CN113736525A - No. 91 leadless aviation gasoline and production method thereof - Google Patents
No. 91 leadless aviation gasoline and production method thereof Download PDFInfo
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Abstract
The invention provides an aviation gasoline composition capable of being used as No. 91 unleaded aviation gasoline and a production method thereof. The aviation gasoline composition provided by the invention meets the requirements of various indexes of No. 91 aviation gasoline such as anti-knock property, evaporability, low-temperature fluidity and stability in the ASTM D910 standard, the ASTM D7547 standard and the GB 1787-. In addition, the aviation gasoline composition does not contain tetraethyl lead, is environment-friendly and can meet the requirement of people on environmental protection.
Description
Technical Field
The invention belongs to the technical field of fuels, and particularly relates to No. 91 unleaded 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. China's aviation gasoline mainly adopts hydrofined gasoline as the main component for producing aviation gasoline. Tetraethyl lead is colorless transparent oily liquid with slightly fruity sweet taste and is widely applied as a gasoline additive. The addition of tetraethyl lead can increase the octane number of the fuel to prevent knocking in the engine, thereby increasing the efficiency and power of the engine. In view of the fact that lead emissions from the combustion of leaded aviation gasoline account for an increasing proportion of industrial lead emissions, more and more countries are beginning to pay attention to unleaded aviation gasoline, and No. 91 unleaded (No. UL 91) high quality aviation gasoline will be the subject of future market demand.
CN 108315060A proposes No. 91 lead-free aviation gasoline and a preparation method thereof, and proposes that No. 91 lead-free aviation gasoline comprises the following components: 80-90% of alkane and 10-20% of arene are blended according to the volume percentage, or are prepared by petrochemical refining technology. The blending oil used in the document is industrial isopentane, xylene and industrial isooctane. However, industrial isopentane is prepared by refining light naphtha, has low yield, lighter price and high naphtha content and is not easy to obtain; the distillation range of the xylene is higher, the relevant standard of the distillation range of ASTM D910 is not easy to meet in the blending process, and the price of the xylene is higher than that of the toluene, so the economic value of the formula is lower.
CN 106590773B proposes a lead-free aviation gasoline and a preparation method thereof, and proposes the components of the aviation gasoline as follows: A)55 to 90 wt% of an alkylate unit oil; B)5 to 15 wt% of pentane component oil, C)0 to 20 wt% of C7 aromatic hydrocarbon component oil; D)0-15 wt.% cumene; and E)0 to 15 wt% of an alkyl ether antiknock agent, wherein the arylamine compound content of the unleaded aviation gasoline is not more than 0.5 wt% and contains not more than 0.01g/L of lead, wherein at least one of components C and D is contained. The motor octane number of the lead-free aviation gasoline is not less than 91. The blending component oils used in this document are an alkylate unit oil, a pentane component oil, a C7 aromatic component oil, cumene and an alkyl ether antiknock agent, and have the following problems: (1) the blending component oil in the formula is more, and the blending process is complex; (2) the alkyl ether antiknock in the formula is generally methyl tert-butyl ether, which is a common gasoline antiknock, but easily penetrates through soil and enters an underground drinking water system, has stable property and difficult decomposition, and can cause certain harm to the nervous system, intestines and stomach and the ecological environment of people; (3) the pentane component oil in the formula is prepared by refining light naphtha, the yield is low, the price is light, and the naphtha is high and is not easy to obtain.
In summary, the conventional aviation gasoline blend of UL91 uses a plurality of component oils, and the component oils are expensive and do not meet the ASTM D910 standard. There remains a need in the art for a No. 91 unleaded aviation gasoline that has a low component oil variety and a low price while meeting ASTM D910 standards.
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 various indexes of No. 91 aviation gasoline, such as antiknock property, evaporability, low-temperature fluidity and stability, in the ASTM D910 standard, the ASTM D7547 standard and the GB 1787-. In addition, the aviation gasoline composition does not contain tetraethyl lead, is environment-friendly and can meet the requirement of people on environmental protection.
