CN115074161B - Aviation gasoline composition, aviation gasoline and preparation method thereof - Google Patents
Aviation gasoline composition, aviation gasoline and preparation method thereof Download PDFInfo
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- CN115074161B CN115074161B CN202110277315.0A CN202110277315A CN115074161B CN 115074161 B CN115074161 B CN 115074161B CN 202110277315 A CN202110277315 A CN 202110277315A CN 115074161 B CN115074161 B CN 115074161B
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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
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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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
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
- C10L1/306—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond) organo Pb compounds
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Abstract
The invention relates to the technical field of aviation fuels, and discloses an aviation gasoline composition, an aviation gasoline and a preparation method thereof. The aviation gasoline composition contains base oil and additives, wherein the base oil contains component oil A, the component oil A contains 2-7 wt% of C4 alkane, 2-6 wt% of C5 alkane, 3-8 wt% of C6 alkane, 20-30 wt% of C7 alkane, 49-65 wt% of C8 alkane, 0.5-3 wt% of C9 alkane and 2-5 wt% of C10 alkane, and the distillation range of the component oil A is 23-160 ℃; the additive contains tetraethyllead. The aviation gasoline composition meets the requirements of various indexes such as antiknock property, evaporability, low-temperature fluidity, stability and the like, has less blending components, does not need to be highly refined, is low in cost and easy to obtain, and has wide sources. In addition, the aviation gasoline composition has low content of lead and aromatic hydrocarbon, small combustion pollution and environmental friendliness. And the preparation process is simple and is very easy to implement.
Description
Technical Field
The invention relates to the technical field of aviation fuels, in particular to an aviation gasoline composition, an aviation gasoline and a preparation method thereof.
Background
Aviation gasoline is a high octane fuel for aircraft and is an important component of aviation fuel. With the rapid development of the general aviation industry and the defense industry in China, the market demand of aviation gasoline is increasing. The upper limit of the lead content of 100 # aviation gasoline used in China at present is 2.4g/Kg, and the upper limit of the lead content of 100 # aviation gasoline abroad is 1.2g/Kg, and the problem of lead pollution caused by burning leaded aviation gasoline in China has attracted wide attention. In order to reduce the environmental problems caused by tetraethyl lead and reduce the harm to human bodies, low-lead aviation gasoline has become a trend of future aviation industry development. 100LL aviation gasoline is gradually the main body of future aviation gasoline market demand in China.
CN104560233a discloses a low-lead aviation gasoline and a preparation method thereof, the composition of the low-lead aviation gasoline is: 40-90% of industrial isooctane, 5-30% of alkane without isooctane, 5-30% of aromatic hydrocarbon, 0.001-0.12% of tetraethyl lead and 0.0008-0.0017% of antioxidant. However, the blending components adopted in the invention have high price, and the aromatic hydrocarbon content is too high, so that the environment is easily polluted.
CN109022059a proposes a lead-free aviation piston engine fuel and a preparation method thereof, the lead-free aviation piston engine fuel comprises the following components: 0.1-8% of n-butane, 4-25% of carbon five, 0.1-33% of toluene, 0.1-33% of xylene and 25-80% of aromatic hydrocarbon 1, wherein the aromatic hydrocarbon 1 consists of C7-C9 aromatic hydrocarbons with a boiling point lower than 200 ℃. However, too high an aromatic content, exceeding the limit of not more than 25% specified in ASTM-D910, can cause significant environmental pollution. The fuel component contains aromatic amine which can meet the requirements of the performance of the gasoline antiknock agent, but can cause serious abrasion of metal materials of parts such as engine valve seats and the like, and can shorten the service life of part of rubber parts or sealing gaskets and deteriorate the sealing performance.
In summary, the 100LL aviation gasoline blending in China at present has more types of component oils, the purity requirement of each component oil is higher, the component oil is prepared by multiple refining, and the production investment cost is higher. In addition, the aromatic hydrocarbon content is higher, further pollution is caused to the environment, and the production and preparation process is complex.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide an aviation gasoline composition and a preparation method thereof, wherein the aviation gasoline composition meets the requirements of various indexes such as antiknock property, evaporation property, low-temperature fluidity, stability and the like, and meanwhile has less blending components, simple preparation process, no need of highly refining each component, low cost, easy obtainment, wide sources and easy implementation. In addition, the aviation gasoline composition has low content of lead and aromatic hydrocarbon, small combustion pollution and environmental friendliness.
In order to achieve the above object, the first aspect of the present invention provides an aviation gasoline composition comprising a base oil and an additive, wherein the base oil comprises a component oil a,
the component oil A contains 2-7 wt% of C4 alkane, 2-6 wt% of C5 alkane, 3-8 wt% of C6 alkane, 20-30 wt% of C7 alkane, 49-65 wt% of C8 alkane, 0.5-3 wt% of C9 alkane and 2-5 wt% of C10 alkane, and the distillation range of the component oil A is 23-160 ℃;
the additive contains tetraethyllead.
Preferably, the base oil further comprises component oil B and/or component oil C, the component oil B comprising more than 95 wt% of C7 aromatic hydrocarbons; the component oil C contains 1-10 wt% of C4 alkane, 40-75 wt% of C5 alkane, 20-50 wt% of C6 alkane and 0.03-0.4 wt% of C7 alkane.
Preferably, the component oil B has a distillation range of 109-111 ℃.
Preferably, the component oil C has a distillation range of 20-70 ℃.
Preferably, the base oil contains 65 to 100% by weight of the component oil A, 0 to 15% by weight of the component oil B and 0 to 20% by weight of the component oil C.
Preferably, the tetraethyl lead content is 0.8-1.2g/kg relative to the base oil; more preferably, the tetraethyl lead content is 0.8-1.0g/kg relative to the base oil.
