CN113845944A - No. 100 ultralow-lead aviation gasoline and production method thereof - Google Patents
No. 100 ultralow-lead aviation gasoline and production method thereof Download PDFInfo
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- 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
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Abstract
The invention provides an aviation gasoline composition capable of being used as No. 100 ultra-low lead aviation gasoline and a production method thereof. The aviation gasoline composition disclosed by the invention has the lead content of not more than 0.45mL/L, and only contains a very small amount of tetraethyl lead compared with the 100LL aviation gasoline with the lead content of 0.53mL/L, so that the pollution to the environment can be reduced to a certain extent. The motor octane number of the aviation gasoline is not less than 99.6, the octane number is high, indexes such as vapor pressure and distillation range and the like meet the requirements of ASTM-D910 standard on 100LL aviation gasoline, the production cost is low, the fuel performance is good, the raw materials are widely and easily obtained, and the production method is simple.
Description
Technical Field
The invention belongs to the technical field of fuels, and particularly relates to No. 100 ultralow-lead aviation gasoline and a preparation method thereof.
Background
Aviation gasoline is a petroleum product used as a fuel for piston-type aircraft engines, and has a sufficiently low crystallization point and a relatively high calorific value, good evaporation properties and sufficient antiknock properties. With the rapid development of the general aviation industry in China, aviation gasoline as an important component of aviation fuel is continuously developed and advanced. Tetraethyl lead is a widely used gasoline additive, and can increase the antiknock capability of gasoline, thereby improving the efficacy of the gasoline. Meanwhile, tetraethyl lead is also a highly toxic substance, poses a threat to the health of people and also destroys the environment.
In view of the increasing emission of lead due to the combustion of lead-containing aviation gasoline, more and more countries are beginning to pay attention to lead-free aviation gasoline. However, since the unleaded aviation gasoline cannot meet the requirement of the octane number of the engine and can cause certain damage to the engine, the piston aviation fuel plan for replacing the leaded aviation gasoline proposed by the FAA in 2010 has not been successful so far. At present, the lead content of the domestic aviation gasoline No. 100LL (No. 100 low-lead aviation gasoline) is 0.53mL/L, and the lead content is still high.
CN 104593101B discloses a high octane number lead-free aviation gasoline and a preparation method thereof, and proposes the lead-free aviation gasoline with the following components: from 5% to 20% MON by volume is at least 107% toluene, from 2% to 10% aniline, from 35% to 65% alkylate or alkylate blend, from 5% to 20% diethyl carbonate and at least 8% isopentane. The aviation gasoline blending component contains aromatic amine which can meet the requirement of gasoline antiknock performance, but has more serious abrasion to metal materials of parts such as engine valve seats and the like, and can shorten the service life of partial rubber parts or sealing gaskets and deteriorate the sealing property. Moreover, the arylamine can generate oxynitride after being combusted, has great harm to the environment, is one of main substances for forming acid rain, and is also an important substance for forming photochemical smog in the atmosphere.
Therefore, there is a need in the art for an ultra-low lead aviation gasoline No. 100 that does not contain an aromatic amine antiknock agent.
Disclosure of Invention
In view of the above problems in the prior art, the invention provides an aviation gasoline composition, which meets the requirements of the ASTM-D910 standard on various indexes such as antiknock property, evaporability, low-temperature fluidity and stability of 100LL aviation gasoline, and simultaneously has low content of tetraethyl lead, is environment-friendly, and has simple preparation process and easy implementation.
Specifically, one aspect of the invention provides an aviation gasoline composition comprising a base oil and an additive, the base oil comprising a blending combination a, a blending component B, and a blending component C; the base oil comprises 65 to 75 weight percent of the blending component A, 10 to 20 weight percent of the blending component B and 15 to 25 weight percent of the blending component C based on the total weight of the base oil;
wherein the blending component A contains 2-9 wt% of C4 alkane, 3-6 wt% of C5 alkane, 4-8 wt% of C6 alkane, 20-30 wt% of C7 alkane, 55-68 wt% of C8 alkane and 0.55-2.3 wt% of C9 alkane based on the total weight of the blending component A;
the blending component B contains one or two selected from meta-xylene and para-xylene, and the total content of the meta-xylene and the para-xylene is more than 94 wt% based on the total weight of the blending component B;
the blending component C contains 0.5 to 4.5 weight percent of C4 alkane, 43 to 72 weight percent of C5 alkane, 24 to 54 weight percent of C6 alkane and 0.05 to 0.5 weight percent of C7 alkane based on the total weight of the blending component C.
In one or more embodiments, the amount of blend component A is from 65 to 70 weight percent.
In one or more embodiments, the amount of blend component B is from 10 to 15 weight percent.
In one or more embodiments, the blending component C is present in an amount of 15 to 20 weight percent.
In one or more embodiments, the initial boiling point of blend component A is 23-50 ℃ and the end point is 140-148 ℃; preferably, the initial boiling point of the blending component A is 40-48 ℃ and the final boiling point is 142-148 ℃.
In one or more embodiments, blend component a contains 4 to 8 weight percent C4 alkane, 3 to 5 weight percent C5 alkane, 4.5 to 7.5 weight percent C6 alkane, 21 to 25 weight percent C7 alkane, 56 to 63 weight percent C8 alkane, and 0.6 to 2 weight percent C9 alkane, based on the total weight of blend component a.
In one or more embodiments, the initial boiling point of the blending component B is 135-138 ℃ and the final boiling point is 139-144 ℃.
In one or more embodiments, blend component B contains 0 to 2 weight percent non-aromatic hydrocarbons based on the total weight of blend component B.
In one or more embodiments, the blending component C has an initial boiling point in the range of from 25 ℃ to 30 ℃ and an end point in the range of from 60 ℃ to 68 ℃.