Specifically, one aspect of the invention provides an aviation gasoline composition comprising a base oil comprising blending component a, blending component B and optionally blending component C; the base oil comprises 73 to 92 weight percent of the blending component A, 8 to 20 weight percent of the blending component B and 0 to 18 weight percent of the blending component C based on the total weight of the base oil;
wherein the blending component A contains 3-7 wt% of C4 alkane, 2-6 wt% of C5 alkane, 3-7 wt% of C6 alkane, 22-30 wt% of C7 alkane, 51-65 wt% of C8 alkane and 0.75-2.5 wt% of C9 alkane based on the total weight of the blending component A;
the blending component B contains 1-5 wt% of C4 alkane, 40-70 wt% of C5 alkane, 25-50 wt% of C6 alkane and 0.05-0.3 wt% of C7 alkane based on the total weight of the blending component B;
the blending component C contains more than 90 wt% of C7 aromatic hydrocarbon based on the total weight of the blending component C.
In one or more embodiments, the base oil has a blend component A content of 75 to 90 weight percent based on the total weight of the base oil.
In one or more embodiments, the base oil has a blending component B content of 9 to 18 weight percent, based on the total weight of the base oil.
In one or more embodiments, the base oil has a blend component C content of 0 to 15 wt.%, based on the total weight of the base oil.
In one or more embodiments, the initial boiling point of blend component A is from 26 to 55 ℃ and the end point is 135-151 ℃; preferably, the initial boiling point of the blending component A is 45-50 ℃ and the final boiling point is 138-145 ℃.
In one or more embodiments, blend component a contains 4 to 6.5 weight percent C4 alkanes, 3 to 6 weight percent C5 alkanes, 3.5 to 7 weight percent C6 alkanes, 22.5 to 26 weight percent C7 alkanes, 55 to 62 weight percent C8 alkanes, and 1 to 2.5 weight percent C9 alkanes, based on the total weight of blend component a.
In one or more embodiments, the blending component B has an initial boiling point of from 21 to 25 ℃ and an end point of from 60 to 63 ℃.
In one or more embodiments, blend component B contains 2.5 to 5 weight percent C4 alkanes, 58 to 68 weight percent C5 alkanes, 28 to 36 weight percent C6 alkanes, and 0.1 to 0.3 weight percent C7 alkanes, based on the total weight of blend component B.
In one or more embodiments, the initial boiling point of blend component C is from 107.3 to 108.5 ℃ and the final boiling point is from 109.5 to 110.5 ℃.
In one or more embodiments, the blend component C also contains C8 aromatics and has a total content of C7 aromatics and C8 aromatics of greater than 95 weight percent, based on the total weight of the blend component C.
In one or more embodiments, the additive does not include tetraethyl lead.
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 91.
In one or more embodiments, the aviation gasoline composition has a motor octane number of from 91 to 93.
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 26-55 ℃, end point of 135-151 ℃ or initial boiling point of 45-50 ℃ and end point of 138-145 ℃ 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 137-146 ℃, the bottom pressure is 0.43-0.53MPa, the top temperature is 51-56 ℃, and the top pressure is 0.41-0.5 MPa.
In one or more embodiments, the component having an initial boiling point of 26-55 ℃, an end point of 135-151 ℃ or an initial boiling point of 45-50 ℃ and an end point of 138-145 ℃ is withdrawn from the side line of the distillation column as the blending component A, or the component having an initial boiling point of 26-55 ℃, an end point of 135-151 ℃ or an initial boiling point of 45-50 ℃ and an end point of 138-145 ℃ is cut from the bottom oil of the distillation column as the blending component A.
The present invention also provides an aviation gasoline composition prepared by the method of preparing an aviation gasoline composition as described in any one of the embodiments herein.
Another aspect of the invention provides an alkane composition comprising, based on the total weight of the alkane composition, 3 to 7 weight percent of a C4 alkane, 2 to 6 weight percent of a C5 alkane, 3 to 7 weight percent of a C6 alkane, 22 to 30 weight percent of a C7 alkane, 51 to 65 weight percent of a C8 alkane, and 0.75 to 2.5 weight percent of a C9 alkane.
In one or more embodiments, the alkane composition has an initial boiling point of 26 to 55 ℃ and an end point of 135-151 ℃.