Preferably, the component oil A contains 4.35 to 6.5 wt% of C4 alkane, 4.5 to 6 wt% of C5 alkane, 3.5 to 5.5 wt% of C6 alkane, 24 to 25.5 wt% of C7 alkane, 50 to 60 wt% of C8 alkane, 0.75 to 1.5 wt% of C9 alkane and 2 to 3 wt% of C10 alkane, and the distillation range of the component oil A is 45 to 160 ℃.
Preferably, the aviation gasoline composition further contains one or more of an antioxidant, an anti-icing agent, an antistatic agent, an anti-corrosion agent, and a dye.
Preferably, the motor octane number of the aviation gasoline composition is not less than 100;
preferably, the aviation gasoline composition has a motor octane number of from 100 to 104.
According to a second aspect of the present invention there is provided a process for the preparation of an aviation gasoline comprising the step of mixing the components of an aviation gasoline composition according to the first aspect of the present invention.
The third aspect of the invention provides a method for preparing aviation gasoline, comprising the following steps:
1) Distilling an alkylation reaction product of the carbon tetraolefin and the isobutane to obtain a component with a distillation range of 23-160 ℃ as component oil A;
2) Mixing the base oil containing component oil A with additives,
wherein the additive contains tetraethyl lead.
Preferably, the component oil A contains 2 to 7 wt% of C4 alkanes, 2 to 6 wt% of C5 alkanes, 3 to 8 wt% of C6 alkanes, 20 to 30 wt% of C7 alkanes, 49 to 65 wt% of C8 alkanes, 0.5 to 3 wt% of C9 alkanes and 2 to 5 wt% of C10 alkanes.
Preferably, the component oil A contains 4.35 to 6.5% by weight of C4 alkanes, 4.5 to 6% by weight of C5 alkanes, 3.5 to 5.5% by weight of C6 alkanes, 24 to 25.5% by weight of C7 alkanes, 50 to 60% by weight of C8 alkanes, 0.75 to 1.5% by weight of C9 alkanes and 2 to 3% by weight of C10 alkanes.
Preferably, in step 2), the base oil further comprises component oil B and/or component oil C.
Preferably, the component oil B contains more than 95 wt% of C7 aromatic hydrocarbons.
Preferably, the component oil C contains 1-10 wt% C4 alkane, 40-75 wt% C5 alkane, 20-50 wt% C6 alkane, and 0.03-0.4 wt% C7 alkane.
Preferably, the component oil B has a distillation range of 109-111 ℃.
Preferably, the component oil C has a distillation range of 20-70 ℃.
Preferably, the base oil contains 65 to 100% by weight of the component oil A, 0 to 15% by weight of the component oil B and 0 to 20% by weight of the component oil C.
Preferably, the amount of tetraethyllead is 0.8-1.2g/kg relative to the base oil; more preferably, the tetraethyl lead content is 0.8-1.0g/kg relative to the base oil.
Preferably, the method further comprises: and (3) further adding one or more of an antioxidant, an anti-icing agent, an antistatic agent, an anticorrosive agent and a dye into the mixed product obtained in the step 2).
Preferably, in step 1), the conditions of the distillation include: the bottom temperature of the distillation column is 135-145 ℃, the bottom pressure of the distillation column is 0.42-0.52MPa, the top temperature of the distillation column is 50-56 ℃, and the top pressure of the distillation column is 0.4-0.5MPa.
Preferably, a component having a distillation range of 23 to 160 ℃ is withdrawn from the side stream of the distillation column of the alkylation unit as component oil a or a component having a distillation range of 23 to 160 ℃ is cut from the bottom oil of the distillation column of the alkylation unit as component oil a; more preferably, a component having a distillation range of 45 to 160℃is withdrawn from the side stream of the distillation column of the alkylation apparatus as component oil A or a component having a distillation range of 45 to 160℃is cut from the bottom oil of the distillation column of the alkylation apparatus as component oil A.
According to a fourth aspect of the present invention there is provided aviation gasoline produced by the method of the third aspect of the present invention.
Through the technical scheme, the aviation gasoline composition, the aviation gasoline and the preparation method thereof are provided, the aviation gasoline meets the ASTM-D910 standard and the GB1787-2018 standard of No. 100LL aviation gasoline, the aromatic hydrocarbon content is low, the lead content is low, the pollution generated during combustion can be reduced, and the environment protection is facilitated.
In addition, the aviation gasoline composition provided by the invention has high octane number, good antiknock performance and high safety coefficient, and can meet the requirement of aviation piston engine fuel on the octane number.
On the other hand, the preparation method of aviation gasoline provided by the invention has the advantages that the required blending components are few, the sources of all the components are wide, the high-grade refining is not needed, the preparation can be carried out by adopting crude products of various oil refining enterprises, and the production cost is greatly reduced.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In the present invention, the 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.
In the present invention, the C4 alkane means an alkane having four carbon atoms, the C5 alkane means an alkane having five carbon atoms, and the C10 means an alkane having ten carbon atoms.
In the present invention, the C7 aromatic hydrocarbon means an aromatic hydrocarbon having seven carbon atoms.
In the invention, the method for measuring the octane number of the motor method is carried out according to the measurement of the octane number of GB-T503-2016 gasoline.
In a first aspect the present invention provides an aviation gasoline composition comprising a base oil and an additive, wherein the base oil comprises a component oil a comprising 2-7 wt.% C4 alkanes, 2-6 wt.% C5 alkanes, 3-8 wt.% C6 alkanes, 20-30 wt.% C7 alkanes, 49-65 wt.% C8 alkanes, 0.5-3 wt.% C9 alkanes and 2-5 wt.% C10 alkanes, and the component oil a has a distillation range of 23-160 ℃. The additive contains tetraethyllead.
In the present invention, preferably, the component oil A contains 4.35 to 6.5% by weight of C4 alkane, 4.5 to 6% by weight of C5 alkane, 3.5 to 5.5% by weight of C6 alkane, 24 to 25.5% by weight of C7 alkane, 50 to 60% by weight of C8 alkane, 0.75 to 1.5% by weight of C9 alkane and 2 to 3% by weight of C10 alkane, and the distillation range of the component oil A is 45 to 160 ℃.
