CN107085059B - Method and device for measuring gasoline octane number - Google Patents
Method and device for measuring gasoline octane number Download PDFInfo
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Abstract
The invention discloses a method for measuring the octane number of gasoline, which comprises the steps of measuring the molecular composition of a gasoline sample and calculating the octane number of the gasoline sample according to the molecular composition of the gasoline. The method of the invention can be used for rapidly, accurately and efficiently measuring the octane number of a gasoline sample, and has low cost.
Description
Technical Field
The invention belongs to the field of gasoline production and blending in the petroleum refining industry.
Background
Gasoline production is an important link in the petroleum refining industry. Countries have strict index requirements on the quality of gasoline, wherein octane number is the first quality index of gasoline specifications. The octane number is an index representing the antiknock performance of the fuel for igniting the piston engine. Octane number Research Octane Number (RON) and Motor Octane Number (MON). The gasoline reference numbers include 92#, 95#, 98# and the like, wherein the numbers represent research octane numbers of gasoline.
Currently octane number is usually measured directly using a single cylinder engine. The research octane number is the antiknock performance of fuel air inlet in the room temperature environment at the engine speed of 600rpm, and the condition of low-speed running is simulated. The motor octane number is the antiknock performance of fuel intake in a high-temperature environment at the engine speed of 900rpm, and the situation of high-speed running is simulated. Both methods are carried out in a standard single cylinder engine, have the defects of expensive equipment, large required sample amount, high environmental noise, more residues, long time consumption, complex operation and the like, and are difficult to meet the requirements of conventional production and inspection.
In recent years, some methods for analyzing and detecting octane number by using modern instruments are developed, wherein the composition or structure of gasoline is firstly measured, and then the relationship between the components and the octane number is analyzed, so that the octane number of the gasoline is calculated. Currently, such methods include gas chromatography, near infrared spectroscopy, sensor methods, nuclear magnetic resonance spectroscopy, raman spectroscopy, topological index methods, and the like. The octane number can be simply and rapidly determined by adopting the methods. However, in all the methods, the octane number is calculated by correlating the composition or structure data of the gasoline with the octane number by adopting a mathematical model, so that the method has the defect of large error, and particularly has obvious error when the gasoline component is greatly changed. The main reason for the error is that this class of methods does not calculate octane number based on the burning nature of the gasoline molecules. Since octane number is the antiknock property of gasoline during combustion, it is essentially a combustion property. During the combustion process, gasoline molecules and air undergo violent oxidation reaction to generate a large amount of free radicals and violent heat release, and the method is a complex chemical process, so that the octane number of the gasoline is difficult to accurately calculate only from the composition of the gasoline. Another cause of error in this type of process is the nonlinear blending effect of the octane numbers. The octane numbers of the different gasoline compositions, when each is present as a separate component, are different from their octane numbers in a mixture. Gasoline is a mixture composed of a large number of gasoline molecules, so that there are complex nonlinear effects in calculating the octane number of gasoline from the composition or structure of gasoline, causing calculation errors.
Disclosure of Invention
The invention provides an octane number measuring system combining a gasoline molecular combustion mechanism, which aims to solve the technical problems of expensive equipment, complex operation, large error, inaccuracy in response to gasoline component change and the like in the existing octane number measuring technology.
The invention provides an octane number determination system combined with a gasoline molecular combustion mechanism. The system consists of a gasoline composition analysis instrument and an octane number calculation module.
The gasoline composition analyzer can be used for measuring the monomer hydrocarbon molecular composition or group composition (i.e. PIONA composition) of gasoline by one or more methods of gas chromatography, near infrared spectroscopy, sensor method, nuclear magnetic resonance spectroscopy, Raman spectroscopy, topological index method and the like.
