasoline and a preparation method thereof.
  • Aviation gasoline is a high-octane fuel used in aircraft, which needs to have sufficiently high anti-knock performance. At present, it mainly depends on the addition of tetraethyl lead to increase its antiknock performance.
  • the high-octane aviation gasoline on the market basically contains tetraethyl lead, such as the latest industrial production of No. 100 low-lead aviation gasoline (No. 100LL aviation gasoline) , Tetraethyl lead content is limited to 1.2g/kg.
  • tetraethyl lead is highly toxic and volatile, lead-free has always been the goal of the aviation gasoline industry.
  • Unleaded No. 94 aviation gasoline (UL94 No. aviation gasoline) does not contain tetraethyl lead, has a high octane number, and can meet the performance requirements of most aero-engines, and is environmentally friendly.
  • CN104593101B proposes a kind of high-octane number unleaded aviation gasoline and its preparation method, the composition of this unleaded aviation gasoline is: by volume, 5-20% MON is at least 107 toluene, 2-10% aniline, 35-65% alkylate or alkylate blend, 5-20% diethyl carbonate and at least 8% isopentane.
  • the MON of toluene mentioned in this patent document is 107, which is inconsistent with the experimental value, and the formula blending effect is doubtful.
  • the aviation gasoline blending component in this patent document contains aromatic amines.
  • aromatic amines are an excellent gasoline antiknock agent and can meet the performance requirements of gasoline antiknock agents, they are harmful to the metal materials of parts such as engine valve seats. There is more serious wear, and it will shorten the life of some rubber parts or gaskets and deteriorate the sealing performance. Moreover, aromatic amines will produce nitrogen oxides after burning, which is extremely harmful to the environment. It is one of the main substances that form acid rain and is also an important substance that forms photochemical smog in the atmosphere.
  • CN108315060A has proposed a kind of No. 91 unleaded aviation gasoline and preparation method thereof, the composition of this No. 91 unleaded aviation gasoline is: by volume percentage 80-90% alkane, 10-20% aromatic hydrocarbon is prepared by reconciling, Or prepared by petrochemical refining technology.
  • the research method octane value of aviation gasoline in this patent document is 97-99, but the motor method octane value specified in the aviation gasoline standard is not mentioned.
  • No. 91 unleaded aviation gasoline has a low octane number, which cannot meet the performance requirements of most aero-engines, and cannot be applied to the piston engines used by most 100LL aviation gasoline.
  • this area needs a kind of unleaded aviation gasoline that can be applied on most 100LL aviation gasoline engines.
  • the present invention provides a kind of aviation gasoline composition, and this aviation gasoline composition satisfies ASTM D7547 standard and ASTM D7592 standard for antiknock property, evaporability, low temperature fluidity and stability etc. At the same time, it can be applied to most 100LL aviation gasoline engines, and can reduce the environmental pollution problems caused by leaded aviation gasoline to a certain extent.
  • one aspect of the present invention provides a kind of aviation gasoline composition
  • described aviation gasoline composition contains base oil and additive
  • described base oil contains blending combination A, blending component B and blending component C ;
  • the base oil includes 50-70% by weight of the blending component A, 15-25% by weight of the blending component B and 15-30% by weight of the blending component Said blending component C;
  • the blending component A contains 2-9% by weight of C4 alkanes, 2-8% by weight of C5 alkanes, 3-10% by weight of C6 alkanes, 22-29% by weight % by weight of C7 alkanes, 56-70 % by weight of C8 alkanes and 0.43-2.5 % by weight of C9 alkanes;
  • the blending component B Based on the total weight of the blending component B, the blending component B contains more than 95% by weight of m-xylene;
  • the blending component C Based on the total weight of the blending component C, the blending component C contains 0.4-7.6% by weight of C4 alkanes, 58-78% by weight of C5 alkanes, 20-31% by weight of C6 alkanes and 0.04-0.3% by weight C7 alkanes.
  • the content of the blending component A is 50-65% by weight.
  • the content of the blending component B is 15-23% by weight.
  • the content of the blending component C is 20-25% by weight.
  • the initial boiling point of the blending component A is 28-50°C, and the final boiling point is 140-157°C; preferably, the initial boiling point of the blending component A is 35-45°C, the final boiling point is 150-157°C.
  • the blending component A contains 5-6.5% by weight of C4 alkanes, 3-6% by weight of C5 alkanes, 3.5-6.5% by weight C6 alkanes, 22.5-25% by weight of C7 alkanes, 56-63% by weight of C8 alkanes and 0.45-2% by weight of C9 alkanes.
  • the blending component B has an initial boiling point of 137-138°C and a final boiling point of 138.5-140°C.
  • the blending component B based on the total weight of the blending component B, contains more than 98% by weight of m-xylene.
  • the blending component C has an initial boiling point of 21-27°C and a final boiling point of 43-58°C.
  • the blending component C contains 3-7% by weight of C4 alkanes, 68-78% by weight of C5 alkanes, 20-24% by weight C6 alkanes and 0.05-0.3% by weight of C7 alkanes.
  • the additive does not include tetraethyl lead.
  • the additives exclude arylamine antiknock agents and methyl t-butyl ether.
  • the additives include one or more selected from antioxidants, anti-icing agents, antistatic agents, anti-corrosion agents and dyes.
  • the aviation gasoline composition has a motor octane number of not less than 94.
  • the aviation gasoline composition has a motor octane number of 94.1-94.8.
  • Another aspect of the present invention provides a method of preparing the aviation gasoline composition of any of the embodiments herein, the method comprising the step of mixing the components of the aviation gasoline composition.
  • the method includes: distilling the alkylation reaction product of C4 olefins and isobutane to obtain an initial boiling point of 28-50° C., an end boiling point of 140-157° C. or The component with a boiling point of 35-45°C and a final boiling point of 150-157°C is used as blending component A.
  • the temperature of the alkylation reaction is 4-10° C.
  • the pressure is 0.4-0.45 MPa
  • the molar ratio of isobutane to C4 olefin is 8-12:1.
  • a distillation tower is used to distill the alkylation reaction product of C4 olefins and isobutane, and the conditions of the distillation include: the temperature at the bottom of the distillation tower is 133-143° C., and the pressure at the bottom of the tower is 0.41-0.53MPa, the temperature at the top of the tower is 51-56°C, and the pressure at the top of the tower is 0.41-0.5MPa.
  • the product with an initial boiling point of 28-50°C and an end boiling point of 140-157°C or an initial boiling point of 35-45°C and an end boiling point of 150-157°C The component is used as blending component A, or cut from the bottom oil of the distillation tower with an initial boiling point of 28-50°C and a final boiling point of 140-157°C or a component with an initial boiling point of 35-45°C and a final boiling point of The point is 150-157°C as blending component A.
  • alkane composition based on the total weight of the alkane composition, the alkane composition contains 2-9% by weight of C4 alkane, 2-8% by weight of C5 alkane, 3-10% by weight C6 alkanes, 22-29% by weight of C7 alkanes, 56-70% by weight of C8 alkanes and 0.43-2.5% by weight of C9 alkanes.
  • the alkane composition has an initial boiling point of 28-50°C and an end boiling point of 140-157°C.
  • the alkane composition contains 5-6.5% by weight of C4 alkanes, 3-6% by weight of C5 alkanes, 3.5-6.5% by weight of C6 alkanes, 22.5-25% by weight of C7 alkanes, 56-63% by weight of C8 alkanes and 0.45-2% by weight of C9 alkanes.
  • the alkane composition has an initial boiling point of 35-45°C and an end boiling point of 150-157°C.
  • the present invention also provides a method for preparing the alkane composition described in any embodiment herein, the method comprising: distilling the alkylation reaction product of C4 olefin and isobutane to obtain an initial boiling point of 28-50°C, The component with the final boiling point of 140-157°C or the initial boiling point of 35-45°C and the final boiling point of 150-157°C is used as blending component A.
  • the temperature of the alkylation reaction is 4-10° C.
  • the pressure is 0.4-0.45 MPa
  • the molar ratio of isobutane to C4 olefin is 8-12:1.
  • a distillation tower is used to distill the alkylation reaction product of C4 olefins and isobutane, and the conditions of the distillation include: the temperature at the bottom of the distillation tower is 133-143° C., and the pressure at the bottom of the tower is 0.41-0.53MPa, the temperature at the top of the tower is 51-56°C, and the pressure at the top of the tower is 0.41-0.5MPa;
  • the product with an initial boiling point of 28-50°C and an end boiling point of 140-157°C or an initial boiling point of 35-45°C and an end boiling point of 150-157°C Components or cut from the bottom oil of the distillation tower with an initial boiling point of 28-50°C and an end boiling point of 140-157°C or a component with an initial boiling point of 35-45°C and an end boiling point of 150-157°C .