The component oil A) is obtained by distilling an alkylation reaction product, specifically, firstly reacting carbon tetraolefin and isobutane in an alkylation device under alkylation conditions, then distilling the reaction product in a distillation tower, and extracting a component with a distillation range of 23-160 ℃ from the side line of the distillation tower or cutting a component with a distillation range of 23-160 ℃ from a bottom fraction; preferably, the components having a distillation range of 45 to 160℃are withdrawn from the side of the distillation column, or the components having a distillation range of 45 to 160℃are cut in the bottom fraction.
In the present invention, the alkylation reaction conditions may be conventional in the art, for example, the reaction temperature may be 4 to 10 ℃, the reaction pressure may be 0.4 to 0.45MPa, and the molar ratio of isobutane to carbon tetraolefin may be 8 to 12:1, the molar ratio of the catalyst to the carbon tetraolefin may be 1-1.2:1.
In addition, the catalyst for the alkylation reaction may be selected as is conventional in the art, and may be, for example, one or more of sulfonic acid, hydrofluoric acid, and concentrated sulfuric acid.
According to the invention, in step 1), the conditions of the distillation include: the bottom temperature of the distillation column is 135-145 ℃, the bottom pressure of the distillation column is 0.42-0.52MPa, the top temperature of the distillation column is 50-56 ℃, and the top pressure of the distillation column is 0.4-0.5MPa.
The inventor of the invention discovers that 100LL aviation gasoline meeting application requirements can be prepared by only adopting the component oil A obtained from the alkylation reaction product, thereby greatly simplifying the preparation process and the production cost of aviation gasoline.
According to the invention, the base oil may preferably also contain component oil B and/or component oil C.
The component oil B contains more than 95 weight percent of C7 aromatic hydrocarbon, and the balance of small amounts of C8 aromatic hydrocarbon, C7 byproducts, benzene and the like. Preferably, the component oil B contains 95 to 99 weight percent of C7 aromatic hydrocarbon. In addition, the distillation range of the component oil B is preferably 109 to 111 ℃.
The component oil B may be commercially available or may be a product from various conventional processes in the art as long as the above requirements are satisfied. Preferably, the component oil B is derived from a C7 aromatic component oil produced by an aromatic extraction device.
In the invention, the C7 aromatic hydrocarbon component oil produced by the aromatic hydrocarbon extraction device refers to a reforming mixed product obtained by reforming the straight-run naphtha, and the C7 fraction is separated by adopting a ring Ding Saye liquid extraction process.
In the present invention, the component oil C contains 1 to 10% by weight of C4 alkane, 40 to 75% by weight of C5 alkane, 20 to 50% by weight of C6 alkane and 0.03 to 0.4% by weight of C7 alkane; preferably, the component oil C contains 3-6 wt% C4 alkane, 60-70 wt% C5 alkane, 25-35 wt% C6 alkane, and 0.05-0.35 wt% C7 alkane. Further, the component oil C preferably has a distillation range of 20 to 70℃and preferably has a distillation range of 21 to 67 ℃.
According to the present invention, the component oil C is commercially available, or may be a product from various conventional processes in the art, as long as the above requirements are satisfied. For example, the component oil C may be derived from one or more of light naphtha produced in a hydrocracking unit, virgin overhead produced in an atmospheric and vacuum distillation unit, and virgin overhead produced in an atmospheric and vacuum distillation unit.
In the present invention, the light naphtha produced by the hydrocracking apparatus may be produced by subjecting a heavy feedstock and hydrogen to a hydrocracking reaction in the presence of a catalyst.
In the invention, the primary top oil produced by the atmospheric and vacuum distillation device can be obtained by separating crude oil in the atmospheric and vacuum distillation device from the top of a tower after primary heat exchange and secondary heat exchange in an electric desalting tank and then in a primary distillation tower.
In the invention, the normal top oil produced by the atmospheric and vacuum device can be oil products distilled from the top of the tower after entering the atmospheric fractionating tower from the primary distillation tower in the atmospheric and vacuum device and being rectified.
Preferably, the component oil C is selected from light naphtha produced by a hydrocracking unit.
According to the present invention, in the aviation gasoline composition, the base oil may contain 65 to 100% by weight of the component oil a, 0 to 15% by weight of the component oil B, and 0 to 20% by weight of the component oil C; preferably, the base oil contains 75 to 85% by weight of the component oil A, 0 to 15% by weight of the component oil B and 0 to 15% by weight of the component oil C.
According to the present invention, the base oil may contain only the component oil a, or may contain the component oil a and the component oil B, the component oil a and the component oil C, or may contain both the component oils A, B and C. The source and the components of the base oil can be freely selected according to the source of the raw materials and the actual situation, thereby greatly widening the source of the raw materials of the aviation gasoline composition and reducing the production limit.
The aviation gasoline composition provided by the invention meets the standard of No. 100LL aviation gasoline, and the motor octane number of No. 100LL aviation gasoline composition is not less than 99.6 according to the ASTM-D910 standard. In order to further improve the safety performance of the aviation gasoline composition, preferably, the motor octane number of the aviation gasoline composition provided by the invention is not less than 100; more preferably, the motor octane number of the aviation gasoline composition provided by the invention is 100-104.
In the present invention, the tetraethyl lead content may be determined based on the motor octane number of the base oil. That is, the higher the motor octane number contributed by the base oil, the less tetraethyl lead that may be required to be added, on the basis that the motor octane number is satisfied by the aviation gasoline composition. Since the motor octane number in the base oil can be controlled to a high level by the above-mentioned blending ratio of the base oil, the content of the tetraethyl lead in the aviation gasoline composition is preferably 0.8 to 1.2g/kg, and more preferably the content of the tetraethyl lead in the aviation gasoline composition is 0.8 to 1.0g/kg.