Preferably, wherein the gasoline composition analysis instrument comprises a gas chromatograph specifically configured to determine the monomeric hydrocarbon molecular composition or family composition of gasoline. The gas chromatography adopted by the invention uses two columns of the pre-cut column and the analytical column, and is additionally provided with the automatic switching ten-way valve to realize the automatic switching of the pre-cut column and the analytical column. And installing a Flame Ionization Detector (FID) after the pre-cut column and the analysis column to detect hydrocarbon molecules and oxygen-containing molecules. And installing a Sulfur Chemiluminescence Detector (SCD) behind the FID detector, combusting the sulfur-containing compound eluted from the column in an SCD combustion chamber, and then reacting with ozone to detect the content of sulfur-containing molecules. The gas chromatography detector is used for measuring the monomer hydrocarbon molecular composition or group composition (namely the PIONA composition) of hydrocarbon molecules, oxygen-containing molecules and sulfur-containing molecules of the gasoline.
The octane number calculation module comprises two parts:
(1) the type and amount of intermediate product free radicals generated by different molecules during ignition, especially peroxide free radicals where vigorous combustion is initiated, are first calculated from gasoline molecular composition or family composition, in conjunction with the combustion mechanism of gasoline molecules. The quantity and the generation speed of the peroxide free radicals directly determine the antiknock characteristic of the gasoline because the peroxide free radicals can initiate chain reaction and combustion. Determining the ignition delay period of the gasoline according to the types and concentrations of free radicals generated in the ignition process of different molecules;
(2) and calculating the gasoline octane number through model correlation according to the ignition delay period of the gasoline.
The main principle and structure of the invention is shown in fig. 1.
Based on the above thought, in one aspect, the present invention provides a method for determining gasoline octane number, comprising the steps of:
(1) determining the molecular composition of a gasoline sample;
(2) and (3) calculating the octane number of the gasoline sample according to the gasoline molecular composition determined in the step (1).
In certain embodiments, step (1) is specifically determining the monomeric hydrocarbon molecular composition and/or the group composition of the gasoline, wherein the monomeric hydrocarbon molecular composition comprises the content of each single molecule in the gasoline, and the group composition comprises the content of normal paraffins, isoparaffins, olefins, naphthenes, and aromatics in the gasoline composition.
In certain embodiments, the molecular composition of the gasoline sample may be determined in step (1) using one or more of gas chromatography, near infrared spectroscopy, sensor methods, nuclear magnetic resonance spectroscopy, raman spectroscopy, topological index methods, and the like.
In certain embodiments, the step (1) comprises determining the monomeric hydrocarbon molecular composition or family composition of gasoline using a gas chromatograph of a particular configuration; the gas chromatography configuration uses two columns of a pre-cut column and an analytical column, and an automatic switching ten-way valve is additionally arranged to realize the automatic switching of the pre-cut column and the analytical column; installing a Flame Ionization Detector (FID) after the pre-cut column and the analysis column to detect hydrocarbon molecules and oxygen-containing molecules; installing a Sulfur Chemiluminescence Detector (SCD) behind the FID detector, burning the sulfur-containing compound eluted from the column in an SCD combustion chamber, and then reacting with ozone to detect the content of sulfur-containing molecules; by the gas chromatography detector with the configuration, the monomer hydrocarbon molecular composition or the family composition (namely, the PIONA composition) of the hydrocarbon molecules, the oxygen-containing molecules and the sulfur-containing molecules of the gasoline is determined for the subsequent octane number calculation step.
In certain embodiments, the step (2) further comprises the following steps:
(i) calculating the generation quantity and speed of free radicals generated in the ignition process of gasoline molecules according to the gasoline molecule composition in the step (1) by combining the combustion mechanism of the gasoline molecules;
(ii) (ii) calculating ignition delay of the gasoline based on the amount and speed of radical generation calculated in step (i);
(iii) (iii) calculating the octane number of the gasoline based on the gasoline ignition delay calculated in step (ii);
(iv) and outputting the octane value.
