CN110070921B - Method for predicting gasoline octane number - Google Patents
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Abstract
The embodiment of the invention provides a method for predicting the octane number of gasoline, belonging to the field of petrochemical industry. The method comprises the following steps: calculating the active nuclear conversion rate according to each component in the gasoline and an active nuclear conversion rate calculation model; and calculating the octane number of the gasoline according to the active nuclear conversion rate and an octane number calculation model. The scheme provides an assumption that the octane number is determined by the conversion rate of active nuclei in a system by researching a combustion chemical model of hydrocarbons in a cylinder and decomposing a combustion process, and calculates the octane number on the basis of the assumption, so that the contribution or loss of a nonlinear blending effect possibly caused to the gasoline octane number in the blending process of various blending components in gasoline can be considered, and the gasoline octane number can be predicted more accurately.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a method for predicting the octane number of gasoline.
Background
The gasoline is blended by a plurality of components, and the inventor of the application finds that the octane number in the blending process shows a more obvious non-linear law no matter the blending component refers to a pure hydrocarbon compound or a certain component oil in the process of realizing the invention. It can be said that the octane number of gasoline is not only related to the octane number of each blending component in gasoline, but also related to the blending characteristics of each component in the blending process. In recent years, during the upgrading of oil products, the adding proportion of high-octane components is more emphasized, and the contribution or loss of the gasoline octane number caused by nonlinear blending effect in the blending process is relatively ignored. The octane number prediction model based on the detailed composition aims to solve the problem, recognizes the octane number of the gasoline on a molecular level and achieves the aim of high-accuracy prediction of the octane number. The core of the model establishment is the establishment of a gasoline composition-octane number mathematical expression relation.
At present, some research institutions at home and abroad give a guess of a mathematical relationship between a small amount of octane number and gasoline, however, the models are mostly deduced by the hypothesis made by experimental rules, the deep understanding and the theoretical research on the octane number blending process are limited by the foundation of an experimental method, and the obtained models also have the defects in the aspects of prediction precision and application range.
Disclosure of Invention
It is an object of embodiments of the present invention to provide a method for predicting gasoline octane number that can improve the accuracy of the prediction of gasoline octane number.
In order to achieve the above object, an embodiment of the present invention provides a method for predicting an octane number of gasoline, the method including: calculating the active nuclear conversion rate according to each component in the gasoline and an active nuclear conversion rate calculation model; and calculating the octane number of the gasoline according to the active nuclear conversion rate and an octane number calculation model.
Optionally, before calculating the gasoline octane number according to the active nuclear conversion rate and an octane number calculation model, the method further comprises: and correcting the active nuclear conversion rate according to the interaction relation of each component in the gasoline and an active conversion rate correction model.
In another aspect, the present disclosure provides a machine-readable storage medium having instructions stored thereon for causing a machine to perform the method for predicting a gasoline octane number described herein.
The octane number is an indicator of the knock resistance of the reaction gasoline, referenced to the amounts of n-heptane and isooctane. The inventor of the present invention recognizes that: 1) octane number is a relative concept; 2) octane number is not only related to gasoline composition but also to the reaction chemistry during combustion, which is responsible for octane nonlinearity during blending. The invention provides a method for establishing a mathematical relational expression of gasoline composition and octane number, which comprises the following steps: by researching a combustion chemical model of hydrocarbons in a cylinder and decomposing a combustion process, an assumption that the octane number is determined by the conversion rate of active nuclei in the system is provided, and the octane number is calculated on the basis of the assumption, so that the contribution or loss of the nonlinear blending effect possibly caused to the gasoline octane number in the blending process of each blending component in the gasoline can be considered, and the gasoline octane number can be accurately predicted.