The aviation gasoline composition provided by the invention can further contain various conventional additives commonly used in the field for meeting and improving the performance of aviation gasoline, such as one or more of antioxidants, anti-icing agents, antistatic agents, anticorrosive agents and the like.
The antioxidant may be any of various antioxidants conventionally used in the art, and may be, for example, one or more of 2, 6-di-t-butyl-4-cresol, 2, 4-dimethyl-6-t-butylphenol, 2, 6-di-t-butylphenol, N '-dipropyl-p-phenylenediamine and N, N' -di-sec-butyl-p-phenylenediamine. In addition, the content of the antioxidant in the aviation gasoline composition is not more than 12mg/L, preferably 10-12mg/L.
The anti-icing agent may be various anti-icing agents which are conventional in the art, and may be, for example, isopropyl alcohol, diethylene glycol monomethyl ether, or the like. Further, the addition amount as the anti-icing agent may be an addition amount conventional in the art.
As the antistatic agent, various antistatic agents conventionally used in the art can be used, and for example, stadis 405 (Octel America Inc, newark, DE 19702) is commercially available, and the maximum addition amount of the antistatic agent is generally not more than 3mg/L, but when the conductivity of the fuel decreases and further addition of the antistatic agent is required, the addition may be continued, but the cumulative total cannot be more than 5mg/L.
The anticorrosive agent may be any anticorrosive agent conventional in the art, and the amount thereof may be added according to the requirements in the art, and will not be described herein.
In addition, to facilitate rapid differentiation of the grade of the aviation gasoline composition, the aviation gasoline composition may further contain a dye. The color of the dye is selected according to the grade of aviation gasoline. For example, no. 80 aviation gasoline is red in color, no. 91 aviation gasoline is brown in color, no. 100 aviation gasoline is green in color, and No. 100LL aviation gasoline is blue in color.
The aviation gasoline composition provided by the invention meets the standard of No. 100LL aviation gasoline, namely, the aviation gasoline composition is added with blue dye, the blue dye can be 1, 4-dialkyl amino-quinone, and the content of the blue dye is not more than 2.7mg/L.
In a second aspect, the present invention provides a method for preparing an aviation gasoline, comprising the step of mixing the components of the aviation gasoline composition described above.
According to the preparation method of the aviation gasoline provided by the second aspect of the present invention, the components in the aviation gasoline composition, the content and the requirements thereof have been specifically described in the aviation gasoline composition provided by the first aspect of the present invention, and are not described herein.
According to the present invention, the components may be mixed together in any order, so long as the mixing is sufficient, and there is no particular limitation. For example, the base oil may be mixed uniformly and then the additive may be added to the mixture, or a part of the base oil may be mixed uniformly with the additive and then the rest of the base oil may be added to the mixture, or the base oil and the additive may be added simultaneously and mixed uniformly, or the like. In the present invention, preferably, the base oil components are mixed uniformly, and then the additives are added to mix uniformly.
The third aspect of the invention provides a method for preparing aviation gasoline, comprising the following steps:
1) Distilling an alkylation reaction product of the carbon tetraolefin and the isobutane in a distillation tower to obtain a component with a distillation range of 23-160 ℃ as component oil A;
2) Mixing the base oil containing component oil A with additives,
wherein the additive contains tetraethyl lead.
According to a third aspect of the invention, the alkylation reaction product may be derived from the product of an alkylation reaction of a carbon tetraolefin and isobutane under alkylation reaction conditions in the presence of a catalyst.
In the present invention, the alkylation reaction conditions may be conventional in the art, for example, the reaction temperature may be 4 to 10 ℃, the reaction pressure may be 0.4 to 0.45MPa, and the molar ratio of isobutane to carbon tetraolefin may be 8 to 12:1, the molar ratio of the catalyst to the carbon tetraolefin may be 1-1.2:1.
In addition, the catalyst for the alkylation reaction may be selected as is conventional in the art, and may be, for example, one or more of sulfonic acid, hydrofluoric acid, and concentrated sulfuric acid.
According to the invention, in step 1), the conditions of the distillation include: the bottom temperature of the distillation column is 135-145 ℃, the bottom pressure of the distillation column is 0.42-0.52MPa, the top temperature of the distillation column is 50-56 ℃, and the top pressure of the distillation column is 0.4-0.5MPa.
The inventor of the invention discovers that the alkylation reaction product is distilled in a distillation tower, and components with the distillation range of 23-160 ℃ are directly extracted from a side line, so that high carbon compounds with the distillation range of more than 160 ℃ can be removed, 49-65 wt% of C8 alkane which can contribute to higher octane number is reserved, and meanwhile, lighter components such as C4, C5 and the like are contained, and the distillation range of the obtained aviation gasoline can be regulated to meet the requirements of aviation gasoline standards.
Therefore, the base oil meeting the requirements can be obtained by only extracting the oil meeting the distillation range from the side line of the distillation tower of the alkylation reaction product, refining the oil and adding more components for blending are not needed, and the base oil of aviation gasoline can be simply and economically obtained by adding a small amount of conventional additives on the basis of the base oil. The method not only avoids the difficulty of high-standard refining by a series of complex processes for obtaining the components of the base oil in the prior art, but also greatly simplifies the process of blending the components of the base oil.
According to the present invention, in addition to the components having the distillation range of 23 to 160℃from the side line, the components satisfying the above distillation range may be cut from the bottom of the distillation column, and the present invention can be achieved as long as the above components are obtained, and the cutting may be performed by a conventional method in the art, and will not be repeated here.
According to the present invention, it is preferable that the alkylation reaction product of a carbon tetraolefin and isobutane is distilled in a distillation column to obtain a component having a distillation range of 45 to 160 ℃ as component oil a.
In addition, the distillation apparatus and the operation method involved in distillation in the present invention may be apparatuses and methods conventional in the art, and will not be described herein.