In some embodiments, the amount and rate of free radical generation during ignition of gasoline molecules are calculated in step (i) based on the gasoline molecular composition or group composition in step 1, in combination with the detailed combustion mechanism of gasoline molecules. In the combustion mechanism of gasoline molecules, peroxide free radicals can initiate chain reaction and combustion, so the quantity and the generation speed of the peroxide free radicals directly determine the antiknock characteristic of gasoline. The chemical equation for a typical peroxide radical generation is shown in figure 2.
Among them, the Combustion mechanism of gasoline molecules may be known in the art, and typical Combustion mechanisms are, for example, m.mehl, h.j. Curran, w.j. Pitz and c.k. Westbrook, "Chemical kinetic modeling of components minor requirements to gasolin," European Combustion testing, Vienna, australa, 2009; or H.J. Curran, P.Gaffuri, W.J. Pitz and C.K.Westbrook, "A Comprehensive Modeling Study of iso-Octane Oxidation," benefit. flame 129 (2002) 253-280; or any other known combustion mechanism.
In certain embodiments, in step (ii) above, the ignition delay is calculated according to the following formula:
IG = m0/SUM(dmi/dt)，i=1,…,n （1）
in the formula:
IG represents ignition delay time of gasoline;
m0representing the quantity of free radicals required at the moment of ignition in the ignition process of gasoline;
SUM represents the SUM;
dmithe i-th radical generation rate is represented by/dt;
n represents the number of free radical species generated by the gasoline molecular composition.
Typical gasoline ignition delay times are shown in figure 3.
In some embodiments, in step (iii) above, the octane number calculated includes Research Octane Number (RON) and Motor Octane Number (MON), and the calculation formula is as follows:
log(RON) = A1+ B1x log(IG700) （2）
log(MON) = A2+ B2x log(IG1000) （3）
in the formula:
A1、B1、A2、B2is a model parameter;
IG700ignition delay at 700K gasoline ignition temperature;
IG1000ignition delay for gasoline at 1000K.
Accordingly, in a particularly preferred embodiment, the present invention provides a method for determining the octane number of a gasoline, comprising the steps of:
(1) measuring the monomer hydrocarbon molecular composition and/or the family composition of a gasoline sample by using one or more of a gas chromatography, a near infrared spectroscopy, a sensor method, a nuclear magnetic resonance spectroscopy, a Raman spectroscopy, a topological index method and the like, wherein the monomer hydrocarbon molecular composition comprises the content of each single molecule in the gasoline, and the family composition comprises the content of normal alkane, isoparaffin, olefin, cycloparaffin and aromatic hydrocarbon in the gasoline composition; preferably, wherein the apparatus used comprises a gas chromatograph of a specific configuration for determining the monomeric hydrocarbon molecular composition or family composition of gasoline; the gas chromatography configuration uses two columns of a pre-cut column and an analytical column, and an automatic switching ten-way valve is additionally arranged to realize the automatic switching of the pre-cut column and the analytical column; installing a Flame Ionization Detector (FID) after the pre-cut column and the analysis column to detect hydrocarbon molecules and oxygen-containing molecules; installing a Sulfur Chemiluminescence Detector (SCD) behind the FID detector, burning the sulfur-containing compound eluted from the column in an SCD combustion chamber, and then reacting with ozone to detect the content of sulfur-containing molecules; determining the monomer hydrocarbon molecular composition or group composition (namely, the PIONA composition) of hydrocarbon molecules, oxygen-containing molecules and sulfur-containing molecules of the gasoline by using the gas chromatography detector for the subsequent octane number calculation step;
(2) calculating the octane number of the gasoline sample according to the gasoline molecular composition determined in the step (1);
wherein the step (2) comprises the following steps:
(i) calculating the generation quantity and speed of free radicals generated in the ignition process of gasoline molecules according to the gasoline molecule composition in the step (1) by combining the combustion mechanism of the gasoline molecules;
(ii) (ii) calculating ignition delay of gasoline based on the radical generation amount and speed calculated in step (i), wherein the formula for calculating ignition delay is as follows:
IG = m0/SUM(dmi/dt)，i=1,…,n （1）
in the formula:
IG represents ignition delay time of gasoline;
m0representing the quantity of free radicals required at the moment of ignition in the ignition process of gasoline;
SUM represents the SUM;
dmithe i-th radical generation rate is represented by/dt;
n represents the number of free radical species generated by the gasoline molecular composition;
(iii) (iii) calculating Research Octane Number (RON) and Motor Octane Number (MON) of the gasoline according to the ignition delay of the gasoline calculated in step (ii), and calculating the following formulas:
log(RON) = A1+ B1x log(IG700) （2）
log(MON) = A2+ B2x log(IG1000) （3）
in the formula:
A1、B1、A2、B2is a model parameter;
IG700ignition delay at 700K gasoline ignition temperature;
IG1000ignition delay for gasoline ignition temperature of 1000K;
(iv) and outputting Research Octane Number (RON) and Motor Octane Number (MON).