In one or more embodiments, the alkane composition comprises 4 to 6.5 wt.% C4 alkane, 3 to 6 wt.% C5 alkane, 3.5 to 7 wt.% C6 alkane, 22.5 to 26 wt.% C7 alkane, 55 to 62 wt.% C8 alkane, and 1 to 2.5 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 45 to 50 ℃ and an end point of 138-145 ℃.
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 26-55 ℃, end point of 135-151 ℃ or initial boiling point of 45-50 ℃ and end point of 138-145 ℃ 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 137-146 ℃, the bottom pressure is 0.43-0.53MPa, the top temperature is 51-56 ℃, and the top pressure is 0.41-0.5 MPa.
In one or more embodiments, the components having an initial point of 26-55 ℃, an end point of 135-.
The present invention also provides an alkane composition prepared by the method of preparing an alkane composition according to any one of the embodiments herein.
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 aviation gasoline is unleaded aviation gasoline, preferably No. 91 unleaded aviation gasoline.
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. 91 unleaded 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 some embodiments, the base oil in the aviation gasoline composition of the present invention comprises, based on the total weight of the base oil: 3.8-6 wt.%, preferably 4-5.8 wt.% C4 alkane, 9.6-14.4 wt.%, preferably 9.8-14.2 wt.% C5 alkane, 6.8-10.5 wt.%, preferably 7-10.3 wt.% C6 alkane, 18-20.9 wt.%, preferably 18.2-20.7 wt.% C7 alkane, 43-53.8 wt.%, preferably 43.2-53.6 wt.%, more preferably 43.4-53.4 wt.% C8 alkane, 0.7-2.2 wt.%, preferably 0.9-2 wt.% C9 alkane, optionally 0-18 wt.%, preferably 5-15 wt.%, more preferably 6-14 wt.% C7 arene, and possibly present impurities.
The base oil in the aviation gasoline composition of the present invention comprises blending component a and blending component B, and optionally may also comprise blending component C.
Blending component A contains or consists of 3-7 wt% of C4 alkane, 2-6 wt% of C5 alkane, 3-7 wt% of C6 alkane, 22-30 wt% of C7 alkane, 51-65 wt% of C8 alkane and 0.75-2.5 wt% of C9 alkane. In the blending component A, the content of C4 alkane is preferably 4-6.5 wt%, the content of C5 alkane is preferably 3-6 wt%, the content of C6 alkane is preferably 3.5-7 wt%, the content of C7 alkane is preferably 22.5-26 wt%, the content of C8 alkane is preferably 55-62 wt%, and the content of C9 alkane is preferably 1-2.5 wt%. For example, in blend component a, C4 alkane may be present in an amount of 4.32 wt%, 5.45 wt%, 5.98 wt%, 6.12 wt%, or 6.13 wt%, C5 alkane may be present in an amount of 3.59 wt%, 4.69 wt%, 5.06 wt%, 5.16 wt%, or 5.78 wt%, C6 alkane may be present in an amount of 4.07 wt%, 4.32 wt%, 5.02 wt%, 6.23 wt%, or 6.51 wt%, C7 alkane may be present in an amount of 23.18 wt%, 24.01 wt%, or 25.34 wt%, C8 alkane may be present in an amount of 57.16 wt%, 58.17 wt%, 58.23 wt%, 59.2 wt%, or 59.98 wt%, and C9 alkane may be present in an amount of 1.27 wt%, 1.37 wt%, 1.63 wt%, 1.69 wt%, or 2.32 wt%.
The initial boiling point of the blending component A is 26-55 ℃, and the final boiling point is 135-151 ℃. Preferably, blend component A has an initial boiling point of from 45 to 50 deg.C, more preferably from 45.5 to 48.5 deg.C. Preferably, the end point of blending component A is 138-145 deg.C, more preferably 139-144 deg.C. For example, the initial boiling point of the component A may be 46.1 ℃, 46.3 ℃, 46.9 ℃, 47.1 ℃ or 48.1 ℃ and the final boiling point of the component A may be 140.2 ℃, 141.1 ℃, 141.9 ℃, 142.1 ℃ or 143.5 ℃. The 10% distillation temperature of the blending component A may be 65-80 deg.C, such as 70-76 deg.C, the 50% distillation temperature may be 100-. 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 3.38 to 6.76 wt.% C4 alkane, 2.94 to 5.98 wt.% C5 alkane, 3.62 to 6.69 wt.% C6 alkane, 22.34 to 29.35 wt.% C7 alkane, 51.31 to 63.84 wt.% C8 alkane, and 0.75 to 2.48 wt.% C9 alkane, and the blend component A has an initial boiling point of 26 to 55 ℃ and an end point of 135 ℃ and 150 ℃.