  • the present invention also provides an alkane composition prepared by the method for preparing an alkane composition described in any embodiment herein.
  • Another aspect of the present invention provides the use of the alkane composition described in any embodiment herein in the preparation of aviation gasoline; preferably, the aviation gasoline is unleaded aviation gasoline.
  • alkylation refers to the process of transferring an alkyl group from one molecule to another, and is a reaction of introducing an alkyl group into a compound molecule.
  • the sum of the percentages of all components in the composition is equal to 100%.
  • the "C+ number" marked before the compound indicates the number of carbon atoms contained in the compound, for example, C4 alkane indicates an alkane containing four carbon atoms, C4 alkene indicates an alkene containing four carbon atoms, and C7 aromatic hydrocarbon indicates an alkene containing seven carbon atoms of aromatic hydrocarbons, and so on.
  • the determination method of motor method octane number is carried out according to the mensuration of GB_T503-2016 gasoline octane number.
  • the invention provides an aviation gasoline composition which can be used as No. 94 unleaded aviation gasoline.
  • the aviation gasoline composition contains base oil and additives. It can be understood that, in the present invention, the base oil refers to the hydrocarbons in the aviation gasoline composition.
  • the base oil in the aviation gasoline composition of the present invention includes blending component A, blending component B and blending component C.
  • Blending component A contains 2-9% by weight of C4 alkane, 2-8% by weight of C5 alkane, 3-10% by weight of C6 alkane, 22-29% by weight of C7 alkane, and 56-70% by weight of C8 alkane and 0.43-2.5% by weight of C9 alkanes, or consist of these components.
  • the content of C4 alkane is preferably 5-6.5% by weight
  • the content of C5 alkane is preferably 3-6% by weight
  • the content of C6 alkane is preferably 3.5-6.5% by weight
  • the content of C7 alkane is preferably 22.5% by weight.
  • the content of C8 alkane is preferably 56-63% by weight
  • the content of C9 alkane is preferably 0.45-2% by weight.
  • the content of C4 alkane can be 5.41% by weight, 5.83% by weight, 5.98% by weight, 6.03% by weight or 6.23% by weight
  • the content of C5 alkane can be 3.34% by weight, 3.39% by weight, 3.45% by weight % by weight, 4.02% by weight or 5.51% by weight
  • the content of C6 alkane can be 4.02% by weight, 5.13% by weight, 5.32% by weight, 5.52% by weight or 6.12% by weight
  • the content of C7 alkane can be 23.12% by weight, 23.34% by weight , 23.41% by weight, 23.99% by weight or 24.05% by weight
  • the content of C8 alkane can be 57.15% by weight, 60.39% by weight, 60.77% by weight, 61.8% by weight or 62.1% by
  • the blending component A has an initial boiling point of 28-50°C and an end boiling point of 140-157°C.
  • the initial boiling point of blending component A is 35-45°C, for example, 39-43°C.
  • the final boiling point of blending component A is 150-157°C, such as 152-156.5°C.
  • the initial boiling point of blending component A is 39.13°C, 40.02°C, 40.3°C, 42.3°C or 42.63°C
  • the final boiling point of blending component A is 152.7°C, 153.3°C, 154.29°C, 155.31°C or 156.1°C.
  • the 10% distillation temperature of blending component A can be 65-80°C, such as 70-75°C
  • the 50% distillation temperature can be 105-115°C, such as 108-113°C
  • the 90% distillation temperature can be 110°C. -120°C, such as 112-117°C.
  • the distillation range is A-B°C means that the initial boiling point is A°C and the final boiling point is B°C.
  • blending component A contains 5.41-6.23% by weight of C4 alkanes, 3.34-5.51% by weight of C5 alkanes, 4.02-6.12% by weight of C6 alkanes, 23.12-24.05% by weight of C7 alkanes, 57.15- 62.1% by weight of C8 alkanes and 0.45-1.74% by weight of C9 alkanes, and the blending component A has an initial boiling point of 28-50°C and a final boiling point of 140-157°C.
  • Blending component A can be obtained by distillation of the alkylation reaction product to obtain components with target initial boiling point and final boiling point.
  • the alkylation reaction product may be a product obtained by carrying out an alkylation reaction between C4 olefins and isobutane.
  • the temperature of the alkylation reaction can be 4-10°C
  • the pressure can be 0.4-0.45MPa
  • the molar ratio of isobutane to C4 olefins (alkene ratio) can be 8-12:1.
  • the alkylation reaction is carried out in the presence of a catalyst.
  • the catalyst for the alkylation reaction can be an acid, such as sulfonic acid, hydrofluoric acid, concentrated sulfuric acid.
  • the molar ratio of catalyst to C4 olefin can be 1-1.2:1.
  • the temperature of the alkylation reaction is about 8° C.
  • the pressure is about 0.45 MPa
  • the catalyst is hydrofluoric acid
  • the alkene ratio is about 10.5:1.
  • Distillation of the alkylation reaction product can be performed in a distillation column.
  • the distillation conditions may be as follows: the bottom temperature of the distillation tower is 133-143° C., the bottom pressure is 0.41-0.53 MPa, the top temperature is 51-56° C., and the top pressure is 0.41-0.5 MPa.
  • the temperature at the bottom of the distillation column is about 141 °C
  • the pressure at the bottom of the column is about 0.45 MPa
  • the temperature at the top of the column is about 53 °C
  • the pressure at the top of the column is about 0.45 MPa.
  • the way to obtain the components with the target initial boiling point and the final boiling point is not particularly limited, for example, the components with the target initial boiling point and the final boiling point can be drawn from the side line of the distillation column or cut from the bottom of the distillation column , methods of extraction and cutting are conventional in the art.
  • the inventors of the present invention found that the blending component A obtained by distillation of the alkylation reaction product with an initial boiling point of 28-50°C and a final boiling point of 140-157°C not only removed High-carbon compounds, which retain 56-70% by weight of C8 alkanes that can contribute to a higher octane number, and contain lighter components such as C4 and C5, and their octane number, distillation range and saturated vapor pressure data are in aviation gasoline Standard ASTM D7547 and ASTM D7592 are close to the relevant index requirements, suitable as the main component of aviation gasoline.
  • the blending component A accounts for 50-70% by weight of the base oil, preferably 50-65% by weight, such as 52% by weight, 58% by weight, 60% by weight, 64% by weight, 65% by weight weight%. Therefore, the present invention also includes blending component A as a kind of alkane composition and its application in the preparation of aviation gasoline, especially unleaded aviation gasoline, such as No. 94 unleaded aviation gasoline, and said aviation gasoline preferably contains 50 % by weight or more, for example, 52% by weight, 58% by weight, 60% by weight, 64% by weight, 65% by weight, or 70% by weight of the compounding component A.
  • the base oil also includes blending component B and blending component C, to further adjust the distillation range and saturated vapor pressure of aviation gasoline, so as to meet the relevant index requirements of aviation gasoline standards ASTM D7547 and ASTM D7592.
  • the octane number and distillation range of the blending combination B are higher, and the saturated vapor pressure is lower.
  • the addition of this component has a greater impact on the increase of the octane number of the base oil.
  • Blending component C has a lower octane number and distillation range and a higher vapor pressure, and is mainly used to adjust the saturated vapor pressure and distillation range of the base oil to meet the standards.
  • the compounding component B contains 95% by weight or more, preferably 98% by weight or more, for example, 98.5% by weight or more of m-xylene.
  • Blending component B can be purchased from commercially available sources, such as commercially available m-xylene products, or the products of various conventional processes in the art, such as petroleum catalytic reforming materials, pyrolysis gasoline, coke oven auxiliary Gasoline is obtained by separation. It can be understood that the blending component B may contain a small amount of impurities, such as 5% by weight or less, such as o-xylene, p-xylene contained in m-xylene obtained by industrially separating p-xylene or coal tar xylene. Xylene, ethylbenzene, toluene and other impurities.
  • the invention improves the saturated vapor pressure of the base oil by adding an appropriate amount of blending component B, and significantly increases the octane number of the base oil.
  • the blending component B accounts for 15-25% by weight of the base oil, such as 15% by weight, 19% by weight, 20% by weight, and 23% by weight.
  • Blending component C contains 0.4-7.6% by weight of C4 alkanes, 58-78% by weight of C5 alkanes, 20-31% by weight of C6 alkanes and 0.04-0.3% by weight of C7 alkanes, or consists of these components.
  • the content of C4 alkane is preferably 3-7 parts by weight
  • the content of C5 alkane is preferably 68-78 weight%
  • the content of C6 alkane is preferably 20-24 weight%
  • the content of C7 alkane is preferably 0.05 -0.3% by weight.