According to the invention, the component oil A obtained according to the above-described process contains 2 to 7% by weight of C4 alkanes, 2 to 6% by weight of C5 alkanes, 3 to 8% by weight of C6 alkanes, 20 to 30% by weight of C7 alkanes, 49 to 65% by weight of C8 alkanes, 0.5 to 3% by weight of C9 alkanes and 2 to 5% by weight of C10 alkanes; preferably, the component oil A contains 4.35 to 6.5% by weight of C4 alkanes, 4.5 to 6% by weight of C5 alkanes, 3.5 to 5.5% by weight of C6 alkanes, 24 to 25.5% by weight of C7 alkanes, 50 to 60% by weight of C8 alkanes, 0.75 to 1.5% by weight of C9 alkanes and 2 to 3% by weight of C10 alkanes.
According to the invention, the additive contains tetraethyl lead in order to increase the antiknock capacity of aviation gasoline.
In the invention, the method further comprises the following steps: in step 2), the base oil further comprises component oil B and/or component oil C.
According to the invention, the component oil B contains more than 95 weight percent of C7 aromatic hydrocarbon and a small amount of C8 aromatic hydrocarbon, C7 byproducts, benzene and the like; preferably, the component oil B contains 95 to 99 weight percent of C7 aromatic hydrocarbon. Preferably, the component oil C has a distillation range of 20-70 ℃.
By mixing the component oil B, the distillation range and saturated vapor pressure of the obtained aviation gasoline can be regulated within the expected range, and the C7 aromatic hydrocarbon can contribute to the octane number, so that the motor octane number of the aviation gasoline is further improved, and the safety performance of the aviation gasoline is improved.
The component oil B may be commercially available or may be a product from various conventional processes in the art as long as the above requirements are satisfied. Preferably, the component oil B is a C7 aromatic component oil produced by an aromatic extraction device, and the source thereof may be consistent with the first aspect of the present invention, and will not be described herein.
In the present invention, the component oil C contains 1 to 10% by weight of C4 alkane, 40 to 75% by weight of C5 alkane, 20 to 50% by weight of C6 alkane and 0.03 to 0.4% by weight of C7 alkane; preferably, the component oil C contains 3-6 wt% C4 alkane, 60-70 wt% C5 alkane, 25-35 wt% C6 alkane, and 0.05-0.35 wt% C7 alkane. Further, the component oil C preferably has a distillation range of 20 to 70℃and preferably has a distillation range of 21 to 67 ℃. Component oil C can be added as required, so that the distillation range of the aviation gasoline can be further adjusted.
The component oil C may be commercially available or may be a product from various conventional processes in the art as long as the above requirements are satisfied. The source may be in accordance with the first aspect of the invention, for example, the component oil C may be derived from one or more of light naphtha produced in a hydrocracking unit, virgin overhead produced in an atmospheric and vacuum distillation unit and virgin overhead produced in an atmospheric and vacuum distillation unit, and will not be described in detail herein.
In the present invention, preferably, the component oil C is light naphtha produced by a hydrocracking unit.
According to the third aspect of the present invention, preferably, the base oil contains 65 to 100% by weight of the component oil a, 0 to 15% by weight of the component oil B, and 0 to 20% by weight of the component oil C. The amount of tetraethyl lead used is 0.8-1.2g/kg relative to the base oil; more preferably, the base oil contains 75 to 85% by weight of the component oil A, 0 to 15% by weight of the component oil B, and 0 to 15% by weight of the component oil C, and the amount of tetraethyllead is 0.8 to 1.0g/kg relative to the base oil.
According to the present invention, the base oil may contain only the component oil a, or may contain the component oil a and the component oil B, the component oil a and the component oil C, or may contain both the component oils A, B and C. The source and the components of the base oil can be freely selected according to the source of the raw materials and the actual situation, thereby greatly widening the source of the raw materials of the aviation gasoline composition and reducing the production limit.
In addition, according to the invention, one or more of an antioxidant, an anti-icing agent, an antistatic agent, an anticorrosive agent and a dye can be further added to the preparation of the aviation gasoline. The kind and the addition amount of the additive may be the same as those of the first aspect of the present invention, and will not be described here.
In addition, dyes can be further added in the preparation of the aviation gasoline, and the color, the type and the addition amount of the dyes can be consistent with those of the first aspect of the invention, and are not repeated here.
According to the aviation gasoline preparation method, the motor octane number of the prepared aviation gasoline is not less than 100; preferably, the motor octane number of the aviation gasoline thus prepared is from 100 to 104.
According to a fourth aspect of the present invention there is provided aviation gasoline produced by the method of the third aspect of the present invention.
The aviation gasoline prepared by the method provided by the third aspect of the invention is No. 100LL aviation gasoline, and each parameter meets the relevant standard of ASTM-D910.
The present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.
In the following examples, parameters were measured according to ASTM-D910.
In the present invention, the antistat Stadis 405 is available from Octel America Inc, newark, DE 19702.
In the following examples, the C7 aromatic component oil produced by the aromatic extraction device was derived from a reformed mixture obtained by subjecting straight-run naphtha to a reforming reaction, and the separated C7 fraction was extracted by a loop Ding Saye liquid extraction process.
In the examples below, the light naphtha produced by the hydrocracking unit employed was derived from a light naphtha produced by hydrocracking a heavy feedstock and hydrogen in the presence of a catalyst.
In the following examples, the atmospheric and vacuum distillation unit was used to produce overhead oil from the atmospheric and vacuum distillation unit, which was distilled from the top of the column after distillation from the primary distillation column into the atmospheric fractionating column.