The alkylation reaction product may be distilled to obtain as blending component a component having an initial boiling point and an end point satisfying the aforementioned requirements for blending component a. The alkylation reaction product may be a product obtained by alkylation of C4 olefin with isobutane. 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 molar ratio of catalyst to C4 olefin (acid to olefin ratio) may be 1-1.2: 1. The catalyst for the alkylation reaction may be an acid, and may be selected from one or more of sulphonic acid, hydrofluoric acid, concentrated sulphuric acid, for example. In some embodiments, the alkylation reaction is at a temperature of about 7.5 ℃, a pressure of about 0.42MPa, the catalyst is hydrofluoric acid, and the alkane to alkene ratio is about 10.5: 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 137-146 ℃, the bottom pressure is 0.43-0.53MPa, the top temperature is 51-56 ℃, and the top pressure is 0.41-0.5 MPa. In some embodiments, the distillation column bottoms temperature is about 142 ℃, the bottoms pressure is about 0.47MPa, the overhead temperature is about 53 ℃, and the overhead pressure is about 0.44 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 extracted from a side line of the distillation column, or the component having the target initial boiling point and end point may be cut out from the bottom of the distillation column. Extraction and cutting may be performed using methods conventional in the art.
The inventor of the invention finds that the blending component A with the initial boiling point of 26-55 ℃ and the final boiling point of 135-151 ℃ obtained by distilling the alkylation reaction product not only removes high-carbon compounds with the boiling range of more than 160 ℃, but also reserves 51-65 wt% of C8 alkane which can contribute to 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 related index requirements of No. 91 unleaded aviation gasoline in the aviation gasoline standard ASTM-D910, 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 73 to 92% by weight, preferably 75 to 90% by weight, for example 76%, 77%, 86% by weight 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 unleaded aviation gasolines, for example unleaded aviation gasoline No. 91, preferably comprising more than 70% by weight of blend component a, for example comprising 73%, 75%, 76%, 77%, 86%, 90%, 92% by weight of blend component a.
In the invention, the base oil also comprises a blending component B and an optional blending component C so as to further adjust the distillation range and the saturated vapor pressure of the aviation gasoline and ensure that the base oil meets the related index requirements of No. 91 unleaded aviation gasoline in the aviation gasoline standard ASTM-D910. The blending component B 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 combination C 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 B contains or consists of 1 to 5 weight percent of C4 alkane, 40 to 70 weight percent of C5 alkane, 25 to 50 weight percent of C6 alkane and 0.05 to 0.3 weight percent of C7 alkane. In the blending component B, the content of C4 alkane is preferably 2.5-5 parts by weight, the content of C5 alkane is preferably 58-68% by weight, the content of C6 alkane is preferably 28-36% by weight, and the content of C7 alkane is preferably 0.1-0.3% by weight. For example, in blend component B, C4 alkane may be present in an amount of 2.8 wt%, 4.1 wt%, 4.3 wt%, or 4.8 wt%, C5 alkane may be present in an amount of 60.9 wt%, 62.6 wt%, 63.8 wt%, 64.1 wt%, or 64.7 wt%, C6 alkane may be present in an amount of 30.8 wt%, 31.9 wt%, 32.8 wt%, 32.9 wt%, or 34.2 wt%, and C7 alkane may be present in an amount of 0.1 wt%, 0.2 wt%, or 0.3 wt%. The initial boiling point of blending component B is preferably from 21 to 25 ℃ and the final boiling point is preferably from 60 to 63 ℃.