In one or more embodiments, blend component C contains 3 to 4.5 weight percent C4 alkanes, 68 to 72 weight percent C5 alkanes, 24 to 30 weight percent C6 alkanes, and 0.1 to 0.5 weight percent C7 alkanes, based on the total weight of blend component C.
In one or more embodiments, the additive includes tetraethyllead, preferably added in an amount of no more than 0.45mL/L, such as 0.27 to 0.43mL/L, based on the total volume of the base oil.
In one or more embodiments, the additive does not include an aromatic amine antiknock agent and methyl tertiary butyl ether.
In one or more embodiments, the additive includes one or more selected from the group consisting of an antioxidant, an anti-icing agent, an antistatic agent, an anti-corrosion agent, and a dye.
In one or more embodiments, the aviation gasoline composition has a motor octane number of not less than 99.6.
In one or more embodiments, the aviation gasoline composition has a motor octane number of from 100 to 102.5.
Another aspect of the invention provides a method of making an aviation gasoline composition according to any one of the embodiments herein, the method comprising the step of mixing the components of the aviation gasoline composition.
In one or more embodiments, the method comprises: distilling the alkylation reaction product of C4 olefin and isobutane to obtain the component with initial boiling point of 23-50 ℃ and end boiling point of 140-148 ℃ as the blending component A.
In one or more embodiments, the alkylation reaction is at a temperature of 4 to 10 ℃, a pressure of 0.4 to 0.45MPa, and a molar ratio of isobutane to C4 olefin of 8 to 12: 1.
In one or more embodiments, the alkylation reaction product of C4 olefins and isobutane is distilled using a distillation column under conditions comprising: the bottom temperature of the distillation tower is 135-146 ℃, the bottom pressure is 0.45-0.55MPa, the top temperature is 50-56 ℃, and the top pressure is 0.43-0.52 MPa.
In one or more embodiments, the component having an initial boiling point of 23 to 50 ℃ and an end point of 140-148 ℃ is withdrawn from the distillation column side stream or cut from the distillation column bottoms as blending component A.
Another aspect of the invention provides an alkane composition comprising, based on the total weight of the alkane composition, 2 to 9 wt% of a C4 alkane, 3 to 6 wt% of a C5 alkane, 4 to 8 wt% of a C6 alkane, 20 to 30 wt% of a C7 alkane, 55 to 68 wt% of a C8 alkane, and 0.55 to 2.3 wt% of a C9 alkane.
In one or more embodiments, the alkane composition has an initial boiling point of 23 to 50 ℃ and an end point of 140-148 ℃.
In one or more embodiments, the alkane composition comprises 4 to 8 wt.% C4 alkane, 3 to 5 wt.% C5 alkane, 4.5 to 7.5 wt.% C6 alkane, 21 to 25 wt.% C7 alkane, 56 to 63 wt.% C8 alkane, and 0.6 to 2 wt.% C9 alkane, based on the total weight of the alkane composition.
In one or more embodiments, the alkane composition has an initial boiling point of 40 ℃ to 48 ℃ and an end point of 142 ℃ to 148 ℃.
The present invention also provides a method of making an alkane composition according to any embodiment herein, the method comprising: distilling the alkylation reaction product of C4 olefin and isobutane to obtain components with initial boiling point of 23-50 ℃ and final boiling point of 140-148 ℃.
In one or more embodiments, the alkylation reaction is at a temperature of 4 to 10 ℃, a pressure of 0.4 to 0.45MPa, and a molar ratio of isobutane to C4 olefin of 8 to 12: 1.
In one or more embodiments, the alkylation reaction product of C4 olefins and isobutane is distilled using a distillation column under conditions comprising: the bottom temperature of the distillation tower is 135-146 ℃, the bottom pressure is 0.45-0.55MPa, the top temperature is 50-56 ℃, and the top pressure is 0.43-0.52 MPa.
In one or more embodiments, the components having an initial boiling point of 23-50 ℃ and an end point of 140-148 ℃ are withdrawn from the distillation column side stream or cut from the distillation column bottoms.
Another aspect of the invention provides the use of a paraffinic hydrocarbon composition as described in any of the embodiments herein in the preparation of an aviation gasoline; preferably, the content of tetraethyl lead in the aviation gasoline is not more than 0.45 mL/L.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the invention, it is to be noted that the terms and expressions which have been stated in the specification and claims are generally understood and defined. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
The terms "comprising," "including," "containing," "having," and the like, herein, encompass the meanings of "consisting essentially of … …" and "consisting of … …," e.g., when "a comprises B and C" is disclosed herein, "a consists of B and C" should be considered to have been disclosed herein.
All features defined herein as numerical ranges or percentage ranges, such as numbers, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Herein, when embodiments or examples are described, it is to be understood that they are not intended to limit the invention to these embodiments or examples. On the contrary, all alternatives, modifications, and equivalents of the methods and materials described herein are intended to be included within the scope of the invention as defined by the appended claims.
It is to be understood that within the scope of the present invention, the above-described technical features of the present invention and the technical features described in detail below (e.g., the embodiments) may be combined with each other to constitute a preferred embodiment.
In the present invention, alkylation refers to a process in which an alkyl group is transferred from one molecule to another, and is a reaction in which an alkyl group is introduced into a molecule of a compound.
In the present invention, the sum of the percentages of all the components in the composition is equal to 100%.
In the present invention, the "C + number" previously indicated for a 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, C7 arene indicates an arene containing seven carbon atoms, and so on.
In the invention, the method for measuring the motor octane number is carried out according to the measurement of the GB _ T503-2016 gasoline octane number.
The invention provides an aviation gasoline composition capable of being used as No. 100 ultralow-lead aviation gasoline, which contains base oil and an additive. It is to be understood that in the present invention, base oil refers to the hydrocarbon material in the aviation gasoline composition. In the invention, the No. 100 aviation gasoline represents that the octane number of the aviation gasoline is more than 99.6. By ultra-low lead is meant that the aviation gasoline has a tetraethyl lead content of no more than 0.45mL/L relative to the total volume of base oil.