Additional features and advantages of embodiments of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the embodiments of the invention without limiting the embodiments of the invention. In the drawings:
FIG. 1 is a flow chart of a method for predicting gasoline octane number provided by an embodiment of the present invention;
FIG. 2 is a flow chart of a method for predicting gasoline octane number according to another embodiment of the present invention;
fig. 3 is a graph illustrating the effect of octane number prediction according to the method for predicting the octane number of gasoline according to the first embodiment of the present invention;
fig. 4 is a graph illustrating the effect of octane number prediction according to the method for predicting the octane number of gasoline provided in the second embodiment of the present invention;
fig. 5 is a graph illustrating the effect of octane number prediction according to the method for predicting the octane number of gasoline provided in the third embodiment of the present invention;
fig. 6A and 6B are graphs illustrating the effect of octane number prediction according to a method for predicting the octane number of gasoline provided by a fourth embodiment of the present invention;
fig. 7A and 7B are graphs illustrating the effect of octane number prediction according to the method for predicting the octane number of gasoline provided by the fifth embodiment of the present invention;
fig. 8 is a graph illustrating the effect of octane number prediction according to the method for predicting the octane number of gasoline according to the sixth embodiment of the present invention; and
fig. 9 is a graph illustrating the effect of octane number prediction according to the method for predicting the octane number of gasoline according to the seventh embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating embodiments of the invention, are given by way of illustration and explanation only, not limitation.
Fig. 1 is a flowchart of a method for predicting gasoline octane number according to an embodiment of the present invention. As shown in fig. 1, an embodiment of the present invention provides a method for predicting gasoline octane number, the method comprising: calculating the active nuclear conversion rate according to each component in the gasoline and an active nuclear conversion rate calculation model; and calculating the octane number of the gasoline according to the active nuclear conversion rate and an octane number calculation model.
The scheme provides an assumption that the octane number is determined by the conversion rate of active nuclei in a system by researching a combustion chemical model of hydrocarbons in a cylinder and decomposing a combustion process, and calculates the octane number on the basis of the assumption, so that the contribution or loss of a nonlinear blending effect possibly caused to the gasoline octane number in the blending process of various blending components in gasoline can be considered, and the gasoline octane number can be predicted more accurately. The scheme simplifies the low-temperature flame front combustion reaction process of the gasoline by means of a combustion mechanism, introduces the hypothesis that the active nuclear conversion rate influences the octane number, establishes an octane number model into three steps of calculation of the active nuclear conversion rate, correction of the active nuclear conversion rate and the incidence relation between the octane number and the active nuclear conversion rate, performs modeling in each step, and finally combines the octane number model into an octane number mechanism model mathematical form based on the detailed hydrocarbon composition.
Besides considering the influence of each component on the conversion rate of active nuclei in the system independently, the components can interact with each other in the combustion process, and a new active nucleus or inert nucleus generation path is added, so that the conversion rate of the active nuclei in the system is influenced. Fig. 2 is a flow chart of a method for predicting gasoline octane number according to another embodiment of the present invention. Preferably, as shown in fig. 2, before calculating the gasoline octane number according to the active nuclear conversion and octane number calculation model, the method further comprises: and correcting the active nuclear conversion rate according to the interaction relation of each component in the gasoline and an active conversion rate correction model.
The following describes three models involved in the above technical solutions respectively:
model 1: active nucleus conversion rate calculation model
Specifically, the calculation model of active nuclear conversion rate may be selected from one of the following to calculate the active nuclear conversion rate Q generated per mole component in the systemac：
Model 1A:
wherein Q isacIs the active nuclear conversion per molar fraction, [ n ]i]Denotes the content of active nuclei formed by the i component, niIs the i component mole fraction, upsiloniIs the volume fraction of the i component, KiIs the conversion rate of pure component i to active nuclei, beta, at the end of the low-temperature pre-flame reactioniIs the blending factor of the i component,
where ρ isiIs the relative density of the i component, MiIs the relative molecular weight of the i component. Beta is aiThe values of (a) are finally regressed by experimental data, but are simply deduced to be related to the ratio of the density and the molecular weight of the i component, as defined by the octane number, and the beta values of isooctane and n-heptaneiWith a value of 1, a reference function can be established therefrom, obtaining beta for each componentiAnd (5) initial value.
Model 1B:
wherein n isiIs the molar fraction of radicals generated by the i component in the low-temperature pre-flame reaction stage, niIs the molar fraction of the i component, θiIs the reaction rate of the i component to form free radicals, q, in the low-temperature pre-flame reaction stageiIs the reaction rate of the i component free radicals to further generate active nuclei. The basis for the model is to assume that the ratio of active core to free radical (i.e., the ability of the free radical to become an active core) determines the octane number.
Model 1C:
the meaning of each parameter in the model 1C is the same as that of each parameter in the model 1B, and the model is formed by adding a guess of competitive oxidation of components on the basis of the model 1B and referring to an adsorption mechanism.