  • the content of C4 alkane is 3.9 wt%, 4.4 wt%, 5.7 wt%, 5.8 wt% or 6.3 wt%
  • the content of C5 alkane is 71.9 wt%, 73.2 wt% , 74.2% by weight or 75.2% by weight
  • the content of C6 alkane is 20.2% by weight, 20.25% by weight, 21.02% by weight, 21.8% by weight or 22.14% by weight
  • the content of C7 alkane is 0.08% by weight, 0.1% by weight, 0.15% by weight , 0.16% by weight or 0.3% by weight.
  • the initial boiling point of blending component C is preferably 21-27°C, such as 23-25.5°C
  • the final boiling point is 43-58°C, such as 43-48°C.
  • Blending component C can be purchased from commercial sources, or it can be a product from various refining processes in the field, for example, it can be purified and refined from light naphtha, as long as the properties meet the aforementioned requirements.
  • blending component C is commercial isopentane.
  • the present invention adjusts the distillation range of aviation gasoline by adding an appropriate amount of blending component C.
  • the blending component C accounts for 15-30% by weight of the base oil, preferably 20-25% by weight, such as 20% by weight, 21% by weight, 23% by weight, and 25% by weight.
  • the base oil comprises 50-70% by weight of blending component A, 15-25% by weight of blending component B and 15-30% by weight of blending component C, or by These ingredients make up.
  • the base oil comprises or consists of 50-65% by weight of Blending Component A, 15-23% by weight of Blending Component B, and 20-25% by weight of Blending Component C .
  • the base oil in the aviation gasoline composition of the present invention comprises: 3.8-5.4% by weight, preferably 4-5.2% by weight of C4 alkanes, 16.6-20% by weight, preferably 16.8-19.8% by weight of C5 alkanes, 7.2-8.4% by weight, preferably 7.4-8.2% by weight of C6 alkanes, 11.8-15.9% by weight, preferably 12-15.7% by weight of C7 alkanes, 31.7-39.7% by weight, preferably 31.9- 39.5% by weight, more preferably 32.1-39.3% by weight of C8 alkanes, 0.1-1.2% by weight, preferably 0.2-1% by weight of C9 alkanes, 14.5-23% by weight, preferably 14.7-22.8% by weight of m-xylene, and possibly Impurities present.
  • Additives in the aviation gasoline composition of the present invention can include additives commonly used in the art to meet and improve the performance of aviation gasoline, such as one or more selected from antioxidants, anti-icing agents, antistatic agents, anticorrosives and dyes Various.
  • the antioxidant suitable for the present invention can be various conventional antioxidants in the art, for example, can be selected from 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butyl One or more of phenol, 2,6-di-tert-butylphenol, N,N'-dipropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, etc., Preferably, it is one or more selected from 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol and 2,6-di-tert-butylphenol. In some embodiments, the antioxidant is 2,6-di-tert-butyl-4-methylphenol. Based on the total volume of the base oil, the content of the antioxidant is no more than 12 mg/L, preferably 10-12 mg/L.
  • the anti-icing agent suitable for the present invention may be various conventional anti-icing agents in the art, for example, one or more selected from isopropanol, diethylene glycol monomethyl ether, and the like. In some embodiments, the anti-icing agent is diethylene glycol monomethyl ether.
  • the addition amount of the anti-icing agent in the aviation gasoline composition can be the conventional addition amount in the art. In some embodiments, based on the total volume of the base oil, the anti-icing agent is added in an amount of 0.1-0.15% by volume, such as 0.12% by volume.
  • the antistatic agent suitable for the present invention can be various conventional antistatic agents in the art, for example, it can be commercially available Stadis 450 (Octel America Inc, Newark, DE 19702). Based on the total volume of the base oil, the amount of antistatic agent added generally does not exceed 3mg/L, such as 2mg/L, but when the electrical conductivity of the fuel decreases and further antistatic agents need to be added, it can continue to be added, but the cumulative total cannot More than 5mg/L.
  • the aviation gasoline composition may also contain dyes.
  • the color of the dye is selected according to the grade of aviation gasoline. For example, the color of No. 80 aviation gasoline is red, the color of No. 91 aviation gasoline is brown, the color of UL91 No. aviation gasoline is colorless, the color of No. 100 aviation gasoline is green, and the color of No. 100LL aviation gasoline is blue.
  • the anti-corrosion agent suitable for the present invention can be various conventional anti-corrosion agents in the field, and its addition amount in the aviation gasoline composition can be added according to the conventional requirements in the field.
  • preservatives include DCI-4A (innospec). In some embodiments, based on the total volume of the base oil, the preservative is added in an amount of 10-30 mg/m 3 , such as 20 mg/m 3 .
  • the aviation gasoline composition of the present invention contains no or substantially no tetraethyl lead.
  • substantially free means that certain substances are not intentionally or specifically added to the aviation gasoline composition.
  • the aviation gasoline compositions of the present invention contain no or substantially no aromatic amine antiknock agents. Examples of aromatic amine antiknock agents include aniline, N-methylaniline and m-toluidine.
  • the aviation gasoline composition of the present invention contains no or substantially no aromatic amines.
  • the aviation gasoline compositions of the present invention contain no or substantially no methyl tert-butyl ether.
  • the aviation gasoline compositions of the present invention contain no or substantially no alkyl ether antiknock agents.
  • alkyl ether antiknock agents examples include methyl t-butyl ether, ethyl t-butyl ether, methyl t-amyl ether, and diisopropyl ether.
  • the aviation gasoline compositions of the present invention contain no antiknock agents.
  • the present invention can obtain a high octane number under the standard of ASTM D7547 by adding an appropriate amount of high-octane blending component B to the aviation gasoline composition.
  • the aviation gasoline composition of the present invention can be prepared by mixing the components of the aviation gasoline composition. Wherein, the components and content requirements of the aviation gasoline composition are as described above.
  • the order of mixing the components is not particularly limited, as long as the mixing is sufficient.
  • the components of the base oil can be mixed uniformly before adding the additives for mixing, and a part of the base oil and the additives can be mixed uniformly before adding the rest of the base oil.
  • the components of the base oil are uniformly mixed, and then the additives are added for uniform mixing.
  • the preparation method of the aviation gasoline composition of the present invention further includes the step of obtaining blending component A.
  • the step of obtaining the blending component A may be: distilling the alkylation reaction product of C4 olefins and isobutane, and obtaining a component whose initial boiling point and final boiling point meet the requirements of the aforementioned blending component A as a blending group Point A.
  • the composition and distillation range of this component can meet the relevant requirements mentioned above.
  • the temperature of the alkylation reaction can be 4-10°C, the pressure can be 0.4-0.45MPa, the alkene ratio can be 8-12:1, and the acid-ene ratio can be 1-1.2:1.
  • the alkylation reaction is carried out in the presence of a catalyst.
  • the catalyst may be an acid, for example, one or more selected from sulfonic acid, hydrofluoric acid, and concentrated sulfuric acid.
  • the molar ratio of catalyst to C4 olefin (acid-olefin ratio) can be 1-1.2:1.
  • Distillation can be performed in a distillation column.
  • the distillation conditions may be as follows: the bottom temperature of the distillation tower is 133-143° C., the bottom pressure is 0.41-0.53 MPa, the top temperature is 51-56° C., and the top pressure is 0.41-0.5 MPa.
  • the way to obtain the components with the target initial boiling point and the final boiling point is not particularly limited, for example, the components with the target initial boiling point and the final boiling point can be drawn from the side line of the distillation column or cut from the bottom of the distillation column . Extraction and cutting can be carried out by conventional methods in the art.
  • the various parameters of the aviation gasoline composition of the present invention meet the requirements of the ASTM D7547 standard and the ASTM D7592 standard.
  • the motor octane number of the aviation gasoline composition of the present invention is not less than 94, such as 94-96, 94-95, 94.1-94.8, 94.3-94.8, which meets the antiknock requirement.
  • the Reid vapor pressure of the aviation gasoline composition of the invention is between 38-48kPa, which meets the requirement of evaporability.
  • the potential colloid of the aviation gasoline composition of the present invention is not more than 6mg/100mL, and the obvious lead precipitation is not more than 3mg/100mL, which meets the stability requirement.
  • the aviation gasoline composition of the present invention has an initial boiling point of 46-56°C, such as 48-55.5°C, and an end boiling point of 110-125°C, such as 115-125°C. In some embodiments, the aviation gasoline composition of the present invention has a net calorific value > 43 MJ/kg, such as > 43.5 MJ/kg. In some embodiments, the aviation gasoline composition of the present invention has a density of 700-715 kg/m 3 . In some embodiments, the aviation gasoline composition of the present invention has a sulfur content ⁇ 0.003%, eg ⁇ 0.0025%. In some embodiments, the aviation gasoline compositions of the present invention have a freezing point of about -58°C. In some embodiments, the aviation gasoline composition of the present invention has a copper strip corrosion (2h, 100°C) of about 1. In some embodiments, the aviation gasoline compositions of the present invention have a water reaction volume of 0.6-0.7 mL.