In another aspect, the present invention also provides an apparatus for determining the octane number of gasoline, the apparatus comprising:
(1) a measuring module, and
(2) a calculation module;
wherein the measuring module comprises an instrument for measuring the composition of the gasoline molecules, and
the calculation module comprises an ignition delay time calculation module and an octane number calculation module.
In some preferred embodiments, the measuring module comprises one or more of a gas chromatography, near infrared spectroscopy, a sensor method, nuclear magnetic resonance spectroscopy, raman spectroscopy, topological index method, etc. to determine the molecular composition and/or the family composition of the gasoline sample. Preferably, the measurement module comprises a gas chromatograph with specific configuration, and the measurement module determines the molecular composition or family composition of the monomer hydrocarbon of the gasoline; the gas chromatography configuration uses two columns of a pre-cut column and an analytical column, and an automatic switching ten-way valve is additionally arranged to realize the automatic switching of the pre-cut column and the analytical column; installing a Flame Ionization Detector (FID) after the pre-cut column and the analysis column to detect hydrocarbon molecules and oxygen-containing molecules; installing a Sulfur Chemiluminescence Detector (SCD) behind the FID detector, burning the sulfur-containing compound eluted from the column in an SCD combustion chamber, and then reacting with ozone to detect the content of sulfur-containing molecules; the gas chromatography detector is used for measuring the monomer hydrocarbon molecular composition or group composition (namely the PIONA composition) of hydrocarbon molecules, oxygen-containing molecules and sulfur-containing molecules of the gasoline.
In some preferred embodiments, the calculation module is capable of calculating the octane number according to the method for determining the octane number of gasoline provided by the present invention based on the measurement result of the gasoline molecular composition measurement module.
The method uses one or more of gas chromatography, near infrared spectroscopy, a sensor method, nuclear magnetic resonance spectroscopy, Raman spectroscopy, a topological index method and the like to measure the monomer hydrocarbon composition or the group composition in the gasoline, and further combines a gasoline molecular combustion mechanism model to calculate the generation quantity and speed of free radicals and further calculate the octane number of the gasoline. Compared with the traditional octane number determination method, the method has the following advantages.
The octane number is calculated based on the gasoline molecular composition, and the robustness is obviously improved. By establishing over 300 detailed gasoline molecular libraries containing gasoline normal paraffins, isoparaffins, olefins, cycloparaffins, aromatic hydrocarbons, oxygen-containing compounds, sulfur-containing compounds and the like, the component change of any gasoline blending component and the new gasoline blending component generated under different working conditions do not exceed the scope of the molecular library. Therefore, the invention can be widely applied to the actual production situation when the gasoline blending component changes.
Based on the gasoline molecular combustion mechanism, the accuracy of the model is greatly improved. Under the condition of not making any model correction, the prediction accuracy of the octane number can reach within 1. Under the condition of correcting a small amount of actual production data, the prediction accuracy of the octane number can reach within 0.5. Under the condition of continuous actual production data correction, the octane number prediction precision can reach within 0.1.