Preparation example 1
1) A mixture of carbon tetraolefin and isobutane (13.64 wt% of n-butene, 0.6 wt% of isobutene, 9.82 wt% of cis-butene, 16.18 wt% of trans-butene, 51.26 wt% of isobutane, 8.35 wt% of n-butane, 0.04 wt% of propylene, 0.06 wt% of propane, and 0.05 wt% of dimethyl ether) was hydrofined, and after satisfying the molar ratio of isobutane to carbon tetraolefin (8.39: 1) In the presence of concentrated sulfuric acid (98.5 wt.%) as catalyst at 7.2 deg.C, 0.42MPa and 0.34 hr space velocity -1 Carrying out alkylation reaction under the condition of (1) to obtain a reaction product;
2) Distilling the reaction product obtained in the step 1) in a distillation tower, wherein the bottom temperature of the distillation tower is 137 ℃, the bottom pressure of the distillation tower is 0.45MPa, the top temperature of the distillation tower is 52 ℃, the top pressure of the distillation tower is 0.4MPa, and the components with the distillation range of 46.1-158 ℃ are extracted from the side line of the distillation tower, so that the side line extracted oil of the distillation tower of the alkylation device can be obtained.
Preparation example 2
1) A mixture of carbon tetraolefin and isobutane (13.60 wt% of n-butene, 0.63 wt% of isobutene, 9.01 wt% of cis-butene, 16.93 wt% of trans-butene, 8.33 wt% of n-butane, 51.31 wt% of isobutane, 0.05 wt% of propylene, 0.07 wt% of propane, and 0.07 wt% of dimethyl ether) was hydrofined, and after satisfying the molar ratio of isobutane to carbon tetraolefin (8.21: 1) In the presence of concentrated sulfuric acid (98.7 wt.%) as catalyst at 7.8 deg.C, 0.42MPa and 0.35 hr space velocity -1 Carrying out alkylation reaction under the condition of (1) to obtain a reaction product;
2) Distilling the reaction product obtained in the step 1) in a distillation tower, wherein the bottom temperature of the distillation tower is 140 ℃, the bottom pressure of the distillation tower is 0.47MPa, the top temperature of the distillation tower is 53 ℃, the top pressure of the distillation tower is 0.41MPa, and the components with the distillation range of 47.3-155.1 ℃ are cut out in the bottom of the distillation tower, so that the cutting oil at the bottom of the distillation tower of the alkylation device can be obtained.
Preparation example 3
1) A mixture of carbon tetraolefin and isobutane (13.77 wt% of n-butene, 0.7 wt% of isobutene, 9.5 wt% of cis-butene, 16.32 wt% of trans-butene, 8.61 wt% of n-butane, 50.98 wt% of isobutane, 0.05 wt% of propylene, 0.06 wt% of propane, and 0.01 wt% of dimethyl ether) was hydrofined to satisfy the molar ratio of isobutane to carbon tetraolefin (8.16: 1) In the presence of concentrated sulfuric acid (99.1 wt%) as catalyst, at a temperature of 8.1 deg.C, a pressure of 0.44MPa and a space velocity of 0.34 hr -1 Carrying out alkylation reaction under the condition of (1) to obtain a reaction product;
2) Distilling the reaction product obtained in the step 1) in a distillation tower, wherein the bottom temperature of the distillation tower is 135 ℃, the bottom pressure of the distillation tower is 0.44MPa, the top temperature of the distillation tower is 52 ℃, the top pressure of the distillation tower is 0.43MPa, and the components with the distillation range of 46.7-158.8 ℃ are extracted from the side line of the distillation tower, so that the side line extracted oil of the distillation tower of the alkylation device is obtained.
Preparation example 4
1) A mixture of carbon tetraolefin and isobutane (14.01 wt% of n-butene, 0.5 wt% of isobutene, 9.05 wt% of cis-butene, 15.32 wt% of trans-butene, 9.22 wt% of n-butane, 51.77 wt% of isobutane, 0.03 wt% of propylene, 0.06 wt% of propane, and 0.04 wt% of dimethyl ether) was hydrofined, and after satisfying the molar ratio of isobutane to carbon tetraolefin (8.35: 1) In the presence of concentrated sulfuric acid (99.1 wt%) as catalyst, at 7.3 deg.C, 0.45MPa and 0.33 hr of space velocity -1 Carrying out alkylation reaction under the condition of (1) to obtain a reaction product;
2) Distilling the reaction product obtained in the step 1) in a distillation tower, wherein the bottom temperature of the distillation tower is 141 ℃, the bottom pressure of the distillation tower is 0.48MPa, the top temperature of the distillation tower is 55 ℃, the top pressure of the distillation tower is 0.43MPa, and the components with the distillation range of 43.1-156.8 ℃ are extracted from the side line of the distillation tower, so that the side line extracted oil of the distillation tower of the alkylation device can be obtained.
Preparation example 5
1) A mixture of carbon tetraolefin and isobutane (13.71 wt% of n-butene, 0.8 wt% of isobutene, 8.99 wt% of cis-butene, 17.03 wt% of trans-butene, 9.02 wt% of n-butane, 50.32 wt% of isobutane, 0.05 wt% of propylene, 0.05 wt% of propane, and 0.03 wt% of dimethyl ether) was hydrofined to satisfy the molar ratio of isobutane to carbon tetraolefin (8.33: 1) In the presence of concentrated sulfuric acid (98.8 wt.%) as catalyst at 7.5 deg.C, 0.44MPa and 0.34 hr of space velocity -1 Carrying out alkylation reaction under the condition of (1) to obtain a reaction product;
2) Distilling the reaction product obtained in the step 1) in a distillation tower, wherein the bottom temperature of the distillation tower is 144 ℃, the bottom pressure of the distillation tower is 0.42MPa, the top temperature of the distillation tower is 50 ℃, the top pressure of the distillation tower is 0.44MPa, and the components with the distillation range of 46.1-154.2 ℃ are extracted from the side line of the distillation tower, so that the side line extracted oil of the distillation tower of the alkylation device can be obtained.