  • the aviation gasoline composition of the present invention has high octane number, good antiknock performance and high safety factor, can meet the requirements of aviation piston engine fuel for octane number, and can be directly used as aviation gasoline, such as UL94 aviation gasoline, which can be used in Most 100# low-lead aviation gasoline engines can also be blended with other aviation gasoline to obtain the required aviation gasoline.
  • the aviation gasoline composition of the present invention is prepared by simply blending several easily available components in the field with a small number of types, and meets the requirements of the ASTM D7547 standard and the ASTM D7592 standard for UL94 aviation gasoline.
  • the aviation gasoline has a high octane number, the motor method octane number is above 94, the vapor pressure and the distillation range all meet the requirements, the required blending components are few and easy to obtain, the preparation method is simple, and the production cost is low.
  • the preparation method of the aviation gasoline composition of the present invention involves less fixed investment and low production cost, especially for oil refining enterprises, it is convenient for modification and easy to implement.
  • the aviation gasoline composition of the present invention does not contain tetraethyl lead, has high octane number, good antiknock performance, high safety factor, can meet the requirements of aviation piston engine fuel on octane number, and can be used as a kind of unleaded aviation gasoline .
  • the aviation gasoline composition of the invention has low content of aromatics, can reduce pollution produced during combustion, and is beneficial to environmental protection.
  • the aviation gasoline composition of the present invention can meet antiknock requirements without containing aromatic amine antiknock agent, methyl tert-butyl ether, aromatic amine compound and/or alkyl ether antiknock agent, and has little environmental pollution , friendly to human health.
  • antistatic agent Stadis 450 was purchased from Octel America Inc, Newark, DE 19702; preservative DCI-4A was purchased from innospec company.
  • the alkylation reaction of C4 olefins and isobutane with an alkene ratio of 10.5:1 was carried out at 8°C, 0.45 MPa and the presence of catalyst hydrofluoric acid.
  • the alkylation reaction product of C4 olefins and isobutane is distilled in a distillation tower, the bottom temperature of the distillation tower is 141°C, the bottom pressure is 0.45MPa, the top temperature is 53°C, and the top pressure is 0.45MPa,
  • the distillation range drawn from the side line of the distillation tower is 39.13-155.31°C, 40.3-154.29°C, 42.3-152.7°C, 42.63-153.3°C or 40.02-156.1°C, namely the alkylated oil modified oil used in Examples 1-5 .
  • Alkylate modified oil of 64% by mass (see Table 1-1 for its properties), 21% by mass of industrial isopentane (see Table 1-2 for its properties) and 15% by mass m-xylene (see Table 1-2 for its properties) Table 1-3) mix, and then add other various additives according to Table 1-4, after reconciling evenly, obtain aviation gasoline, the property of this aviation gasoline is as shown in Table 1-5 below.
  • Alkylate modified oil of 52% by mass (see Table 2-1 for its properties), 25% by mass of industrial isopentane (see Table 2-2 for its properties) and 23% by mass m-xylene (see Table 2-2 for its properties) Table 2-3) mix, and then add other various additives according to Table 1-4, after reconciling evenly, obtain aviation gasoline, the property of this aviation gasoline is as shown in Table 2-4 below.
  • Alkylate modified oil of 60% by mass (see Table 3-1 for its properties), 20% by mass of industrial isopentane (see Table 3-2 for its properties) and 20% by mass m-xylene (see Table 3-2 for its properties) Table 3-3) mix, and then add other various additives according to Table 1-4, after reconciling evenly, obtain aviation gasoline, the property of this aviation gasoline is shown in the following table 3-4.