The cost of gasoline measurement is reduced. The method can replace expensive single-cylinder engine octane number testing equipment, and accurately determine the octane number of the gasoline at lower cost and higher speed.
Is more convenient to use. Even under the condition that no measured octane number data is accumulated for correction, the method can be rapidly applied to accurately measure the octane number of the gasoline.
And the maintenance is more convenient. The invention grasps the combustion essence of gasoline molecules, can be suitable for different gasoline blending working conditions and different gasoline production requirements, and greatly reduces the maintenance requirement on the model.
Drawings
FIG. 1 is a schematic diagram of an octane number determination system according to the present invention.
Figure 2. typical gasoline molecule peroxide radical generating chemistry.
FIG. 3 ignition delay of gasoline at different ignition temperatures.
Figure 4. data of the molecular composition of a portion of the monomeric hydrocarbons of an arabian light crude straight run naphtha.
Figure 5. partial reaction network of naphtha molecular combustion mechanism.
Figure 6. free radical number and ignition delay during light naphtha ignition for saute.
FIG. 7 shows the composition data of the atmospheric and vacuum distillation unit oil PIONA of a certain oil refinery in the northwest of China.
FIG. 8 shows a partial reaction network of a common kerosene molecular combustion mechanism.
FIG. 9 shows the amount of free radicals and the ignition delay in the process of igniting the atmospheric and vacuum distillation unit of an oil refinery in northwest China.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments.
[ example 1 ]
The present invention uses gas chromatography and a detailed mechanism of gasoline combustion to determine the octane number of the saudi arabian light crude naphtha.
(1) The monomeric hydrocarbon molecular composition of sauter light crude straight run naphtha was determined using gas chromatography in a specific configuration as shown in figure 1. Part of the molecular composition data is shown in figure 4.
(2) And (3) calculating the generation quantity and speed of free radicals generated during the ignition process of the gasoline molecules according to the gasoline molecule composition in the step 1 and by combining the detailed combustion mechanism of the gasoline molecules. The mechanism used includes 385 molecules and radicals, 1895 chemical reactions. The reaction mechanism network of a portion of the naphtha molecules is shown in figure 5.
(3) The ignition delay of gasoline is calculated based on the radical generation amount and speed calculated in step 2. The ignition delay calculation function is shown in formula (1).
IG = m0/SUM(dmi/dt)，i=1,…,n （1）
In the formula:
IG represents ignition delay time of gasoline;
m0representing the quantity of free radicals required at the moment of ignition in the ignition process of gasoline;
SUM represents the SUM;
dmithe i-th radical generation rate is represented by/dt;
n represents the number of free radical species generated by the gasoline molecular composition.
The number of free radicals and ignition delay during combustion of naphtha from sauter light crude are shown in figure 6.
(4) And calculating the octane number of the gasoline through a model according to the ignition delay of the gasoline calculated in the step 3. The calculation formulas of Research Octane Number (RON) and Motor Octane Number (MON) are respectively shown in formula (2) and formula (3):
log(RON) = A1+ B1x log(IG700) （2）
log(MON) = A2+ B2x log(IG1000) （3）
in the formula:
A1、B1、A2、B2the parameter values in this embodiment are 0.32, -0.79, 0.48, -0.51, respectively, for the model parameters;
IG700the ignition delay at 700K gasoline ignition temperature was 0.0149 seconds in this example;
IG1000the ignition delay is 0.00271 seconds in this example for a gasoline ignition temperature of 1000K.
(5) Finally, the research octane number of the sauter light crude naphtha calculated in this example was 58.0, and the motor octane number was 61.5.