Blending component B is commercially available or may be derived from products of various refinery processes in the art, provided that the properties meet the aforementioned requirements. For example, blending component B may be one or more selected from light naphtha (including light naphtha produced by a hydrocracking unit), atmospheric and vacuum overhead produced by an atmospheric and vacuum distillation unit, and atmospheric and vacuum initial overhead produced by an atmospheric and vacuum distillation unit. The light naphtha produced by the hydrocracking device is an oil product which is prepared by the hydrocracking reaction of a heavy raw material 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, blending component B is a light naphtha or an atmospheric and vacuum overhead produced by a hydrocracking unit.
The distillation range of the aviation gasoline can be adjusted by adding a proper amount of the blending component B. In the aviation gasoline composition of the present invention, blending component B makes up 8 to 20 wt%, preferably 9 to 18 wt%, for example 11.1 wt%, 14 wt%, 16.5 wt% of the base oil.
The blending component C contains more than 90 wt% of C7 aromatic hydrocarbon, and the balance of a small amount of C8 aromatic hydrocarbon, C7 by-products, benzene and the like. Preferably, blend component C contains 90 to 97 wt.%, e.g., 90 to 95 wt.%, 92 to 95 wt.% of C7 aromatics. In some embodiments, blend component C contains 1 to 5 wt.%, e.g., 2 to 4.5 wt.% C8 aromatics. In some embodiments, the total content of C7 aromatics and C8 aromatics in blend component C is greater than 95 wt.%, e.g., 95-99 wt.%, 96-99 wt.%. Preferably, blending component C has an initial boiling point of from 107.3 to 108.5 ℃ and an end point of from 109.5 to 110.5 ℃, for example from 109.5 to 110.2 ℃.
Blending component C is commercially available or may be derived from products of various refinery processes in the art, so long as the properties meet the aforementioned requirements. For example, blending component C can be a C7 aromatic component oil produced by an aromatics extraction unit. The C7 aromatic component oil produced by the aromatic extraction device is C7 fraction separated from a reformed mixed product obtained by reforming straight-run naphtha by adopting a sulfolane liquid-liquid extraction process.
In the present invention, blending component C is optionally added as required. The octane number of the base oil can be improved by adding a proper amount of the blending component C. In the aviation gasoline composition of the present invention, blending component C is present in an amount of 0 to 18% by weight, for example 0 to 15%, 0 to 10%, 5 to 15%, 6.5%, 7% by weight, based on the base oil.
In the aviation gasoline composition of the invention, the base oil comprises or consists of 73 to 92 wt% of blending component A, 8 to 20 wt% of blending component B and 0 to 18 wt% of blending component C. In some embodiments, the base oil comprises or consists of 75 to 90 wt.% of blend component A, 0 to 18 wt.% (e.g., 9 to 18 wt.%) of blend component B, and 0 to 15 wt.% (e.g., 0 to 10 wt.%) of blend component C. In some embodiments, the base oil includes blend component A and blend component B, excluding blend component C, wherein blend component A may be present in an amount of 82 to 92 wt.%, such as 84 to 90 wt.%, 86 to 89 wt.%, and blend component B may be present in an amount of 8 to 18 wt.%, such as 10 to 16 wt.%, 11 to 14 wt.%. In some embodiments, the base oil comprises a blending component A, a blending component B, and a blending component C, wherein the blending component A can be present in an amount of 73 to 82 wt%, such as 75 to 80 wt%, 75 to 77 wt%, and the blending component B can be present in an amount of 8 to 20 wt%, such as 9 to 18 wt%. The amount of blending component C may be from 5 to 18% by weight, for example from 6 to 15% by weight.
The additives in the aviation gasoline composition of the present invention may 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.
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 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。
The aviation gasoline composition of the present invention comprises no or substantially no tetraethyllead. As used herein, "substantially free" means that certain materials are not intentionally or specifically added to the aviation gasoline composition. In some embodiments, the aviation gasoline composition of the present invention does not comprise, or is substantially free of, aromatic amine antiknock agents. 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. In some embodiments, the aviation gasoline composition of the present invention does not comprise an antiknock agent.
The aviation gasoline composition of the present invention may be prepared by mixing the components of the aviation gasoline composition described previously. The present invention includes a process for preparing an aviation gasoline composition of the present invention comprising the step of mixing the components of the aviation gasoline composition. Wherein, the components and the content of the aviation gasoline composition are required to be as described in the foregoing.