In some embodiments, the base oil in the aviation gasoline composition of the present invention comprises, based on the total weight of the base oil: 3.4 to 6 wt.%, preferably 3.6 to 5.8 wt.% of C4 alkanes, 15.8 to 16.9 wt.%, preferably 16 to 16.7 wt.% of C5 alkanes, 8.3 to 9.9 wt.%, preferably 8.5 to 9.7 wt.% of C6 alkanes, 14.3 to 16.6 wt.%, preferably 14.5 to 16.4 wt.% of C7 alkanes, 37.5 to 41.8 wt.%, preferably 37.7 to 41.6 wt.%, more preferably 37.9 to 41.4 wt.% of C8 alkanes, 0.3 to 1.4 wt.%, preferably 0.5 to 1.2 wt.% of C9 alkanes, 11.2 to 14.5 wt.%, preferably 11.4 to 14.3 wt.% of C8 aromatics, and possibly impurities. Preferably, the major component of the C8 aromatics in the base oil of the aviation gasoline composition of the present invention is one or more selected from the group consisting of para-xylene and meta-xylene, for example 80 wt% or more, 90 wt% or more or 95 wt% or more of the C8 aromatics are one or two selected from the group consisting of para-xylene and meta-xylene.
The base oil in the aviation gasoline composition comprises a blending component A, a blending component B and a blending component C.
Blending component A contains or consists of 2-9 wt% of C4 alkane, 3-6 wt% of C5 alkane, 4-8 wt% of C6 alkane, 20-30 wt% of C7 alkane, 55-68 wt% of C8 alkane and 0.55-2.3 wt% of C9 alkane.
The amount of C4 alkane in blend component A is preferably 4 to 8 wt%, and may be, for example, 4.56 wt%, 5.37 wt%, 6.02 wt%, 6.73 wt%, or 7.69 wt%. The content of C5 alkane is preferably 3 to 5 wt%, and may be, for example, 3.77 wt%, 3.9 wt%, 4.02 wt%, 4.13 wt%, or 4.61 wt%. The content of C6 alkane is preferably 4.5 to 7.5 wt%, and may be, for example, 5.17 wt%, 6.02 wt%, 6.58 wt%, 6.61 wt%, or 6.88 wt%. The content of C7 alkane is preferably 21 to 25 wt%, and may be, for example, 22.37 wt%, 23.01 wt%, 23.06 wt%, 23.39 wt%, or 24.01 wt%. The content of C8 alkanes is preferably 56-63 wt%, and may be, for example, 58.36 wt%, 58.37 wt%, 58.92 wt%, 59.01 wt%, or 60.8 wt%. The content of the C9 alkane is preferably 0.6 to 2% by weight, and may be, for example, 0.92%, 1.07%, 1.35%, 1.6% or 1.7% by weight.
In some embodiments, the initial boiling point of blend component A is from 23 to 50 ℃ and the end point is 140-148 ℃. Preferably, blend component A has an initial boiling point of 40 to 48 ℃ or 42 to 46 ℃, for example 43.21 ℃, 43.67 ℃, 44.03 ℃, 44.21 ℃ or 45.23 ℃. Preferably, the end point of the blending component A is 142-148 ℃ or 144-148 ℃ such as 144.31 ℃, 146.95 ℃, 147.21 ℃, 147.23 ℃ or 147.81 ℃. The 10% distillation temperature of the blending component A may be 65-80 deg.C, such as 70-75 deg.C, the 50% distillation temperature may be 105-112 deg.C, such as 107-110 deg.C, the 90% distillation temperature may be 110-120 deg.C, such as 110-116 deg.C. In the present invention, the term "distillation range of A-B ℃ means that the initial boiling point is A ℃ and the final boiling point is B ℃.
In some embodiments, blend component A contains 4.13 to 8.96 wt.% C4 alkane, 3.71 to 4.68 wt.% C5 alkane, 4.12 to 7.13 wt.% C6 alkane, 21.36 to 29.47 wt.% C7 alkane, 56.70 to 66.36 wt.% C8 alkane, and 0.61 to 1.98 wt.% C9 alkane, and the blend component A has an initial boiling point of 23 to 50 ℃ and an end boiling point of 140-148 ℃. In some embodiments, blend component A contains 4.56 to 7.69 wt.% C4 alkane, 3.77 to 4.61 wt.% C5 alkane, 5.17 to 6.88 wt.% C6 alkane, 22.37 to 24.01 wt.% C7 alkane, 58.36 to 60.8 wt.% C8 alkane, and 0.92 to 1.7 wt.% C9 alkane, and the initial boiling point of blend component A is 23 to 50 ℃ and the end point is 140-148 ℃.
Blending component A can be obtained by distilling an alkylation reaction product obtained by performing alkylation reaction on C4 olefin and isobutane to obtain a component with a target initial boiling point and a target final boiling point. The temperature of the alkylation reaction can be 4-10 ℃, the pressure can be 0.4-0.45MPa, and the molar ratio of isobutane to C4 olefin (alkane-alkene ratio) can be 8-12: 1. The alkylation reaction is carried out in the presence of a catalyst, which may be an acid, such as sulfonic acid, hydrofluoric acid, concentrated sulfuric acid. The molar ratio of catalyst to C4 olefin (acid to olefin ratio) may be 1-1.2: 1. In some embodiments, the alkylation reaction is at a temperature of about 7 ℃, a pressure of about 0.43MPa, the catalyst is hydrofluoric acid, and the alkane to alkene ratio is about 10: 1. The distillation of the alkylation reaction product may be carried out in a distillation column. The conditions of the distillation may be: the bottom temperature of the distillation tower is 135-146 ℃, the bottom pressure is 0.45-0.55MPa, the top temperature is 50-56 ℃, and the top pressure is 0.43-0.52 MPa. In some embodiments, the distillation column bottoms temperature is about 138 ℃, the bottoms pressure is about 0.5MPa, the overhead temperature is about 53 ℃, and the overhead pressure is about 0.5 MPa. The manner of obtaining the component having the target initial boiling point and end point is not particularly limited, and for example, the component having the target initial boiling point and end point may be withdrawn from a side of the distillation column or cut out from the bottom of the distillation column, and the methods of withdrawing and cutting are conventional in the art.