In this example, the research octane number and the motor octane number of sauter light crude naphtha were accurately determined by using a gas chromatography and gasoline combustion mechanism model, an ignition delay calculation model, and an octane number calculation model. Under the condition of no data correction, the errors of the measured value and the single-cylinder engine octane number test value are respectively 0.6 and 0.3, the precision required by the optimization of gasoline production is achieved, and the planned scheduling of gasoline production can be effectively guided to petrochemical enterprises. Meanwhile, the measurement cost is reduced by 5 times compared with the traditional octane number test of the single-cylinder engine.
[ example 2 ]
The invention relates to an embodiment for measuring the atmospheric and vacuum distillation device atmospheric and vacuum distillation octane number of a certain oil refining enterprise in northwest China by using a near infrared and gasoline combustion simplified mechanism model.
(1) The PIONA composition of a common overhead oil of a certain oil refinery in northwest china was determined using a gas chromatograph with a specific configuration as shown in fig. 1. Part of the PIONA composition data is shown in fig. 7.
(2) And (3) calculating the generation quantity and speed of free radicals generated in the ignition process of the gasoline according to the composition data of the normal top oil PIONA in the step 1 and by combining the simplified combustion mechanism of the gasoline. The mechanism used includes 56 molecular components and radicals, 279 chemical reactions. The reaction mechanism network of some common ceiling molecules is shown in FIG. 8.
(3) The ignition delay of gasoline is calculated based on the radical generation amount and speed calculated in step 2. The ignition delay calculation function is shown in formula (1).
IG = m0/SUM(dmi/dt)，i=1,…,n （1）
In the formula:
IG represents ignition delay time of gasoline;
m0representing the quantity of free radicals required at the moment of ignition in the ignition process of gasoline;
SUM represents the SUM;
dmithe i-th radical generation rate is represented by/dt;
n represents the number of free radical species generated by the gasoline molecular composition.
The amount of free radicals and the ignition delay during combustion of the common top oil of this example are shown in FIG. 9.
(4) And calculating the octane number of the gasoline through a model according to the ignition delay of the gasoline calculated in the step 3. The calculation formulas of Research Octane Number (RON) and Motor Octane Number (MON) are respectively shown in formula (2) and formula (3):
log(RON) = A1+ B1x log(IG700) （3）
log(MON) = A2+ B2x log(IG1000) （4）
in the formula:
A1、B1、A2、B2the parameter values are 0.46, -0.74, 0.61, -0.46 in the embodiment respectively;
IG700the ignition delay at 700K for gasoline ignition is 0.0153 seconds in this example;
IG1000for gasoline the ignition temperature is 1000KThe ignition delay was 0.00273 seconds in this example.
(5) Finally, the research octane number of the sauter light crude naphtha calculated in this example was 63.6, and the motor octane number was 61.6.
In the embodiment, the PIONA composition of the atmospheric top oil is measured by using near infrared rays, and is combined with a gasoline combustion mechanism model, an ignition delay calculation model and an octane number calculation model, so that the research octane number and the motor octane number of the atmospheric top oil are accurately measured. Under the condition of no data correction, the errors of the measured value and the single-cylinder engine octane number test value are respectively 0.7 and 0.2, the precision required by the optimization of gasoline production is achieved, and the planned scheduling of gasoline production can be effectively guided to petrochemical enterprises. Meanwhile, the octane number of the engine is reduced by more than 10 times in the determination speed compared with the octane number of the traditional single-cylinder engine, and the determination work can be completed within 15 minutes. The accuracy is higher than the calculation precision of the octane number directly related to the peak area of the traditional near infrared spectrum, and the error is reduced to the range of 0.1-0.5 from the traditional range of 1-2. The measurement cost is reduced by more than 6 times compared with the traditional octane number test of the single-cylinder engine.