The order of mixing the components in preparing the aviation gasoline composition of the present invention is not particularly limited as long as mixing is sufficient. In some embodiments, the base oil components are mixed to homogeneity before the additives are added to the base oil. In other embodiments, a portion of the base oil is first blended with the additives and then the remaining portion of the base oil is added, or the base oil and additives are added simultaneously and blended, and the like.
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 a component 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 this component are such that the corresponding requirements for blending component A as described hereinbefore are met. The temperature of the alkylation reaction can be 4-10 ℃, the pressure can be 0.4-0.45MPa, and the alkane-alkene ratio can be 8-12: 1. The alkylation reaction is carried out in the presence of a catalyst. The molar ratio of catalyst to C4 olefin (acid to olefin ratio) may be 1-1.2: 1. The catalyst for the alkylation reaction may be an acid, and may be selected from one or more of sulphonic acid, hydrofluoric acid, concentrated sulphuric acid, for example. 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 137-146 ℃, the bottom pressure is 0.43-0.53MPa, the top temperature is 51-56 ℃, and the top pressure is 0.41-0.5 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 extracted from a side line of the distillation column, or the component having the target initial boiling point and end point may be 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 provided by the invention has various parameters meeting the standards of No. 91 unleaded aviation gasoline in the ASTM D910 standard, the ASTM D7547 standard and the GB 1787-2018 standard. The motor octane number of the aviation gasoline composition is not less than 91, such as 91-93, and meets the requirement of antiknock property. The Reid vapor pressure of the aviation gasoline composition is between 38 and 49kPa, 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 from 40 ℃ to 48 ℃, such as from 42 ℃ to 46.5 ℃, and an end point of from 125 ℃ to 140 ℃, such as from 128 ℃ to 135 ℃. In some embodiments, the aviation gasoline composition of the present invention has a net heating value of 43MJ/kg or greater, such as 44MJ/kg or greater. In some embodiments, the aviation gasoline composition of the present invention has a density of 690-705kg/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 about 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, particularly UL91 aviation gasoline, 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 and have fewer types in a simple mixing manner, and simultaneously meets the ASTM D910 standard, the ASTM D7547 standard and the GB 1787-2018 standard of aviation gasoline No. UL 91. The aviation gasoline has high octane number, the motor octane number is more than 91, such as 91-93, the vapor pressure and the distillation range meet the requirements, the required blending components are few, simple and easily available, the source is wide, high refining is not required, the aviation gasoline can be prepared by adopting crude products of oil refining enterprises, 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 disclosed by the invention does not contain tetraethyl lead, 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, and can be used as lead-free aviation gasoline, particularly as aviation gasoline UL 91. The aviation gasoline composition has low aromatic hydrocarbon content, can reduce pollution generated during combustion, and is beneficial to environmental protection. The aviation gasoline composition can meet the requirement of antiknock property under the condition of not containing aromatic amine antiknock agent, methyl tertiary butyl ether, aromatic amine compound and/or alkyl ether antiknock agent, 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.
In the following examples, the C7 aromatic component oil produced by the aromatic extraction device is a C7 fraction separated from a reformed mixed product obtained by reforming straight-run naphtha by a sulfolane liquid-liquid extraction process.
Preparation example
C4 olefin and isobutane with an alkane-olefin ratio of 10.5:1 were alkylated at 7.5 ℃ under 0.42MPa in the presence of a catalyst, hydrofluoric acid. The alkylation reaction product of C4 olefin and isobutane was distilled in a distillation column at a bottom temperature of 142 deg.C and a bottom pressure of 0.47MPa, at a top temperature of 53 deg.C and a top pressure of 0.44MPa, with distillation ranges of 46.3-140.2 deg.C, 46.1-143.5 deg.C or 47.1-141.1 deg.C being drawn from the side of the column, or with components cut from the bottom of the column at a flow path of 46.9-142.1 deg.C or 48.1-141.9 deg.C, i.e., the side draw oils from the column of the alkylation unit used in examples 1-5, respectively.
Example 1
Mixing 88.9 mass% of side draw oil (the property of which is shown in the table 1-1) of a distillation tower of an alkylation device and 11.1 mass% of light naphtha (the property of which is shown in the table 1-2) produced by a hydrocracking device, adding other additives according to the table 1-3, and uniformly blending to obtain the aviation gasoline, wherein the property of the aviation gasoline is shown in the table 1-4.