Preparation example 6
1) A mixture of carbon tetraolefin and isobutane (12.77 wt% of n-butene, 0.5 wt% of isobutene, 11.01 wt% of cis-butene, 14.33 wt% of trans-butene, 8.22 wt% of n-butane, 53.02 wt% of isobutane, 0.04 wt% of propylene, 0.08 wt% of propane, and 0.03 wt% of dimethyl ether) was hydrofined, and after satisfying the molar ratio of isobutane to carbon tetraolefin (8.47: 1) In the presence of concentrated sulfuric acid (98.7 wt.%) as catalyst at 6.9 deg.C, 0.45MPa and 0.34 hr of space velocity -1 Carrying out alkylation reaction under the condition of (1) to obtain a reaction product;
2) Distilling the reaction product obtained in the step 1) in a distillation tower, wherein the bottom temperature of the distillation tower is 136 ℃, the bottom pressure of the distillation tower is 0.52MPa, the top temperature of the distillation tower is 54 ℃, the top pressure of the distillation tower is 0.41MPa, and the components with the distillation range of 45.1-155.8 ℃ are cut out in the bottom of the distillation tower, so that the cutting oil at the bottom of the distillation tower of the alkylation device is obtained.
Preparation example 7
1) A mixture of carbon tetraolefin and isobutane (15.01 wt% of n-butene, 0.6 wt% of isobutene, 8.5 wt% of cis-butene, 15.22 wt% of trans-butene, 8.68 wt% of n-butane, 51.87 wt% of isobutane, 0.05 wt% of propylene, 0.05 wt% of propane, and 0.02 wt% of dimethyl ether) was hydrofined, and after the molar ratio of isobutane to carbon tetraolefin was satisfied (8.24: 1) In the presence of concentrated sulfuric acid (99.1 wt%) as catalyst, at 7.7 deg.C, 0.43MPa and 0.34 hr space velocity -1 Carrying out alkylation reaction under the condition of (1) to obtain a reaction product;
2) Distilling the reaction product obtained in the step 1) in a distillation tower, wherein the bottom temperature of the distillation tower is 140 ℃, the bottom pressure of the distillation tower is 0.44MPa, the top temperature of the distillation tower is 53 ℃, the top pressure of the distillation tower is 0.41MPa, and the components with the distillation range of 45.9-158.9 ℃ are cut out from the bottom of the distillation tower, so that the cutting oil at the bottom of the distillation tower of the alkylation device can be obtained.
Example 1
0.8g/kg tetraethyl lead is added into side-draw oil (prepared by preparation example 1, the properties of which are shown in table 1-1) of a distillation tower of an alkylation device, and other additives are added according to table 1-2 to obtain aviation gasoline after uniform blending, wherein the properties of the aviation gasoline are shown in table 1-3 below:
TABLE 1-1
TABLE 1-2
Tables 1 to 3
Example 2
The process of example 1 was carried out, except that the side draw oil of the distillation column of the alkylation apparatus prepared in preparation example 1 was replaced with the bottom cut oil of the distillation column of the alkylation apparatus prepared in preparation example 2 (its properties are shown in Table 2-1), on the basis of which 0.8g/kg of tetraethyl lead was added, and then, other additives were added according to Table 1-2, and after blending uniformly, aviation gasoline was obtained. The properties of this aviation gasoline are shown in the following Table 2-2:
TABLE 2-1
TABLE 2-2
Example 3
The process of example 1 was carried out, except that the side-draw oil of the distillation column of the alkylation apparatus prepared in preparation example 1 was replaced with the side-draw oil of the distillation column of the alkylation apparatus prepared in preparation example 3 (the properties thereof are shown in Table 3-1), and on the basis, 0.8g/kg of tetraethyl lead was added, and then, other additives were added according to Table 1-2, and after blending uniformly, aviation gasoline was obtained. The properties of this aviation gasoline are shown in Table 3-2 below:
TABLE 3-1
TABLE 3-2
Example 4
88 wt% of distillation column side oil of an alkylation unit (prepared in preparation example 4, the properties of which are shown in Table 4-1) and 12 wt% of light naphtha produced by a hydrocracking unit (the properties of which are shown in Table 2-2) are mixed, 1.0g/kg of tetraethyl lead is added, and other additives are added according to Table 1-2, and after uniform blending, aviation gasoline is obtained, the properties of which are shown in Table 4-3 below:
TABLE 4-1
TABLE 4-2
TABLE 4-3
Example 5
75.5 wt.% of the alkylate distillation column sidedraw oil (prepared from preparation example 5, properties of which are shown in Table 5-1), 14.2 wt.% of the C7 aromatic component oil produced by the aromatic extraction device (properties of which are shown in Table 5-2) and 10.3 wt.% of the normal top oil produced by the atmospheric and vacuum device (properties of which are shown in Table 5-3) were mixed, 1.1g/Kg of tetraethyl lead was added, and then the other additives were added according to Table 1-2, and after blending was uniform, aviation gasoline was obtained, the properties of which are shown in Table 5-4 below:
TABLE 5-1
TABLE 5-2
TABLE 5-3
Tables 5 to 4
Example 6
86 wt% of the bottom cutting oil of the distillation tower of the alkylation unit (prepared by preparation example 6, the properties of which are shown in Table 6-1) and 14 wt% of light naphtha produced by the hydrocracking unit (the properties of which are shown in Table 6-2) are mixed, 1.1g/kg of tetraethyl lead is added, and other additives are added according to Table 1-2, and after uniform blending, aviation gasoline is obtained, the properties of which are shown in Table 6-3 below:
TABLE 6-1
TABLE 6-2
TABLE 6-3
Example 7
83.5 wt% of cutting oil at the bottom of a distillation column of an alkylation unit (prepared by preparation example 7, the properties of which are shown in Table 7-1), 12 wt% of C7 aromatic component oil produced by an aromatic extraction unit (the properties of which are shown in Table 7-2) and 4.5 wt% of normal top oil produced by an atmospheric and vacuum distillation unit (the properties of which are shown in Table 7-3) were mixed, 1.2g/kg of tetraethyl lead was added, and then other additives were added according to Table 1-2, and after blending was uniform, aviation gasoline was obtained, the properties of which are shown in Table 7-4 below:
TABLE 7-1
TABLE 7-2
TABLE 7-3
TABLE 7-4
As can be seen from the results of the above examples, when aviation gasoline is prepared, aviation gasoline meeting the No. 100LL standard in ASTM-D910 can be prepared by adding tetraethyl lead and conventional additives by selecting one component oil A within the distillation range and the component content defined by the invention. The motor octane number of the obtained aviation gasoline is higher than 100, and the adding amount of tetraethyl lead is low.