The inventor of the invention finds that the blending component A with the initial boiling point of 23-50 ℃ and the final boiling point of 140-148 ℃ obtained by distilling the alkylation reaction product not only removes high-carbon compounds with the boiling range of more than 160 ℃, but also reserves 55-68 wt% of C8 alkane which can contribute higher octane number, and simultaneously contains lighter components such as C4, C5, and the like, and the octane number, the boiling range and the saturated vapor pressure data of the blending component A are close to the requirements of the ASTM-D910 standard for No. 100 ultra-low lead (No. 100 VLL) aviation gasoline, and the blending component A is suitable for being used as the main component of aviation gasoline. In the aviation gasoline composition of the present invention, blending component a makes up 65 to 75 wt%, preferably 65 to 70 wt% of the base oil. The invention therefore also includes a blend component a as a paraffinic composition and its use in the preparation of aviation gasolines, in particular low-lead aviation gasolines, for example aviation gasolines No. 100VLL, which preferably comprise more than 50% by weight, for example more than 65% by weight, 70% by weight, 75% by weight of blend component a.
In the invention, the base oil also comprises a blending component B and a blending component C so as to further adjust the distillation range and the saturated vapor pressure of the aviation gasoline and ensure that the aviation gasoline meets the relevant index requirements of the aviation gasoline standard ASTM-D910. The blending combination B has higher octane number and distillation range and low saturated vapor pressure, and the addition amount of the component has larger influence on the improvement range of the base oil octane number. The blending component C has low octane number and distillation range and high vapor pressure and is mainly used for adjusting the saturated vapor pressure and distillation range of the base oil so as to ensure that the base oil meets the standard.
The blending component B contains one or both of m-xylene and p-xylene, and the total content of m-xylene and p-xylene is 94% by weight or more. It is understood that, herein, the total content of meta-xylene and para-xylene of blend component B means the content of meta-xylene or para-xylene when blend component B contains only meta-xylene or para-xylene, or the sum of the contents of meta-xylene and para-xylene when blend component B contains both meta-xylene and para-xylene. Blending component B is commercially available, for example, as a commercially available meta-xylene product or para-xylene product, or as a product of various conventional processes in the art, provided that the above requirements are met. In some embodiments, blend component B is a paraxylene blend component produced by a paraxylene unit. The paraxylene blending component produced by the paraxylene device is paraxylene prepared by extracting catalytic reformate. It will be appreciated that the blending component B may contain minor amounts, e.g. less than 6 wt%, of impurities such as non-aromatics, ortho-xylene, toluene and the like. The content of non-aromatic hydrocarbons is usually 2% by weight or less, for example 1.5% by weight or less. The ortho-xylene content is generally below 1.5% by weight. The toluene content is usually 1.5% by weight or less.
In some embodiments, blend component B is blend component B1 comprising 94 to 97 weight percent para-xylene and possibly 0 to 1.5 weight percent toluene, 0 to 1.5 weight percent ortho-xylene, 0 to 1.5 weight percent non-aromatics, and/or 0 to 1.5 weight percent meta-xylene. In some embodiments, blend component B is blend component B2 containing 94 to 97 weight percent meta-xylene and possibly 0 to 1.5 weight percent toluene, 0 to 1.5 weight percent ortho-xylene, 0 to 1.5 weight percent non-aromatics, and/or 0 to 1.5 weight percent para-xylene. In some embodiments, blend component B is a combination of blend component B1 and blend component B2, the mass ratio of which is not particularly limited and can be, for example, 1: 2 to 2: 1.
the invention adjusts the saturated vapor pressure of the aviation gasoline within the expected range by adding a proper amount of the blending component B, and the blending component B can contribute to the octane number and improve the antiknock property of the aviation gasoline. In the aviation gasoline composition of the present invention, blending component B makes up 10 to 20 wt%, for example 12 wt%, 15 wt% of the base oil.
Blending component C contains or consists of 0.5-4.5 wt% of C4 alkane, 43-72 wt% of C5 alkane, 24-54 wt% of C6 alkane and 0.05-0.5 wt% of C7 alkane. The amount of C4 alkane in the blend component C is preferably 3 to 4.5 parts by weight, and may be, for example, 3.5%, 3.8%, 3.9% or 4.5% by weight. The content of C5 alkanes is preferably 68 to 72 wt%, and may be, for example, 69.1 wt%, 69.4 wt%, 70 wt%, 70.5 wt%, or 71.2 wt%. The content of C6 alkane is preferably 24 to 30 wt%, and may be, for example, 24.9 wt%, 25.1 wt%, 26 wt%, 26.1 wt%, or 26.9 wt%. The content of the C7 alkane is preferably 0.1 to 0.5 wt%, and may be, for example, 0.1 wt%, 0.2 wt%, or 0.5 wt%. The initial boiling point of the component C is preferably from 25 to 30 ℃ such as from 25 to 28 ℃ and the final boiling point is preferably from 60 to 68 ℃ such as from 63 to 68 ℃.