TABLE 1-1
Tables 1 to 2
Tables 1 to 3
Tables 1 to 4
Example 2
Mixing 86 mass% of side draw oil of a distillation tower of an alkylation unit (the property of the side draw oil is shown in a table 2-1) and 14 mass% of light naphtha (the property of the side draw oil is shown in a table 2-2) produced by a hydrocracking unit, adding other additives according to the table 1-3, and uniformly blending to obtain the aviation gasoline, wherein the property of the aviation gasoline is shown in the table 2-3.
TABLE 2-1
Tables 2 to 2
Tables 2 to 3
Example 3
Mixing 76 mass percent of side draw oil of a distillation tower of an alkylation device (the property of the side draw oil is shown in a table 3-1), 9 mass percent of atmospheric and vacuum overhead oil (the property of the side draw oil is shown in a table 3-2) and 15 mass percent of aromatic component oil of C7 (the property of the aromatic component oil is shown in a table 3-3) produced by an aromatic extraction device, adding other additives according to the table 1-3, 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
75 mass percent of alkylation unit distillation tower bottom cutting oil (the property of which is shown in the table 4-1), 18 mass percent of light naphtha (the property of which is shown in the table 4-2) produced by a hydrocracking unit and 7 mass percent of C7 aromatic component oil (the property of which is shown in the table 4-3) produced by an aromatic extraction unit are mixed, then other additives are added according to the table 1-3, and after uniform blending, the aviation gasoline is obtained, wherein the property of the aviation gasoline is shown in the table 4-4.
TABLE 4-1
TABLE 4-2
Tables 4 to 3
Tables 4 to 4
Example 5
77 mass percent of alkylation device distillation tower bottom cutting oil (the property of which is shown in the table 5-1), 16.5 mass percent of atmospheric and vacuum overhead oil (the property of which is shown in the table 5-2) and 6.5 mass percent of C7 aromatic component oil (the property of which is shown in the table 5-3) produced by an aromatic extraction device are mixed, then other additives are added according to the table 1-3, and after uniform blending, the aviation gasoline is obtained, wherein the property of the aviation gasoline is shown in the table 5-4.
TABLE 5-1
TABLE 5-2
Tables 5 to 3
Tables 5 to 4
From the results of the above examples, it can be seen that the number 91 unleaded aviation gasoline can be successfully blended by uniformly mixing various components which are easily obtained in the field such as alkylate, light naphtha, C7 aromatic component oil and the like, and then adding additives such as an anti-icing agent, a preservative and the like. The blending component oil of No. 91 unleaded aviation gasoline has wide raw material sources, can be directly used without high refining, can produce aviation gasoline by slight modification of general oil refining enterprises, has low fixed investment and is easy to implement.
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, characterized in that the aviation gasoline composition comprises a base oil and an additive, wherein the base oil comprises a blending component A, a blending component B and an optional blending component C; the base oil comprises 73 to 92 weight percent of the blending component A, 8 to 20 weight percent of the blending component B and 0 to 18 weight percent of the blending component C based on the total weight of the base oil;
wherein the blending component A contains 3-7 wt% of C4 alkane, 2-6 wt% of C5 alkane, 3-7 wt% of C6 alkane, 22-30 wt% of C7 alkane, 51-65 wt% of C8 alkane and 0.75-2.5 wt% of C9 alkane based on the total weight of the blending component A;
the blending component B contains 1-5 wt% of C4 alkane, 40-70 wt% of C5 alkane, 25-50 wt% of C6 alkane and 0.05-0.3 wt% of C7 alkane based on the total weight of the blending component B;
the blending component C contains more than 90 wt% of C7 aromatic hydrocarbon 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 75-90 wt%;
the content of the blending component B is 9-18 wt%;
the content of the blending component C is 0 to 15 weight percent.