Claims (8)
1. A method for determining the octane number of gasoline, comprising the steps of:
(1) determining the molecular composition of a gasoline sample;
(2) calculating the octane number of the gasoline sample according to the gasoline molecular composition determined in the step (1);
wherein the step (2) specifically comprises the following steps:
(i) calculating the generation quantity and speed of free radicals generated in the ignition process of gasoline molecules according to the gasoline molecule composition in the step (1) by combining the combustion mechanism of the gasoline molecules;
(ii) (ii) calculating ignition delay of gasoline based on the radical generation amount and speed calculated in step (i) by the following formula:
IG＝m0/SUM(dmi/dt)，i＝1,…,n (1)
in the formula:
IG represents ignition delay time of gasoline;
m0representing the quantity of free radicals required at the moment of ignition in the ignition process of gasoline;
SUM represents the SUM;
dmithe i-th radical generation rate is represented by/dt;
n represents the number of free radical species generated by the gasoline molecular composition;
(iii) (iii) calculating the octane number of the gasoline based on the ignition delay of the gasoline calculated in step (ii), the calculated octane number including Research Octane Number (RON) and/or Motor Octane Number (MON), and the calculation formulas are as follows:
log(RON)＝A1+B1xlog(IG700) (2)
log(MON)＝A2+B2xlog(IG1000) (3)
in the formula:
A1、B1、A2、B2is a model parameter;
IG700ignition delay at 700K gasoline ignition temperature;
IG1000ignition delay at gasoline ignition temperature of 1000K;
(iv) and outputting the octane value.
2. The method for determining the octane number of gasoline as claimed in claim 1, wherein the step (1) is to determine the molecular composition and/or the group composition of the monomer hydrocarbon of the gasoline, wherein the molecular composition of the monomer hydrocarbon comprises the content of each single molecule in the gasoline, and the group composition comprises the content of normal paraffin, isoparaffin, olefin, naphthene and aromatic hydrocarbon in the gasoline.
3. The method of determining the octane number of gasoline of claim 1 or 2 wherein in step (1) the molecular composition of the gasoline sample is determined using one or more of a gas chromatography instrument, a near infrared spectroscopy instrument, a sensor instrument, a nuclear magnetic resonance spectroscopy instrument, a raman spectroscopy instrument, and a topological index instrument.
4. The method for determining the octane number of gasoline according to claim 1 or 2, wherein the monomer hydrocarbon molecular composition or group composition of gasoline is determined in the step (1) using a gas chromatograph of a specific configuration; the gas chromatography configuration uses two columns of a pre-cut column and an analytical column, and an automatic switching ten-way valve is additionally arranged to realize the automatic switching of the pre-cut column and the analytical column; installing a Flame Ionization Detector (FID) after the pre-cut column and the analysis column to detect hydrocarbon molecules and oxygen-containing molecules; installing a Sulfur Chemiluminescence Detector (SCD) behind the FID detector, burning the sulfur-containing compound eluted from the column in an SCD combustion chamber, and then reacting with ozone to detect the content of sulfur-containing molecules; the gas chromatography detector is used for measuring the monomer molecular composition or the family composition of hydrocarbon molecules, oxygen-containing molecules and sulfur-containing molecules of the gasoline for the subsequent octane number calculation step.