The blending component C is commercially available, and may be, for example, light naphtha or various processes commonly used in the art for producing light naphtha, as long as the above requirements are satisfied, and may be, for example, light naphtha produced by a hydrocracking unit, an atmospheric and vacuum initial overhead oil of an atmospheric and vacuum distillation unit, or an atmospheric and vacuum overhead oil of an atmospheric and vacuum distillation unit. The light naphtha produced by the hydrocracking unit is the light naphtha which is prepared by the hydrocracking reaction of heavy raw materials in the presence of a catalyst and hydrogen. The atmospheric and vacuum primary top oil is an oil product distilled from the top of a tower after raw oil in an atmospheric and vacuum device enters an electric desalting tank through primary heat exchange and enters a primary tower for separation through secondary heat exchange. The atmospheric and vacuum atmospheric top oil is an oil product which enters an atmospheric fractionating tower from a primary distillation tower in an atmospheric and vacuum distillation device and is distilled from the top of the tower after being rectified. In some embodiments, blend component B is a hydrocracker produced light naphtha or a hydrocracker light naphtha refinery blend component. In some embodiments, blend component B is an atmospheric and vacuum overhead oil.
The distillation range of the aviation gasoline is further adjusted by adding a proper amount of the blending component C. In the aviation gasoline composition of the present invention, blending component C comprises 15 to 25 wt%, for example 18 wt%, 20 wt% of the base oil.
In the aviation gasoline composition of the invention, the base oil comprises or consists of 65 to 75 wt% of the blending component A, 10 to 20 wt% of the blending component B and 15 to 25 wt% of the blending component C. In some embodiments, the base oil comprises or consists of 65 to 70 weight percent of blend component A, 10 to 15 weight percent of blend component B, and 15 to 20 weight percent of blend component C.
The additive in the aviation gasoline composition of the present invention comprises tetraethyl lead. The amount of tetraethyl lead added is not more than 0.45mL/L, preferably not more than 0.43mL/L, for example 0.27-0.43mL/L, based on the total volume of base oil. The aviation gasoline composition of the present invention has a content of tetraethyl lead that is significantly lower than the limiting requirement of the ASTM-D910 standard for the content of tetraethyl lead in aviation gasoline No. 100 LL.
In the aviation gasoline composition of the invention, the content of the tetraethyl lead can be determined according to the motor octane number of the base oil, i.e. in order to make the motor octane number of the aviation gasoline composition reach a target value, the higher the motor octane number contributed by the base oil, the less tetraethyl lead needs to be added. The motor octane number of the base oil is controlled to be higher by controlling the high-octane number component of the blending component A, selecting the blending component B with higher octane number and adopting the components and the proportion of the base oil, so that the motor octane number of the aviation gasoline composition can meet the requirement of No. 100 aviation gasoline by only adding a very small amount (not more than 0.45mL/L) of tetraethyl lead. In some embodiments, the aviation gasoline composition has a tetraethyl lead content of 0.27 to 0.43gmL/L based on the total volume of base oil.
The additives in the aviation gasoline composition of the present invention may also include additives commonly used in the art to meet and improve aviation gasoline performance, such as one or more selected from antioxidants, anti-icing agents, anti-static agents, anti-corrosion agents, dyes, and the like.
The antioxidant suitable for use in the present invention may be various antioxidants conventional in the art, and for example, may be selected from 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, N' -di-sec-butyl-p-phenylenediamine and the like, and preferably from one or more of 2, 6-di-t-butyl-4-cresol, 2, 4-dimethyl-6-t-butylphenol and 2, 6-di-t-butylphenol. In some embodiments, the antioxidant is 2, 6-di-tert-butyl-4-methylphenol. The content of the antioxidant is not more than 12mg/L, preferably 10-12mg/L based on the total volume of the base oil.
The anti-icing agent suitable for the present invention may be various anti-icing agents conventional in the art, and for example, may be selected from one or more of isopropyl alcohol, diethylene glycol monomethyl ether, and the like. In some embodiments, the anti-icing agent is diethylene glycol monomethyl ether. The amount of the anti-icing agent added to the aviation gasoline composition may be an amount conventionally added in the art. In some embodiments, the anti-icing agent is added in an amount of 0.1 to 0.15 volume percent, for example 0.12 volume percent, based on the total volume of the base oil.
Antistatic agents suitable for use in the present invention can be any of a variety of antistatic agents conventional in the art, such as, for example, Stadis 450, a commercially available product (Octel America Inc, Newark, DE 19702). The amount of the antistatic agent added is generally not more than 3mg/L, for example, 2mg/L, based on the total volume of the base oil, 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 amount cannot exceed 5 mg/L.
The corrosion inhibitors suitable for use in the present invention may be any of a variety of corrosion inhibitors conventional in the art, and may be added to the aviation gasoline composition in amounts conventional in the art. Examples of the preservative include DCI-4A (Innospec Co.). In some embodiments, the preservative is added in an amount of 10 to 30mg/m based on the total volume of the base oil3E.g. 20mg/m3。
In addition, to facilitate rapid differentiation of the grade of the aviation gasoline composition, the aviation gasoline composition may also contain a dye. The colour of the dye is selected according to the grade of aviation gasoline. For example, aviation gasoline 80 is red, aviation gasoline 91 is brown, aviation gasoline UL91 is colorless, aviation gasoline 100 is green, and aviation gasoline 100LL is blue. The aviation gasoline composition meets the standard of aviation gasoline No. 100 LL. Thus, in some embodiments, the additive includes a blue dye, such as 1, 4-dialkylaminoanthraquinone, preferably in an amount of no greater than 2.7mg/L, such as 2.3mg/L, based on the total volume of the base oil.