In addition, various components which are easy to obtain in the field, such as C7 aromatic component oil produced by an aromatic extraction device, light naphtha produced by a hydrocracking device, primary top oil produced by an atmospheric and vacuum distillation device, normal top oil produced by the atmospheric and vacuum distillation device, and the like, can be added to further adjust the saturated vapor pressure and the distillation range of aviation gasoline. The raw materials are widely available, the high-purity gasoline can be directly used without high-purity refining, aviation gasoline can be produced by slightly modifying common oil refining enterprises, the fixed investment is low, and the high-purity gasoline is easy to implement.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (20)
1. An aviation gasoline composition, characterized in that the aviation gasoline composition contains a base oil and an additive, wherein the base oil contains component oil A,
the component oil A contains 4.35-6.5 wt% of C4 alkane, 4.5-6 wt% of C5 alkane, 3.5-5.5 wt% of C6 alkane, 24-25.5 wt% of C7 alkane, 50-60 wt% of C8 alkane, 0.75-1.5 wt% of C9 alkane and 2-3 wt% of C10 alkane, and the distillation range of the component oil A is 45-160 ℃;
wherein the component oil A is obtained by distilling an alkylation reaction product of carbon tetraolefin and isobutane and obtaining a component with a distillation range of 45-160 ℃;
the additive contains tetraethyl lead, and the content of the tetraethyl lead is 0.8-1.2g/kg.
2. The aviation gasoline composition of claim 1, wherein the base oil further comprises component oil B and/or component oil C;
the component oil B contains more than 95 weight percent of C7 aromatic hydrocarbon;
the component oil C contains 1-10 wt% of C4 alkane, 40-75 wt% of C5 alkane, 20-50 wt% of C6 alkane and 0.03-0.4 wt% of C7 alkane.
3. The aviation gasoline composition of claim 2, wherein the component oil B has a distillation range of 109-111 ℃.
4. The aviation gasoline composition of claim 2, wherein the component oil C has a distillation range of 20-70 ℃.
5. The aviation gasoline composition of any one of claims 2-4, wherein the base oil contains 65-100 wt% of the component oil a, 0-15 wt% of the component oil B, and 0-20 wt% of the component oil C.
6. The aviation gasoline composition of any one of claims 1-4, wherein the tetraethyl lead content is 0.8-1.0g/kg relative to the base oil.
7. The aviation gasoline composition of any one of claims 1-4, wherein the aviation gasoline composition further comprises one or more of an antioxidant, an anti-icing agent, an antistatic agent, an anti-corrosion agent, and a dye.
8. The aviation gasoline composition of any one of claims 1-4, wherein the aviation gasoline composition has a motor octane number of not less than 100.
9. The aviation gasoline composition of claim 8, wherein the aviation gasoline composition has a motor octane number of 100-104.
10. A method of preparing an aviation gasoline, the method comprising the step of mixing the components of an aviation gasoline composition, the aviation gasoline composition being as claimed in any one of claims 1 to 9.
11. The preparation method of aviation gasoline is characterized by comprising the following steps:
1) Distilling an alkylation reaction product of the carbon tetraolefin and the isobutane to obtain a component with a distillation range of 45-160 ℃ as component oil A;
2) Mixing the base oil containing component oil A with additives,
wherein the additive contains tetraethyl lead, and the dosage of the tetraethyl lead is 0.8-1.2g/kg;
the component oil A contains 4.35-6.5 wt% of C4 alkane, 4.5-6 wt% of C5 alkane, 3.5-5.5 wt% of C6 alkane, 24-25.5 wt% of C7 alkane, 50-60 wt% of C8 alkane, 0.75-1.5 wt% of C9 alkane and 2-3 wt% of C10 alkane.
12. The method of claim 11, wherein in step 2), the base oil further comprises component oil B and/or component oil C;
the component oil B contains more than 95 weight percent of C7 aromatic hydrocarbon;
the component oil C contains 1-10 wt% of C4 alkane, 40-75 wt% of C5 alkane, 20-50 wt% of C6 alkane and 0.03-0.4 wt% of C7 alkane.
13. The process according to claim 12, wherein the component oil B has a distillation range of 109-111 ℃.
14. The process of claim 12, wherein the component oil C has a distillation range of 20-70 ℃.
15. The method of any of claims 12-14, wherein the base oil comprises 65-100 wt% of the component oil a, 0-15 wt% of the component oil B, and 0-20 wt% of the component oil C.
16. The method according to any one of claims 11-14, wherein the tetraethyl lead content is 0.8-1.0g/kg relative to the base oil.
17. The method according to any one of claims 11-14, wherein the method further comprises: and (3) further adding one or more of an antioxidant, an anti-icing agent, an antistatic agent, an anticorrosive agent and a dye into the mixed product obtained in the step 2).
18. The method according to any one of claims 11-14, wherein in step 1), the conditions of the distillation include: the bottom temperature of the distillation column is 135-145 ℃, the bottom pressure of the distillation column is 0.42-0.52MPa, the top temperature of the distillation column is 50-56 ℃, and the top pressure of the distillation column is 0.4-0.5MPa.
19. The process according to any one of claims 11 to 14, wherein in step 1), a component having a distillation range of 45 to 160 ℃ is withdrawn from the side stream of the distillation column of the alkylation apparatus as component oil a or a component having a distillation range of 45 to 160 ℃ is cut from the bottom oil of the distillation column of the alkylation apparatus as component oil a.
20. Aviation gasoline obtainable by the process of any one of claims 11 to 19.
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