5. A method for determining the octane number of gasoline, comprising the steps of:
(1) measuring the monomer hydrocarbon molecular composition and/or the family composition of a gasoline sample by using one or more of a gas chromatography instrument, a near infrared spectroscopy instrument, a sensing instrument, a nuclear magnetic resonance spectroscopy instrument, a Raman spectroscopy instrument and a topological index instrument, wherein the monomer hydrocarbon molecular composition comprises the content of each single molecule in gasoline, and the family composition comprises the content of normal alkane, isoparaffin, olefin, naphthene and aromatic hydrocarbon in the gasoline composition; the gas chromatographic instrument is configured with two columns, namely a pre-cut column and an analytical column, and is additionally provided with an automatic switching ten-way valve to realize automatic switching of the pre-cut column and the analytical column, a Flame Ionization Detector (FID) is installed behind the pre-cut column and the analytical column to detect hydrocarbon molecules and oxygen-containing molecules, a Sulfur Chemiluminescence Detector (SCD) is installed behind the FID detector, sulfur-containing compounds eluted from the columns are combusted in an SCD combustion chamber and then react with ozone to detect the content of the sulfur-containing molecules, and the monomer molecular composition or the family composition of the hydrocarbon molecules, the oxygen-containing molecules and the sulfur-containing molecules of gasoline is determined by the gas chromatographic detector so as to be used for the subsequent octane number calculation step;
(2) calculating the octane number of the gasoline sample according to the gasoline molecular composition determined in the step (1);
wherein the step (2) comprises the following steps:
(i) calculating the generation quantity and speed of free radicals generated in the ignition process of gasoline molecules according to the gasoline molecule composition in the step (1) by combining the combustion mechanism of the gasoline molecules;
(ii) (ii) calculating ignition delay of gasoline based on the radical generation amount and speed calculated in step (i), wherein the formula for calculating ignition delay is as follows:
IG＝m0/SUM(dmi/dt)，i＝1,…,n (1)
in the formula:
IG represents ignition delay time of gasoline;
m0representing the quantity of free radicals required at the moment of ignition in the ignition process of gasoline;
SUM represents the SUM;
dmithe i-th radical generation rate is represented by/dt;
n represents the number of free radical species generated by the gasoline molecular composition;
(iii) (iii) calculating Research Octane Number (RON) and Motor Octane Number (MON) of the gasoline according to the ignition delay of the gasoline calculated in step (ii), and calculating the following formulas:
log(RON)＝A1+B1xlog(IG700) (2)
log(MON)＝A2+B2xlog(IG1000)(3)
in the formula: a. the1、B1、A2、B2Is a model parameter;
IG700ignition delay at 700K gasoline ignition temperature;
IG1000ignition delay at gasoline ignition temperature of 1000K;
(iv) and outputting Research Octane Number (RON) and Motor Octane Number (MON).
6. Device for determining the octane number of a gasoline, characterized in that it comprises the following parts:
(1) a measuring module, and
(2) a calculation module;
wherein the measuring module comprises an instrument for measuring the composition of the gasoline molecules, and
the calculation module comprises an ignition delay time calculation module and an octane number calculation module.
7. The apparatus of claim 6, wherein the measurement module comprises one or more of a gas chromatography instrument, a near infrared spectroscopy instrument, a sensing instrument, a nuclear magnetic resonance spectroscopy instrument, a raman spectroscopy instrument, and a topological index instrument for determining the molecular composition and/or the family composition of the gasoline sample; the gas chromatographic instrument is configured with two columns, namely a pre-cut column and an analytical column, and is additionally provided with an automatic switching ten-way valve to realize automatic switching of the pre-cut column and the analytical column, a Flame Ionization Detector (FID) is installed behind the pre-cut column and the analytical column to detect hydrocarbon molecules and oxygen-containing molecules, a Sulfur Chemiluminescence Detector (SCD) is installed behind the FID detector, sulfur-containing compounds eluted from the columns are combusted in an SCD combustion chamber and then react with ozone to detect the content of the sulfur-containing molecules, and the monomer molecular composition or the family composition of the hydrocarbon molecules, the oxygen-containing molecules and the sulfur-containing molecules of gasoline is determined by the gas chromatographic detector.
8. The device according to claim 6 or 7, wherein the calculation module is capable of calculating the octane number from the measurement of the gasoline molecular composition measurement module according to the method defined in any one of claims 1 to 5.
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| CN115050427A (en) * | 2021-03-09 | 2022-09-13 | 中国石油化工股份有限公司 | Method, device, medium and electronic equipment for predicting gasoline octane number |
| CN114724644B (en) * | 2022-03-25 | 2023-04-07 | 中国石油大学(北京) | Method and equipment for predicting gasoline octane number based on intermolecular interaction |
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