  • Alkylate modified oil of 58% by mass (see Table 4-1 for its properties), 23% by mass of industrial isopentane (see Table 4-2 for its properties) and 19% by mass m-xylene (see Table 4-2 for its properties) Table 4-3) mix, and then add other various additives according to Table 1-4, after reconciling evenly, obtain aviation gasoline, the property of this aviation gasoline is shown in the following table 4-4.

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Abstract

本发明提供一种可作为94号无铅航空汽油的航空汽油组合物及其生产方法，所述航空汽油组合物含有基础油和添加剂，所述基础油含有调合组合A、调合组分B和调合组分C。本发明的航空汽油组合物不含有四乙基铅，对环境友好，其马达法辛烷值在94-96之间，辛烷值高，蒸气压和馏程等指标均满足ASTM D7547标准和ASTM D7592标准对于UL94号航空汽油的要求，可以用于大部分的100号低铅航空汽油所用的发动机。本发明的航空汽油组合物所需的调合组分少并且来源广泛，燃料性能好，生产成本低，生产方法简单。

Description

一种94号无铅航空汽油及其生产方法
本申请要求于2021年10月12日提交中国专利局、申请号为CN202111186649.3、发明名称为“一种94号无铅航空汽油及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于燃料技术领域，具体涉及一种94号无铅航空汽油及其制备方法。
背景技术
航空汽油是一种用于飞机的高辛烷值燃料，需要具备足够高的抗爆性能。目前主要靠添加四乙基铅来增加其抗爆性能，市场上的高辛烷值航空汽油基本上都含有四乙基铅，如最新工业化生产的100号低铅航空汽油(100LL号航空汽油)，四乙基铅含量限定为1.2g/kg。但是随着航空汽油消耗的增加，飞机发动机的铅排放量增加，进而引起的大气污染越来越严重。由于四乙基铅毒性高，易挥发，无铅化一直是航空汽油产业发展的目标。而无铅94号航空汽油(UL94号航空汽油)不含有四乙基铅，辛烷值高，且能够满足大部分航空发动机的性能要求，对环境友好。
CN104593101B提出了一种高辛烷值无铅航空汽油及其制备方法，该无铅航空汽油的组成为：按体积计，5-20％的MON为至少107的甲苯，2-10％的苯胺，35-65％的烷基化物或烷基化物共混物，5-20％碳酸二乙酯和至少8％的异戊烷。该专利文献所提及甲苯MON为107，与实验值不符，配方调合效果存疑。另外，该专利文献中航空汽油调合组分中含有芳胺，芳胺虽然是一种优良的汽油抗爆剂，能够满足汽油抗爆剂性能的要求，却对发动机阀座等零部件金属材料有更严重的磨损，且会使部分橡胶零件或密封垫的寿命缩短、密封性变差。而且芳胺经燃烧后会产生氮氧化合物，其对环境的损害作用极大，它是形成酸雨的主要物质之一，也是形成大气中光化学烟雾的重要物质。
CN108315060A提出了一种91号无铅航空汽油及其制备方法，该91 号无铅航空汽油的组成为：按体积百分计的80-90％的烷烃，10-20％的芳烃通过调和制备，或通过石化炼制技术制备得到。该专利文献中航空汽油的研究法辛烷值为97-99，但未提及航空汽油标准中规定的马达法辛烷值数值。并且91号无铅航空汽油辛烷值较低，不能满足大部分航空发动机的性能要求，无法应用于绝大多数的100LL号航空汽油所用的活塞式发动机。
综上，本领域需要一种能在绝大多数100LL号航空汽油发动机上应用的无铅航空汽油。
发明内容
有鉴于现有技术存在的上述问题，本发明提供一种航空汽油组合物，该航空汽油组合物在满足ASTM D7547标准和ASTM D7592标准对于抗爆性、蒸发性、低温流动性及安定性等各项指标要求的同时，能在绝大多数100LL号航空汽油发动机上应用，在一定程度上能降低含铅航空汽油所带来的环境污染问题。
具体而言，本发明的一个方面提供一种航空汽油组合物，所述航空汽油组合物含有基础油和添加剂，所述基础油含有调合组合A、调合组分B和调合组分C；以所述基础油总重计，所述基础油包括50-70重量％的所述调合组分A、15-25重量％的所述调合组分B和15-30重量％的所述调合组分C；
其中，以调合组分A总重计，所述调合组分A含有2-9重量％的C4烷烃、2-8重量％的C5烷烃、3-10重量％的C6烷烃、22-29重量％的C7烷烃、56-70重量％的C8烷烃和0.43-2.5重量％的C9烷烃；
以调合组分B总重计，所述调合组分B含有95重量％以上的间二甲苯；
以调合组分C总重计，所述调合组分C含有0.4-7.6重量％的C4烷烃、58-78重量％的C5烷烃、20-31重量％的C6烷烃和0.04-0.3重量％的C7烷烃。
在一个或多个实施方案中，以所述基础油总重计，所述调合组分A的含量为50-65重量％。
在一个或多个实施方案中，以所述基础油总重计，所述调合组分B的含量为15-23重量％。
在一个或多个实施方案中，以所述基础油总重计，所述调合组分C的含量为20-25重量％。
在一个或多个实施方案中，所述调合组分A的初馏点为28-50℃，终馏点为140-157℃；优选地，所述调合组分A的初馏点为35-45℃，终馏点为150-157℃。
在一个或多个实施方案中，以调合组分A总重计，所述调合组分A含有5-6.5重量％的C4烷烃、3-6重量％的C5烷烃、3.5-6.5重量％的C6烷烃、22.5-25重量％的C7烷烃、56-63重量％的C8烷烃和0.45-2重量％的C9烷烃。
在一个或多个实施方案中，所述调合组分B的初馏点为137-138℃，终馏点为138.5-140℃。
在一个或多个实施方案中，以调合组分B总重计，所述调合组分B含有98％重量以上的间二甲苯。
在一个或多个实施方案中，所述调合组分C的初馏点为21-27℃，终馏点为43-58℃。
在一个或多个实施方案中，以调合组分C总重计，所述调合组分C含有3-7重量％的C4烷烃、68-78重量％的C5烷烃、20-24重量％的C6烷烃和0.05-0.3重量％的C7烷烃。
在一个或多个实施方案中，所述添加剂不包括四乙基铅。
在一个或多个实施方案中，所述添加剂不包括芳胺抗爆剂和甲基叔丁基醚。
在一个或多个实施方案中，所述添加剂包括选自抗氧剂、防冰剂、抗静电剂、防腐蚀剂和染料中的一种或多种。
在一个或多个实施方案中，所述航空汽油组合物的马达法辛烷值不小于94。
在一个或多个实施方案中，所述航空汽油组合物的马达法辛烷值为94.1-94.8。
本发明的另一个方面提供制备本文任一实施方案所述的航空汽油组合物的方法，所述方法包括混合所述航空汽油组合物的各组分的步骤。
在一个或多个实施方案中，所述方法包括：对C4烯烃和异丁烷的烷基化反应产物进行蒸馏，获取初馏点为28-50℃、终馏点为140-157℃或初馏点为35-45℃、终馏点为150-157℃的组分作为调合组分A。
在一个或多个实施方案中，烷基化反应的温度为4-10℃，压力为0.4-0.45MPa，异丁烷与C4烯烃的摩尔比为8-12:1。
在一个或多个实施方案中，使用蒸馏塔对C4烯烃和异丁烷的烷基化反应产物进行蒸馏，所述蒸馏的条件包括：蒸馏塔塔底温度为133-143℃，塔底压力为0.41-0.53MPa，塔顶温度为51-56℃，塔顶压力为0.41-0.5MPa。
在一个或多个实施方案中，从蒸馏塔侧线抽出初馏点为28-50℃、终馏点为140-157℃或初馏点为35-45℃、终馏点为150-157℃的组分作为调合组分A，或从蒸馏塔塔底油中切割初馏点为28-50℃、终馏点为140-157℃的组分或初馏点为35-45℃、终馏点为150-157℃作为调合组分A。
本发明的另一个方面提供一种烷烃组合物，以烷烃组合物总重计，所述烷烃组合物含有2-9重量％的C4烷烃、2-8重量％的C5烷烃、3-10重量％的C6烷烃、22-29重量％的C7烷烃、56-70重量％的C8烷烃和0.43-2.5重量％的C9烷烃。
在一个或多个实施方案中，所述烷烃组合物的初馏点为28-50℃，终馏点为140-157℃。
在一个或多个实施方案中，以烷烃组合物总重计，所述烷烃组合物含有5-6.5重量％的C4烷烃、3-6重量％的C5烷烃、3.5-6.5重量％的C6烷烃、22.5-25重量％的C7烷烃、56-63重量％的C8烷烃和0.45-2重量％的C9烷烃。
在一个或多个实施方案中，所述烷烃组合物的初馏点为35-45℃，终馏点为150-157℃。
本发明还提供制备本文任一实施方案所述的烷烃组合物的方法，所述方法包括：对C4烯烃和异丁烷的烷基化反应产物进行蒸馏，获取初馏点 为28-50℃、终馏点为140-157℃或初馏点为35-45℃、终馏点为150-157℃的组分作为调合组分A。
在一个或多个实施方案中，烷基化反应的温度为4-10℃，压力为0.4-0.45MPa，异丁烷与C4烯烃的摩尔比为8-12:1。
在一个或多个实施方案中，使用蒸馏塔对C4烯烃和异丁烷的烷基化反应产物进行蒸馏，所述蒸馏的条件包括：蒸馏塔塔底温度为133-143℃，塔底压力为0.41-0.53MPa，塔顶温度为51-56℃，塔顶压力为0.41-0.5MPa；