In some embodiments, the aviation gasoline composition of the present invention does not comprise, or is substantially free of, aromatic amine antiknock agents. As used herein, "substantially free" means that certain materials are not intentionally or specifically added to the aviation gasoline composition. Examples of the aromatic amine antiknock agent include aniline, N-methylaniline and m-toluidine. In some embodiments, the aviation gasoline composition of the present invention does not comprise or substantially does not comprise aromatic amine-based compounds. In some embodiments, the aviation gasoline composition of the present invention comprises no or substantially no methyl tertiary butyl ether. In some embodiments, the aviation gasoline composition of the present invention comprises no or substantially no alkyl ether antiknock agent. Examples of alkyl ether antiknock agents include methyl tert-butyl ether, ethyl tert-butyl ether, methyl tert-amyl ether, and diisopropyl ether.
The aviation gasoline composition of the invention can be prepared by mixing the components of the aviation gasoline composition, wherein the components of the aviation gasoline composition and the content thereof are required to be as described above. The order of mixing the components is not particularly limited as long as mixing is sufficient. For example, the components of the base oil may be mixed uniformly and then the additive may be added to mix, or a portion of the base oil may be mixed uniformly with the additive and then the remaining portion of the base oil may be added. In the present invention, preferably, the components of the base oil are mixed uniformly, and then the additive is added and mixed uniformly.
In some embodiments, the process for preparing an aviation gasoline composition of the present invention further comprises the step of obtaining blend component a. The step of obtaining blending component a may be: distilling the alkylation reaction product of C4 olefin and isobutane to obtain an oil product with an initial boiling point and a final boiling point meeting the requirements of the blending component A as the blending component A. The composition and distillation range of the oil meet the relevant requirements as described hereinbefore. The temperature of the alkylation reaction can be 4-10 ℃, the pressure can be 0.4-0.45MPa, and the molar ratio of isobutane to C4 olefin (alkane-alkene ratio) can be 8-12: 1. The alkylation reaction is carried out in the presence of a catalyst. The catalyst may be an acid, for example may be selected from one or more of sulphonic acid, hydrofluoric acid, concentrated sulphuric acid. The molar ratio of catalyst to C4 olefin (acid to olefin ratio) may be 1-1.2: 1. The distillation may be carried out in a distillation column. The conditions of the distillation may be: the bottom temperature of the distillation tower is 135-146 ℃, the bottom pressure is 0.45-0.55MPa, the top temperature is 50-56 ℃, and the top pressure is 0.43-0.52 MPa. The manner of obtaining the component having the target initial boiling point and end point is not particularly limited, and for example, the component having the target initial boiling point and end point may be withdrawn from a side of the distillation column or cut out from the bottom of the distillation column. Extraction and cutting may be performed using methods conventional in the art.
The aviation gasoline composition of the invention has various parameters meeting the requirements of the ASTM-D910 standard on aviation gasoline No. 100 LL. The motor octane number of the aviation gasoline composition is not less than 99.6, such as 99.6-102.5, 100-102.5 and 100.3-102.1, and meets the requirement of antiknock property. The Reid vapor pressure of the aviation gasoline composition is between 38 and 48kPa, and the requirement of evaporability is met. The potential colloid of the aviation gasoline composition is not more than 6mg/100mL, obviously lead precipitation is not more than 3mg/100mL, and the stability requirement is met.
In some embodiments, the aviation gasoline composition of the present invention has an initial boiling point of 40 to 55 deg.C, such as 42 to 54 deg.C, and an end point of 130-150 deg.C, such as 138-145 deg.C. In some embodiments, the aviation gasoline composition of the present invention has a net heating value of 43MJ/kg or greater, such as 43.8MJ/kg or greater. In some embodiments, the aviation gasoline composition of the present invention has a density of 700-711kg/m3. In some embodiments, the aviation gasoline compositions of the present invention have a sulfur content of 0.003% or less, such as 0.0025% or less. In some embodiments, the aviation gasoline composition of the present invention has a freeze point of about-58 ℃. In some embodiments, the aviation gasoline composition of the present invention has a copper flake corrosion (2h, 100 ℃) of about 1. In some embodiments, the aviation gasoline composition of the present invention has a water reaction volume of 0.6 to 0.7 mL.
The aviation gasoline composition has high octane number, good anti-knock performance and high safety coefficient, can meet the requirement of aviation piston engine fuel on the octane number, can be directly used as aviation gasoline, such as aviation gasoline No. 100VLL, and can also be blended with other aviation gasoline to form the required aviation gasoline.
The invention has the following beneficial effects:
the aviation gasoline composition is prepared by blending a few components which are easily obtained in the field in a simple mixing manner, and meets the requirements of the ASTM-D910 standard on aviation gasoline No. 100 LL. The aviation gasoline has high octane number, the motor octane number is more than 99.6, the vapor pressure and the distillation range meet the requirements, the required blending components are few and are simple and easy to obtain, the preparation method is simple, and the production cost is low. The preparation method of the aviation gasoline composition has the advantages of low fixed investment, low production cost, convenient modification and easy implementation, especially for oil refining enterprises.
The aviation gasoline composition has the advantages of low tetraethyl lead content, high octane number, good anti-knock performance and high safety factor, can be used as ultralow-lead aviation gasoline, can meet the requirement of aviation piston engine fuel on the octane number, and has little environmental pollution. The aviation gasoline composition has low aromatic hydrocarbon content, can reduce pollution generated during combustion, and is beneficial to environmental protection. Preferably, the aviation gasoline composition can meet the requirement of antiknock property under the condition of not adding aromatic amine antiknock agent, methyl tert-butyl ether, aromatic amine compounds and/or alkyl ether antiknock agent and only adding ultra-low amount of tetraethyl lead, has small environmental pollution and is friendly to human health.
The present invention will be illustrated below by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples are, unless otherwise indicated, conventional in the art. The starting materials in the examples, unless otherwise stated, are commercially available.
In the following examples, the parameters were measured according to ASTM-D910.
In the following examples, antistatic agents Stadis 450 are available from Octel America Inc, Newark, DE 19702; preservative DCI-4A was purchased from Innospec.