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 26-55 ℃, and the final boiling point is 135-151 ℃; preferably, the initial boiling point of the blending component A is 45-50 ℃, and the final boiling point is 138-145 ℃;
the blending component A contains 4-6.5 wt% of C4 alkane, 3-6 wt% of C5 alkane, 3.5-7 wt% of C6 alkane, 22.5-26 wt% of C7 alkane, 55-62 wt% of C8 alkane and 1-2.5 wt% of C9 alkane based on the total weight of the blending component A;
the initial boiling point of the blending component B is 21-25 ℃, and the final boiling point is 60-63 ℃;
the blending component B contains 2.5 to 5 weight percent of C4 alkane, 58 to 68 weight percent of C5 alkane, 28 to 36 weight percent of C6 alkane and 0.1 to 0.3 weight percent of C7 alkane based on the total weight of the blending component B;
the initial boiling point of the blending component C is 107.3-108.5 ℃, and the final boiling point is 109.5-110.5 ℃;
the blending component C also contains C8 aromatic hydrocarbon, and the total content of the C7 aromatic hydrocarbon and the C8 aromatic hydrocarbon is more than 95 weight percent based on the total weight of the blending component C;
the additive does not include tetraethyl lead;
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 of any one of claims 1 to 3 wherein said aviation gasoline composition has a motor octane number of not less than 91;
preferably, the aviation gasoline composition has a motor octane number of from 91 to 93.
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 distillation point of 26-55 ℃, an end distillation point of 135-151 ℃ or an initial distillation point of 45-50 ℃ and an end distillation point of 138-145 ℃ 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 137-146 ℃, the bottom pressure is 0.43-0.53MPa, the top temperature is 51-56 ℃, and the top pressure is 0.41-0.5 MPa;
preferably, the component with the initial distillation point of 26-55 ℃, the end point of 135-151 ℃ or the initial distillation point of 45-50 ℃ and the end point of 138-145 ℃ is extracted from the side line of the distillation column as the blending component A, or the component with the initial distillation point of 26-55 ℃, the end point of 135-151 ℃ or the initial distillation point of 45-50 ℃ and the end point of 138-145 ℃ is 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, 3 to 7 weight percent of a C4 alkane, 2 to 6 weight percent of a C5 alkane, 3 to 7 weight percent of a C6 alkane, 22 to 30 weight percent of a C7 alkane, 51 to 65 weight percent of a C8 alkane, and 0.75 to 2.5 weight percent of a C9 alkane;
preferably, the alkane composition has an initial boiling point of 26-55 ℃ and an end point of 135-151 ℃.
9. The alkane composition of claim 8,
the alkane composition comprises 4 to 6.5 weight percent of C4 alkane, 3 to 6 weight percent of C5 alkane, 3.5 to 7 weight percent of C6 alkane, 22.5 to 26 weight percent of C7 alkane, 55 to 62 weight percent of C8 alkane and 1 to 2.5 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 45-50 ℃, and the final boiling point is 138-145 ℃.
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 a component with an initial distillation point of 26-55 ℃, an end distillation point of 135-151 ℃ or an initial distillation point of 45-50 ℃ and an end distillation point of 138-145 ℃ 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.
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 137-146 ℃, the bottom pressure is 0.43-0.53MPa, the top temperature is 51-56 ℃, and the top pressure is 0.41-0.5 MPa;
preferably, the components with the initial distillation point of 26-55 ℃, the end point of 135-151 ℃ or the initial distillation point of 45-50 ℃ and the end point of 138-145 ℃ are extracted from the side line of the distillation column, or the components with the initial distillation point of 26-55 ℃, the end point of 135-151 ℃ or the initial distillation point of 45-50 ℃ and the end point of 138-145 ℃ are 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 aviation gasoline is unleaded aviation gasoline, preferably No. 91 unleaded aviation gasoline.
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| CN104673409A (en) * | 2013-12-03 | 2015-06-03 | 华东理工大学 | Lead-free high-quality clean aviation gasoline |
| CN106590773A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Lead-free aviation gasoline and preparation method thereof |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104673409A (en) * | 2013-12-03 | 2015-06-03 | 华东理工大学 | Lead-free high-quality clean aviation gasoline |
| CN106590773A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Lead-free aviation gasoline and preparation method thereof |
| 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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| WO2023060751A1 (en) * | 2021-10-12 | 2023-04-20 | 华东理工大学 | Ul94 unleaded aviation gasoline and production method therefor |
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