在一个或多个实施方案中，从蒸馏塔侧线抽出初馏点为28-50℃、终馏点为140-157℃或初馏点为35-45℃、终馏点为150-157℃的组分，或从蒸馏塔塔底油中切割初馏点为28-50℃、终馏点为140-157℃或初馏点为35-45℃、终馏点为150-157℃的组分。
本发明还提供采用本文任一实施方案所述的制备烷烃组合物的方法制备得到的烷烃组合物。
本发明的另一个方面提供本文任一实施方案所述的烷烃组合物在制备航空汽油中的用途；优选地，所述航空汽油为无铅航空汽油。
具体实施方式
使本领域技术人员可了解本发明的特点及效果，以下谨就说明书及权利要求书中提及的术语及用语进行一般性的说明及定义。除非另有指明，否则文中使用的所有技术及科学上的字词，均为本领域技术人员对于本发明所了解的通常意义，当有冲突情形时，应以本说明书的定义为准。
本文描述和公开的理论或机制，无论是对或错，均不应以任何方式限制本发明的范围，即本发明内容可以在不为任何特定的理论或机制所限制的情况下实施。
本文中，“包含”、“包括”、“含有”、“具有”以及类似的用语涵盖了“基本由……组成”和“由……组成”的意思，例如，当本文公开了“A包含B和C”时，“A由B和C组成”应当认为已被本文所公开。
在本文中，所有以数值范围或百分比范围形式界定的特征如数值、数量、含量与浓度仅是为了简洁及方便。据此，数值范围或百分比范围的描述应视为已涵盖且具体公开所有可能的次级范围及范围内的个别数值(包 括整数与分数)。
本文中，当描述实施方案或实施例时，应理解，其并非用来将本发明限定于这些实施方案或实施例。相反地，本发明所描述的方法及材料的所有的替代物、改良物及均等物，均可涵盖于权利要求书所限定的范围内。
应理解，在本发明范围中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成优选的技术方案。
本发明中，烷基化是指烷基由一个分子转移到另一个分子的过程，是向化合物分子中引入烷基的反应。
本发明中，组合物中所有组分的百分含量之和等于100％。
本发明中，化合物前标注的“C+数字”表示该化合物所含的碳原子数，例如C4烷烃表示含有四个碳原子的烷烃，C4烯烃表示含有四个碳原子的烯烃，C7芳烃表示含有七个碳原子的芳烃，依次类推。
本发明中，马达法辛烷值的测定方法按照GB_T503-2016汽油辛烷值的测定进行。
本发明提供一种可作为94号无铅航空汽油的航空汽油组合物，该航空汽油组合物含有基础油和添加剂。可以理解的是，本发明中，基础油是指航空汽油组合物中的烃类物质。
本发明的航空汽油组合物中的基础油包括调合组分A、调合组分B和调合组分C。
调合组分A含有2-9重量％的C4烷烃、2-8重量％的C5烷烃、3-10重量％的C6烷烃、22-29重量％的C7烷烃、56-70重量％的C8烷烃和0.43-2.5重量％的C9烷烃，或由这些组分组成。调合组分A中，C4烷烃的含量优选为5-6.5重量％，C5烷烃的含量优选为3-6重量％，C6烷烃的含量优选为3.5-6.5重量％，C7烷烃的含量优选为22.5-25重量％，C8烷烃的含量优选为56-63重量％，C9烷烃的含量优选为0.45-2重量％。例如，调合组分A中，C4烷烃的含量可以为5.41重量％、5.83重量％、5.98重量％、6.03重量％或6.23重量％，C5烷烃的含量可以为3.34重量％、3.39重量％、3.45重量％、4.02重量％或5.51重量％，C6烷烃的含量可以为 4.02重量％、5.13重量％、5.32重量％、5.52重量％或6.12重量％，C7烷烃的含量可以为23.12重量％、23.34重量％、23.41重量％、23.99重量％或24.05重量％，C8烷烃的含量可以为57.15重量％、60.39重量％、60.77重量％、61.8重量％或62.1重量％，C9烷烃的含量可以为0.45重量％、0.62重量％、0.63重量％、1.2重量％或1.74重量％。
在一些实施方案中，调合组分A的初馏点为28-50℃，终馏点为140-157℃。优选地，调合组分A的初馏点为35-45℃，例如39-43℃。优选地，调合组分A的终馏点为150-157℃，例如152-156.5℃。在一些实施方案中，调合组分A的初馏点为39.13℃、40.02℃、40.3℃、42.3℃或42.63℃，调合组分A的终馏点为152.7℃、153.3℃、154.29℃、155.31℃或156.1℃。调合组分A的10％馏出温度可以为65-80℃、例如70-75℃，50％馏出温度可以为105-115℃、例如108-113℃，90％馏出温度可以为110-120℃、例如112-117℃。本发明中，“馏程为A-B℃”表示初馏点为A℃，终馏点为B℃。
在一些实施方案中，调合组分A含有5.41-6.23重量％的C4烷烃、3.34-5.51重量％的C5烷烃、4.02-6.12重量％的C6烷烃、23.12-24.05重量％的C7烷烃、57.15-62.1重量％的C8烷烃和0.45-1.74重量％的C9烷烃，且调合组分A的初馏点为28-50℃，终馏点为140-157℃。
调合组分A可以通过对烷基化反应产物进行蒸馏获取具有目标初馏点和终馏点的组分而得到。烷基化反应产物可以是C4烯烃和异丁烷进行烷基化反应得到的产物。烷基化反应的温度可以为4-10℃，压力可以为0.4-0.45MPa，异丁烷与C4烯烃的摩尔比(烷烯比)可以为8-12:1。烷基化反应在催化剂存在下进行。烷基化反应的催化剂可以是酸，例如磺酸、氢氟酸、浓硫酸。催化剂与C4烯烃的摩尔比(酸烯比)可以为1-1.2:1。在一些实施方案中，烷基化反应的温度为约8℃，压力为约0.45MPa，催化剂为氢氟酸，烷烯比为约10.5:1。对烷基化反应产物进行蒸馏可以在蒸馏塔中进行。蒸馏的条件可以是：蒸馏塔塔底温度为133-143℃，塔底压力为0.41-0.53MPa，塔顶温度为51-56℃，塔顶压力为0.41-0.5MPa。在一些实施方案中，蒸馏塔塔底温度为约141℃，塔底压力为约0.45MPa， 塔顶温度为约53℃，塔顶压力为约0.45MPa。获取具有目标初馏点和终馏点的组分的方式不受特别限制，例如，可以从蒸馏塔的侧线抽出或从蒸馏塔的塔底切割出具有目标初馏点和终馏点的组分，抽出和切割的方法是本领域常规的。
本发明的发明人发现，对烷基化反应产物蒸馏获得的初馏点为28-50℃、终馏点为140-157℃的调合组分A，不仅去除了馏程为160℃以上的高碳化合物，保留了可以贡献较高辛烷值的56-70重量％的C8烷烃，同时含有C4、C5等较轻的组分，其辛烷值、馏程和饱和蒸气压数据在航空汽油标准ASTM D7547和ASTM D7592相关指标要求附近，适合作为航空汽油的主体成分。本发明的航空汽油组合物中，调合组分A占到基础油的50-70重量％，优选50-65重量％，例如52重量％、58重量％、60重量％、64重量％、65重量％。因此，本发明也包括作为一种烷烃组合物的调合组分A及其在制备航空汽油、特别是无铅航空汽油、例如94号无铅航空汽油中的应用，所述航空汽油优选包含50重量％以上、例如52重量％、58重量％、60重量％、64重量％、65重量％、70重量％的调合组分A。
本发明中，所述基础油还包括调合组分B和调合组分C，以进一步调整航空汽油的馏程和饱和蒸气压，使之满足航空汽油标准ASTM D7547和ASTM D7592相关指标要求。调合组合B的辛烷值和馏程较高，和饱和蒸气压低，该组分的加入量对基础油辛烷值的提高幅度有较大影响。调合组分C的辛烷值和馏程较低、蒸气压高，主要用于调节基础油的饱和蒸气压和馏程以使其符合标准。
调合组分B含有95重量％以上、优选98重量％以上、例如98.5重量％以上的间二甲苯。调合组分B可以从市售途径购得，例如可以是市售的间二甲苯产品，也可以是本领域各种常规工艺的产物，例如由石油催化重整料、裂解汽油、焦炉副产汽油经分离而得。可以理解的是，调合组分B可以包含少量、例如5重量％以下的杂质，例如工业上对石油二甲苯或煤焦油二甲苯进行分离所获取的间二甲苯中含有的邻二甲苯、对二甲苯、乙基苯、甲苯等杂质。
本发明通过添加适量的调合组分B改善基础油的饱和蒸气压，并且显著提高基础油的辛烷值。本发明的航空汽油组合物中，调合组分B占到基础油的15-25重量％，例如15重量％、19重量％、20重量％、23重量％。
调合组分C含有0.4-7.6重量％的C4烷烃、58-78重量％的C5烷烃、20-31重量％的C6烷烃和0.04-0.3重量％的C7烷烃，或由这些成分组成。调合组分C中，C4烷烃的含量优选为3-7重量份，C5烷烃的含量优选为68-78重量％，C6烷烃的含量优选为20-24重量％，C7烷烃的含量优选为0.05-0.3重量％。在一些实施方案中，调合组分C中，C4烷烃的含量为3.9重量％、4.4重量％、5.7重量％、5.8重量％或6.3重量％，C5烷烃的含量为71.9重量％、73.2重量％、74.2重量％或75.2重量％，C6烷烃的含量为20.2重量％、20.25重量％、21.02重量％、21.8重量％或22.14重量％，C7烷烃的含量为0.08重量％、0.1重量％、0.15重量％、0.16重量％或0.3重量％。调合组分C的初馏点优选为21-27℃、例如23-25.5℃，终馏点为43-58℃、例如43-48℃。
调合组分C可以从市售途径购得，也可以来自本领域各类炼油工艺的产物，例如可以由轻石脑油提纯精制而成，只要性质满足前述要求即可。在一些实施方案中，调合组分C为工业异戊烷。
本发明通过添加适量的调合组分C调节航空汽油的馏程。本发明的航空汽油组合物中，调合组分C占到基础油的15-30重量％，优选20-25重量％，例如20重量％、21重量％、23重量％、25重量％。