In the following examples, the light naphtha produced by the hydrocracking apparatus is a light naphtha obtained by subjecting a heavy feedstock and hydrogen to a hydrocracking reaction in the presence of a catalyst.
In the following examples, the atmospheric and vacuum overhead oil is an oil product which enters an atmospheric fractionating tower from a primary distillation tower in an atmospheric and vacuum device and is distilled from the top of the tower after being rectified.
Preparation example
C4 olefin and isobutane with an alkane-olefin ratio of 10:1 were alkylated at 7 ℃ under 0.43MPa in the presence of catalyst hydrofluoric acid. The alkylation reaction product of C4 olefin and isobutane is distilled in a distillation tower, the temperature of the bottom of the distillation tower is 138 ℃, the pressure of the bottom of the distillation tower is 0.5MPa, the temperature of the top of the distillation tower is 53 ℃, the pressure of the top of the distillation tower is 0.5MPa, components with the distillation ranges of 43.67-146.95 ℃, 45.23-147.23 ℃, 44.03-144.31 ℃ or 44.21-147.81 ℃ are extracted from the side line of the distillation tower, namely the alkylate modified oil used in examples 1-4 respectively, and the components with the distillation ranges of 43.21-147.21 ℃ are cut from the bottom of the distillation tower of the alkylation device used in example 5, namely the bottom cutting oil of the distillation tower of the alkylation device used in example 5.
Example 1
65 mass percent of alkylate modified oil (the property of which is shown in the table 1-1), 20 mass percent of light naphtha (the property of which is shown in the table 1-2) produced by a hydrocracking device and 15 mass percent of meta-xylene (the property of which is shown in the table 1-3) are mixed, 0.35mL/L of tetraethyl lead is added, other additives are added according to the table 1-4, and after uniform blending, the aviation gasoline is obtained, wherein the property of the aviation gasoline is shown in the table 1-5.
TABLE 1-1
Tables 1 to 2
Tables 1 to 3
Tables 1 to 4
Tables 1 to 5
Example 2
70 mass percent of alkylate modified oil (the property of which is shown in the table 2-1), 18 mass percent of light naphtha (the property of which is shown in the table 2-2) produced by a hydrocracking device and 12 mass percent of meta-xylene (the property of which is shown in the table 2-3) are mixed, 0.38mL/L of tetraethyl lead is added, other additives are added according to the table 1-4, and the aviation gasoline is obtained after uniform blending, wherein the property of the aviation gasoline is shown in the table 2-4.
TABLE 2-1
Tables 2 to 2
Tables 2 to 3
Tables 2 to 4
Example 3
Mixing 65 mass percent of alkylate modified oil (the property of which is shown in the table 3-1), 20 mass percent of atmospheric and vacuum overhead oil (the property of which is shown in the table 3-2) and 15 mass percent of paraxylene (the property of which is shown in the table 3-3), adding 0.41mL/L of tetraethyl lead, adding other additives according to the table 1-4, and uniformly blending to obtain the aviation gasoline, wherein the property of the aviation gasoline is shown in the table 3-4.
TABLE 3-1
TABLE 3-2
Tables 3 to 3
Tables 3 to 4
Example 4
65 mass percent of alkylate modified oil (the property of which is shown in the table 4-1), 20 mass percent of light naphtha (the property of which is shown in the table 4-2) produced by a hydrocracking device, 7.5 mass percent of m-xylene (the property of which is shown in the table 4-3) and 7.5 mass percent of p-xylene (the property of which is shown in the table 4-4) are mixed, 0.4mL/L of tetraethyl lead is added, other additives are added according to the table 1-4, and after uniform blending, the aviation gasoline is obtained, and the property of the aviation gasoline is shown in the table 4-5.
TABLE 4-1
TABLE 4-2
Tables 4 to 3
Tables 4 to 4
Tables 4 to 5
Example 5
Mixing 65 mass percent of alkylation unit distillation tower bottom cutting oil (the property of which is shown in the table 5-1), 20 mass percent of atmospheric and vacuum overhead oil (the property of which is shown in the table 5-2), 10 mass percent of m-xylene (the property of which is shown in the table 5-3) and 5 mass percent of p-xylene (the property of which is shown in the table 5-4), adding 0.43mL/L of tetraethyl lead, adding other additives according to the table 1-4, and uniformly blending to obtain the aviation gasoline, wherein the property of the aviation gasoline is shown in the table 5-5.
TABLE 5-1
TABLE 5-2
Tables 5 to 3
Tables 5 to 4
Tables 5 to 5
From the results of the above examples, it can be seen that the aviation gasoline can be successfully blended by uniformly mixing various easily available components such as the alkylate modified oil, the light naphtha, the xylene blending component and the like in the field and then adding additives such as tetraethyl lead, an anti-icing agent, a preservative and the like. The aviation gasoline has lower lead content than 100LL aviation gasoline, is environment-friendly and has little harm to human body.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. An aviation gasoline composition, which comprises a base oil and an additive, wherein the base oil comprises a blending component A, a blending component B and a blending component C; the base oil comprises 65 to 75 weight percent of the blending component A, 10 to 20 weight percent of the blending component B and 15 to 25 weight percent of the blending component C based on the total weight of the base oil;
wherein the blending component A contains 2-9 wt% of C4 alkane, 3-6 wt% of C5 alkane, 4-8 wt% of C6 alkane, 20-30 wt% of C7 alkane, 55-68 wt% of C8 alkane and 0.55-2.3 wt% of C9 alkane based on the total weight of the blending component A;
the blending component B contains one or two selected from meta-xylene and para-xylene, and the total content of the meta-xylene and the para-xylene is more than 94 wt% based on the total weight of the blending component B;
the blending component C contains 0.5 to 4.5 weight percent of C4 alkane, 43 to 72 weight percent of C5 alkane, 24 to 54 weight percent of C6 alkane and 0.05 to 0.5 weight percent of C7 alkane based on the total weight of the blending component C.