本发明的航空汽油组合物中，基础油包括50-70重量％的调合组分A、15-25重量％的调合组分B和15-30重量％的调合组分C，或由这些成分组成。在一些实施方案中，基础油包括50-65重量％的调合组分A、15-23重量％的调合组分B和20-25重量％的调合组分C，或由这些成分组成。
在一些实施方案中，以基础油的总重计，本发明的航空汽油组合物中的基础油包含：3.8-5.4重量％、优选4-5.2重量％的C4烷烃，16.6-20重量％、优选16.8-19.8重量％的C5烷烃，7.2-8.4重量％、优选7.4-8.2重量％的C6烷烃，11.8-15.9重量％、优选12-15.7重量％的C7烷烃，31.7-39.7 重量％、优选31.9-39.5重量％、更优选32.1-39.3重量％的C8烷烃，0.1-1.2重量％、优选0.2-1重量％的C9烷烃，14.5-23重量％、优选14.7-22.8重量％的间二甲苯，和可能存在的杂质。
本发明的航空汽油组合物中的添加剂可以包括本领域常用于满足和提高航空汽油性能的添加剂，例如选自抗氧剂、防冰剂、抗静电剂、防腐蚀剂和染料等中的一种或多种。
适用于本发明的抗氧剂可以为本领域常规的各种抗氧剂，例如可以选自2,6-二叔丁基-4-甲酚、2,4-二甲基-6-叔丁基酚、2,6-二叔丁基酚、N,N’-二丙基-对苯二胺、N,N’-二仲丁基-对苯二胺等中的一种或多种，优选为选自2,6-二叔丁基-4-甲酚、2,4-二甲基-6-叔丁基酚和2,6-二叔丁基酚中的一种或多种。在一些实施方案中，抗氧剂为2,6-二叔丁基-4-甲酚。以基础油的总体积计，抗氧剂的含量不超过12mg/L，优选为10-12mg/L。
适用于本发明的防冰剂可以为本领域常规的各种防冰剂，例如可以选自异丙醇、二乙二醇单甲醚等中的一种或多种。在一些实施方案中，防冰剂为二乙二醇单甲醚。防冰剂在航空汽油组合物中的添加量可以为本领域常规的添加量。在一些实施方案中，以基础油的总体积计，防冰剂的添加量为0.1-0.15体积％、例如0.12体积％。
适用于本发明的抗静电剂可以为本领域常规的各种抗静电剂，例如可以为商购品Stadis 450(Octel America Inc,Newark,DE 19702)。以基础油的总体积计，抗静电剂的添加量一般不超过3mg/L、例如2mg/L，但当燃料的导电率下降需要进一步添加抗静电剂时，可以继续添加，但累计总量不能超过5mg/L。
另外，为便于对航空汽油组合物的等级进行快速区分，航空汽油组合物还可以含有染料。所述染料的颜色根据航空汽油的等级进行选择。例如，80号航空汽油的颜色为红色，91号航空汽油的颜色为褐色，UL91号航空汽油的颜色为无色，100号航空汽油的颜色为绿色，100LL号航空汽油的颜色为蓝色。
适用于本发明的防腐蚀剂可以为本领域常规的各种防腐蚀剂，其在航空汽油组合物中的添加量可以按照本领域常规的要求进行添加。防腐剂的 实例包括DCI-4A(innospec公司)。在一些实施方案中，以基础油的总体积计，防腐剂的添加量为10-30mg/m 3、例如20mg/m 3。
本发明的航空汽油组合物不包含或基本不包含四乙基铅。本文中，“基本不包含”指的是不故意或不特地向航空汽油组合物中添加某些物质。在一些实施方案中，本发明的航空汽油组合物不包含或基本不包含芳胺抗爆剂。芳胺抗爆剂的实例包括苯胺、N-甲基苯胺和间甲苯胺。在一些实施方案中，本发明的航空汽油组合物不包含或基本不包含芳胺类化合物。一些实施方案中，本发明的航空汽油组合物不包含或基本不包含甲基叔丁醚。在一些实施方案中，本发明的航空汽油组合物不包含或基本不包含烷基醚抗爆剂。烷基醚抗爆剂的实例包括甲基叔丁基醚、乙基叔丁基醚、甲基叔戊基醚和二异丙基醚。在一些实施方案中，本发明的航空汽油组合物不包含抗爆剂。在不使用抗爆剂的情况下，本发明通过向航空汽油组合物中加入适量高辛烷值的调合组分B，在满足ASTM D7547的标准下，可以获取高的辛烷值。
本发明的航空汽油组合物可以通过混合航空汽油组合物的各组分而制得。其中，航空汽油组合物的各组分及其含量要求如前文所述。
制备本发明的航空汽油组合物时，混合各组分的顺序不受特别限制，只要混合充分即可。例如，可以先将基础油的各组分混合均匀后再加入添加剂进行混合，也先将一部分基础油与添加剂混合均匀后再加入其余部分的基础油。本发明中，优选地，将基础油的各组分混合均匀后，再加入添加剂进行混匀。
在一些实施方案中，本发明的航空汽油组合物的制备方法还包括获取调合组分A的步骤。获取调合组分A的步骤可以是：对C4烯烃和异丁烷的烷基化反应产物进行蒸馏，获取初馏点和终馏点满足前述调合组分A要求的组分作为调合组分A。该组分的组成和馏程能够满足前文所述的相关要求。烷基化反应的温度可以为4-10℃，压力可以为0.4-0.45MPa，烷烯比可以为8-12:1，酸烯比可以为1-1.2:1。烷基化反应在催化剂存在下进行。催化剂可以是酸，例如可以选自磺酸、氢氟酸、浓硫酸中的一种或多种。催化剂与C4烯烃的摩尔比(酸烯比)可以为1-1.2:1。蒸馏可以在蒸 馏塔中进行。蒸馏的条件可以是：蒸馏塔塔底温度为133-143℃，塔底压力为0.41-0.53MPa，塔顶温度为51-56℃，塔顶压力为0.41-0.5MPa。获取具有目标初馏点和终馏点的组分的方式不受特别限制，例如，可以从蒸馏塔的侧线抽出或从蒸馏塔的塔底切割出具有目标初馏点和终馏点的组分。抽出和切割可以采用本领域的常规方法进行。
本发明的航空汽油组合物的各项参数满足ASTM D7547标准和ASTM D7592标准的要求。本发明的航空汽油组合物的马达法辛烷值不小于94、例如为94-96、94-95、94.1-94.8、94.3-94.8，满足抗爆性要求。本发明的航空汽油组合物的雷德蒸气压在38-48kPa之间，满足蒸发性要求。本发明的航空汽油组合物的潜在胶质不大于6mg/100mL，显见铅沉淀不大于3mg/100mL，满足安定性要求。
在一些实施方案中，本发明的航空汽油组合物的初馏点为46-56℃、例如48-55.5℃，终馏点为110-125℃、例如115-125℃。在一些实施方案中，本发明的航空汽油组合物的净热值≥43MJ/kg、例如≥43.5MJ/kg。在一些实施方案中，本发明的航空汽油组合物的密度为700-715kg/m 3。在一些实施方案中，本发明的航空汽油组合物的硫含量≤0.003％、例如≤0.0025％。在一些实施方案中，本发明的航空汽油组合物的冰点为约-58℃。在一些实施方案中，本发明的航空汽油组合物的铜片腐蚀(2h，100℃)为约1。在一些实施方案中，本发明的航空汽油组合物的水反应体积为0.6-0.7mL。
本发明的航空汽油组合物辛烷值高，抗爆性能好，安全系数高，能满足航空活塞式发动机燃料对辛烷值的要求，可直接用作航空汽油，例如UL94号航空汽油，可用于大部分的100号低铅航空汽油所用的发动机，也可以与其他航空汽油调配成所需的航空汽油。
本发明具有以下有益效果：
本发明的航空汽油组合物由种类数较少的几种本领域易得的组分通过简单混合的方式调合制备而成，并且满足ASTM D7547标准和ASTM D7592标准对于UL94号航空汽油的要求。该航空汽油辛烷值高，马达法辛烷值在94以上，蒸气压和馏程均满足要求，所需调合组分少且简单易得，制备方法简单，生产成本低。本发明的航空汽油组合物的制备方法所 涉及的固定投资少，生产成本低，特别是对炼油企业来说，改造方便，容易实施。
本发明的航空汽油组合物不含四乙基铅，辛烷值高，抗爆性能好，安全系数高，能满足航空活塞式发动机燃料对辛烷值的要求，可作为一种无铅航空汽油。本发明的航空汽油组合物芳烃含量低，可以降低燃烧时产生的污染，有利于环保。本发明的航空汽油组合物能够在不包含芳胺抗爆剂、甲基叔丁基醚、芳胺类化合物和/或烷基醚抗爆剂的情况下满足抗爆性要求，对环境污染小，对人类健康友好。
下文将以具体实施例的方式阐述本发明。应理解，这些实施例仅仅是阐述性的，并非意图限制本发明的范围。实施例中所用到的方法、试剂和材料，除非另有说明，否则为本领域常规的方法、试剂和材料。实施例中的原料，除非另有说明，否则可通过市售途径购得。
以下实施例中，各项参数均按照ASTM-D910标准测得。
以下实施例中，抗静电剂Stadis 450购自Octel America Inc,Newark,DE 19702；防腐剂DCI-4A购自innospec公司。
制备例
在8℃、0.45MPa和催化剂氢氟酸存在下使烷烯比为10.5:1的C4烯烃和异丁烷进行烷基化反应。将C4烯烃和异丁烷的烷基化反应产物在蒸馏塔中进行蒸馏，蒸馏塔塔底温度为141℃，塔底压力为0.45MPa，塔顶温度为53℃，塔顶压力为0.45MPa，从蒸馏塔侧线抽出馏程为39.13-155.31℃、40.3-154.29℃、42.3-152.7℃、42.63-153.3℃或40.02-156.1℃，即分别为实施例1-5所用的烷基化油改质油。
实施例1
将64质量％的烷基化油改质油(其性质见表1-1)、21质量％的工业异戊烷(其性质见表1-2)和15质量％间二甲苯(其性质见表1-3)混合，再按表1-4加入其他各项添加剂，调和均匀后，得到航空汽油，该航空汽 油的性质如下表1-5所示。
表1-1
Figure PCTCN2021138428-appb-000001
表1-2
Figure PCTCN2021138428-appb-000002
表1-3
Figure PCTCN2021138428-appb-000003
表1-4
Figure PCTCN2021138428-appb-000004
表1-5
Figure PCTCN2021138428-appb-000005
Figure PCTCN2021138428-appb-000006