2. The aviation gasoline composition of claim 1 wherein the base oil has a composition that satisfies one or more of the following characteristics based on the total weight of the base oil:
the content of the blending component A is 65-70 wt%;
the content of the blending component B is 10-15 wt%;
the content of the blending component C is 15-20 wt%.
3. The aviation gasoline composition of claim 1 wherein said aviation gasoline composition has one or more of the following characteristics:
the initial boiling point of the blending component A is 23-50 ℃, and the final boiling point is 140-148 ℃; preferably, the initial boiling point of the blending component A is 40-48 ℃, and the final boiling point is 142-148 ℃;
the blending component A contains 4-8 wt% of C4 alkane, 3-5 wt% of C5 alkane, 4.5-7.5 wt% of C6 alkane, 21-25 wt% of C7 alkane, 56-63 wt% of C8 alkane and 0.6-2 wt% of C9 alkane based on the total weight of the blending component A;
the initial distillation point of the blending component B is 135-138 ℃, and the final distillation point is 139-144 ℃;
the blending component B contains 0-2 wt% of non-aromatic hydrocarbon based on the total weight of the blending component B;
the initial boiling point of the blending component C is 25-30 ℃, and the final boiling point is 60-68 ℃;
the blending component C contains 3-4.5 wt% of C4 alkane, 68-72 wt% of C5 alkane, 24-30 wt% of C6 alkane and 0.1-0.5 wt% of C7 alkane based on the total weight of the blending component C;
the additive comprises tetraethyl lead, preferably, the addition amount of the tetraethyl lead is not more than 0.45mL/L, such as 0.27-0.43mL/L, based on the total volume of the base oil;
the additive does not comprise aromatic amine antiknock agent and methyl tert-butyl ether;
the additive includes one or more selected from the group consisting of an antioxidant, an anti-icing agent, an antistatic agent, an anti-corrosion agent, and a dye.
4. The aviation gasoline composition according to any one of claims 1 to 3 wherein said aviation gasoline composition has a motor octane number of not less than 99.6;
preferably, the aviation gasoline composition has a motor octane number of from 100 to 102.5.
5. A process for preparing the aviation gasoline composition of any one of claims 1 to 4 comprising the step of mixing the components of the aviation gasoline composition.
6. The method of claim 5, wherein the method comprises: distilling the alkylation reaction product of C4 olefin and isobutane to obtain a component with an initial boiling point of 23-50 ℃ and an end boiling point of 140-148 ℃ as a blending component A;
preferably, the alkylation reaction is carried out at a temperature of 4-10 deg.C, a pressure of 0.4-0.45MPa, and a molar ratio of isobutane to C4 olefin of 8-12: 1.
7. The process of claim 6 wherein the alkylation reaction product of C4 olefins and isobutane is distilled using a distillation column under conditions comprising: the bottom temperature of the distillation tower is 135-146 ℃, the bottom pressure is 0.45-0.55MPa, the top temperature is 50-56 ℃, and the top pressure is 0.43-0.52 MPa;
preferably, a component having an initial boiling point of 23 to 50 ℃ and an end point of 140-148 ℃ is withdrawn from the side line of the distillation column or cut from the bottom oil of the distillation column as the blending component A.
8. An alkane composition comprising, based on the total weight of the alkane composition, from 2 to 9 weight percent of a C4 alkane, from 3 to 6 weight percent of a C5 alkane, from 4 to 8 weight percent of a C6 alkane, from 20 to 30 weight percent of a C7 alkane, from 55 to 68 weight percent of a C8 alkane, and from 0.55 to 2.3 weight percent of a C9 alkane;
preferably, the alkane composition has an initial boiling point of 23-50 ℃ and an end point of 140-148 ℃.
9. The alkane composition of claim 8,
the alkane composition comprises 4 to 8 weight percent of C4 alkane, 3 to 5 weight percent of C5 alkane, 4.5 to 7.5 weight percent of C6 alkane, 21 to 25 weight percent of C7 alkane, 56 to 63 weight percent of C8 alkane and 0.6 to 2 weight percent of C9 alkane based on the total weight of the alkane composition; and/or
The initial boiling point of the alkane composition is 40-48 ℃, and the final boiling point is 142-148 ℃.
10. A process for preparing the alkane composition of claim 8 or 9, characterized in that the process comprises: distilling the alkylation reaction product of C4 olefin and isobutane to obtain components with initial boiling point of 23-50 ℃ and final boiling point of 140-148 ℃;
preferably, the alkylation reaction is carried out at a temperature of 4-10 deg.C, a pressure of 0.4-0.45MPa, and a molar ratio of isobutane to C4 olefin of 8-12: 1.
11. The process of claim 10 wherein the alkylation reaction product of C4 olefins and isobutane is distilled using a distillation column under conditions comprising: the bottom temperature of the distillation tower is 135-146 ℃, the bottom pressure is 0.45-0.55MPa, the top temperature is 50-56 ℃, and the top pressure is 0.43-0.52 MPa;
preferably, the components having an initial boiling point of 23-50 ℃ and an end point of 140-148 ℃ are withdrawn from the side line of the distillation column or cut from the bottom oil of the distillation column.
12. Use of the alkane composition of claim 8 or 9 or obtained by the process of claim 10 or 11 for the preparation of aviation gasoline; preferably, the content of tetraethyl lead in the aviation gasoline is not more than 0.45 mL/L.
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| CN1052323A (en) * | 1989-12-07 | 1991-06-19 | 州际化学有限公司 | Blended gasoline and preparation method thereof |
| US20120029251A1 (en) * | 2010-07-28 | 2012-02-02 | Chevron U.S.A. Inc. | High octane aviation fuel composition |
| CN106590772A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Low-lead aviation gasoline and preparation method thereof |
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