实施例2
将52质量％的烷基化油改质油(其性质见表2-1)、25质量％的工业异戊烷(其性质见表2-2)和23质量％间二甲苯(其性质见表2-3)混合，再按表1-4加入其他各项添加剂，调和均匀后，得到航空汽油，该航空汽油的性质如下表2-4所示。
表2-1
Figure PCTCN2021138428-appb-000007
表2-2
Figure PCTCN2021138428-appb-000008
Figure PCTCN2021138428-appb-000009
表2-3
Figure PCTCN2021138428-appb-000010
表2-4
Figure PCTCN2021138428-appb-000011
实施例3
将60质量％的烷基化油改质油(其性质见表3-1)、20质量％的工业异戊烷(其性质见表3-2)和20质量％间二甲苯(其性质见表3-3)混合，再按表1-4加入其他各项添加剂，调和均匀后，得到航空汽油，该航空汽油的性质如下表3-4所示。
表3-1
Figure PCTCN2021138428-appb-000012
表3-2
Figure PCTCN2021138428-appb-000013
表3-3
Figure PCTCN2021138428-appb-000014
表3-4
Figure PCTCN2021138428-appb-000015
Figure PCTCN2021138428-appb-000016
实施例4
将58质量％的烷基化油改质油(其性质见表4-1)、23质量％的工业异戊烷(其性质见表4-2)和19质量％间二甲苯(其性质见表4-3)混合，再按表1-4加入其他各项添加剂，调和均匀后，得到航空汽油，该航空汽油的性质如下表4-4所示。
表4-1
Figure PCTCN2021138428-appb-000017
表4-2
Figure PCTCN2021138428-appb-000018
表4-3
Figure PCTCN2021138428-appb-000019
Figure PCTCN2021138428-appb-000020
表4-4
Figure PCTCN2021138428-appb-000021
实施例5
将65质量％的烷基化油改质油(其性质见表5-1)、20质量％的工业异戊烷(其性质见表5-2)和15质量％间二甲苯(其性质见表5-3)混合，再按表1-4加入其他各项添加剂，调和均匀后，得到航空汽油，该航空汽油的性质如下表5-4所示。
表5-1
Figure PCTCN2021138428-appb-000022
Figure PCTCN2021138428-appb-000023
表5-2
Figure PCTCN2021138428-appb-000024
表5-3
Figure PCTCN2021138428-appb-000025
表5-4
Figure PCTCN2021138428-appb-000026
由以上实施例结果可以看出，将烷基化油改质油、工业异戊烷、间二甲苯等本领域容易获取的各种组分混合均匀后加入抗冰剂、防腐剂等添加剂即可成功调和得到航空汽油。本发明的航空汽油能在大多数100LL号航空汽油发动机上成功使用，降低了铅含量的排放，有利于环境保护。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (23)

  1. 一种航空汽油组合物，所述航空汽油组合物含有基础油和添加剂，其特征在于，所述基础油含有调合组分A、调合组分B和调合组分C；以所述基础油总重计，所述基础油包括50-70重量％的所述调合组分A、15-25重量％的所述调合组分B和15-30重量％的所述调合组分C；
    其中，以调合组分A总重计，所述调合组分A含有2-9重量％的C4烷烃、2-8重量％的C5烷烃、3-10重量％的C6烷烃、22-29重量％的C7烷烃、56-70重量％的C8烷烃和0.43-2.5重量％的C9烷烃；
    以调合组分B总重计，所述调合组分B含有95重量％以上的间二甲苯；
    以调合组分C总重计，所述调合组分C含有0.4-7.6重量％的C4烷烃、58-78重量％的C5烷烃、20-31重量％的C6烷烃和0.04-0.3重量％的C7烷烃。
  2. 如权利要求1所述的航空汽油组合物，其特征在于，以所述基础油总重计，所述基础油的组成满足以下一项或多项特征：
    所述调合组分A的含量为50-65重量％；
    所述调合组分B的含量为15-23重量％；
    所述调合组分C的含量为20-25重量％。
  3. 如权利要求1所述的航空汽油组合物，其特征在于，所述航空汽油组合物具有以下一项或多项特征：
    所述调合组分A的初馏点为28-50℃，终馏点为140-157℃；
    以调合组分A总重计，所述调合组分A含有5-6.5重量％的C4烷烃、3-6重量％的C5烷烃、3.5-6.5重量％的C6烷烃、22.5-25重量％的C7烷烃、56-63重量％的C8烷烃和0.45-2重量％的C9烷烃；
    所述调合组分B的初馏点为137-138℃，终馏点为138.5-140℃；
    以调合组分B总重计，所述调合组分B含有98％重量以上的间二甲苯；
    所述调合组分C的初馏点为21-27℃，终馏点为43-58℃；
    以调合组分C总重计，所述调合组分C含有3-7重量％的C4烷烃、68-78重量％的C5烷烃、20-24重量％的C6烷烃和0.05-0.3重量％的C7烷烃；
    所述添加剂不包括四乙基铅；
    所述添加剂不包括芳胺抗爆剂和甲基叔丁基醚；
    所述添加剂包括选自抗氧剂、防冰剂、抗静电剂、防腐蚀剂和染料中的一种或多种。
  4. 如权利要求3所述的航空汽油组合物，其特征在于，所述调合组分A的初馏点为35-45℃，终馏点为150-157℃。
  5. 如权利要求1-4中任一项所述的航空汽油组合物，其特征在于，所述航空汽油组合物的马达法辛烷值不小于94。
  6. 如权利要求5所述的航空汽油组合物，其特征在于，所述航空汽油组合物的马达法辛烷值为94-96。
  7. 如权利要求6任一项所述的航空汽油组合物，其特征在于，所述航空汽油组合物的马达法辛烷值为94.1-94.8。
  8. 制备权利要求1-7中任一项所述的航空汽油组合物的方法，其特征在于，所述方法包括混合所述航空汽油组合物的各组分的步骤。
  9. 如权利要求8所述的方法，其特征在于，所述方法包括：对C4烯烃和异丁烷的烷基化反应的产物进行蒸馏，获取初馏点为28-50℃、终馏点为140-157℃的组分作为调合组分A。
  10. 如权利要求9所述的方法，其特征在于，所述烷基化反应的温度为4-10℃，压力为0.4-0.45MPa，异丁烷与C4烯烃的摩尔比为8-12:1。
  11. 如权利要求9所述的方法，其特征在于，使用蒸馏塔进行蒸馏，所述蒸馏的条件包括：蒸馏塔塔底温度为133-143℃，塔底压力为0.41-0.53MPa，塔顶温度为51-56℃，塔顶压力为0.41-0.5MPa。
  12. 如权利要求11所述的方法，其特征在于，从所述蒸馏塔侧线抽出初馏点为28-50℃、终馏点为140-157℃的组分作为调合组分A。
  13. 如权利要求11或12所述的方法，其特征在于，从所述蒸馏塔塔底油中切割初馏点为28-50℃、终馏点为140-157℃的组分作为调合组分 A。
  14. 一种烷烃组合物，其特征在于，以烷烃组合物总重计，所述烷烃组合物含有2-9重量％的C4烷烃、2-8重量％的C5烷烃、3-10重量％的C6烷烃、22-29重量％的C7烷烃、56-70重量％的C8烷烃和0.43-2.5重量％的C9烷烃。
  15. 如权利要求14所述的烷烃组合物，其特征在于，所述烷烃组合物的初馏点为28-50℃，终馏点为140-157℃。
  16. 如权利要求14所述的烷烃组合物，其特征在于，
    以烷烃组合物总重计，所述烷烃组合物含有5-6.5重量％的C4烷烃、3-6重量％的C5烷烃、3.5-6.5重量％的C6烷烃、22.5-25重量％的C7烷烃、56-63重量％的C8烷烃和0.45-2重量％的C9烷烃；和/或
    所述烷烃组合物的初馏点为35-45℃，终馏点为150-157℃。
  17. 制备权利要求14～16任一项所述的烷烃组合物的方法，其特征在于，所述方法包括：对C4烯烃和异丁烷的烷基化反应的产物进行蒸馏，获取初馏点为28-50℃、终馏点为140-157℃的组分作为调合组分A。
  18. 如权利要求17所述的方法，其特征在于，所述烷基化反应的温度为4-10℃，压力为0.4-0.45MPa，异丁烷与C4烯烃的摩尔比为8-12:1。
  19. 如权利要求17所述的方法，其特征在于，使用蒸馏塔进行蒸馏，所述蒸馏的条件包括：蒸馏塔塔底温度为133-143℃，塔底压力为0.41-0.53MPa，塔顶温度为51-56℃，塔顶压力为0.41-0.5MPa。
  20. 如权利要求19所述的方法，其特征在于，从所述蒸馏塔侧线抽出初馏点为28-50℃、终馏点为140-157℃的组分。
  21. 如权利要求19或20所述的方法，其特征在于，从所述蒸馏塔塔底油中切割初馏点为28-50℃、终馏点为140-157℃的组分。
  22. 权利要求14～16任一项所述的烷烃组合物或采用权利要求17～21任一项所述的方法制备得到的烷烃组合物在制备航空汽油中的用途。
  23. 如权利要求22所述的用途，其特征在于，所述航空汽油为无铅航空汽油。
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