Model 2: activity conversion rate correction model
Besides considering the influence of each component on the conversion rate of active nuclei in the system independently, the components can interact with each other in the combustion process, and a new active nucleus or inert nucleus generation path is added, so that the conversion rate of the active nuclei in the system is influenced. A steady state equation can be established by different assumptions on the mechanism, and the functional relation between the newly added active nucleus and the composition is obtained. Two model forms of 2A and 2B are given, the number of newly added active nucleus can be calculated, and the newly added active nucleus can be added into the active nucleus conversion rate calculation model to calculate the active nucleus conversion rate QacAnd finishing the correction.
The activity conversion correction model may be selected from one of the following to correct for active nuclear conversion QacAnd (5) correcting:
model 2A:
model 2A is derived from the steady state equation established for reaction mechanism AFrom a steady state equation of 2A', where k isi、
Respectively, the reaction rate of the reaction mechanism A, ni、njAre the mole fractions of the i component and the j component respectively,
is the newly added active nucleus conversion rate of the i component.
Reaction mechanism A
When the model is used for inspecting the combustion reaction of a certain component, other components are assumed to be used as catalytic factors of the reaction and influence the reaction process of the component. Wherein A, B, C represents a blending component, [ A ]]Represents the active core produced by this pathway for component A,
represents the hydroxyl radical generated by the active nucleus through a series of branched chain reactions. In the process, once the active nucleus is generated, a branch chain reaction can be rapidly carried out to generate a large amount of hydroxyl radicals, the hydroxyl radicals are rapidly subjected to exothermic combustion to generate detonation, and how each blending component generates the active nucleus is the speed-determining step of the low-temperature flame front reaction, so that the conversion rate of the active nucleus is an important index influencing the detonation.
Model 2B:
model 2B was derived from the steady state equation established for reaction mechanism B, shown below as 2B', tijIs the interaction parameter of the i-component and the j-component, ni、njAre the mole fractions of the i component and the j component respectively,
is the newly added active nucleus conversion rate of the system.
Reaction mechanism B
The model considers that when a certain component is considered to react during combustion, the two components in the system interact with each other to promote the generation of active nuclei or inert nuclei in the system and influence the proportion of the total active nuclei. Wherein A, B, C represents a blending component, [ M ]]Represents the newly generated active nucleus of the pathway,
represents the hydroxyl radical generated by the active nucleus through a series of branched chain reactions.
Model 3: octane number calculation model
According to the knock principle analysis, the active nuclear conversion rate is considered to be positively correlated with the knock intensity. Whereas, according to the octane number standard, knock intensity and therefore active nuclear conversion are negatively correlated with octane number. Therefore, various model guesses of the relation between the active nuclear conversion rate and the octane number can be provided. The invention provides four octane number calculation models, wherein the octane number calculation models are selected from one of the following four types:
model 3A (linear function): RON ═ aQac+b
Model 3B (reciprocal function): RON ═ a/Qac+b
Model 3C (quadratic function): RON ═ a (Q)ac+b)2+c
Model 3D (exponential function): RON ═ exp (aQ)ac+b)
Wherein RON is the octane number, QacIs the active nucleus conversion, and a, b, c are correction parameters. These parameters should be adjusted in modeling to ensure the rule that the octane number is negatively correlated with the active nuclear conversion rate.
The three models described above are summarized in the following table:
finally, the mathematical relation of the octane number prediction model can be a combination of the three models in the following way:
octane number ═ model 3 (model 1+ model 2)
When combined, both models 1, 2 are optional parts and may not be considered at all. When only the model 3 is considered and the linear model 3A is adopted, the octane number model finally obtained is the simplest linear model. When such a predictive model is used for a single component, the octane number to the left of the formula is the octane number of that pure component, and ON is usediInstead, v on the rightiThe value of (1) can eliminate most unknown parameters in the model, thereby achieving the purpose of simplifying the model. In addition, when the active nucleus conversion rate in model 1 is modified using model 2, the newly added active nucleus may be added to the molecule of model 1, or:
converting the amount of the newly added active core into the newly added i component mole fraction, wherein:
ni＝(1+Ii)nior ni＝(1+Imix/ni)ni
After the above treatment, the modified i-fraction was substituted into model 1 to calculate the active nuclear conversion.
The invention can respectively model the three models and guess a plurality of models, and form a final octane number prediction model by using the three models, and can simplify the relevant parameters of the models according to the pure hydrocarbon octane number data and determine the theoretical explanation and initial value of each parameter in the models. Finally, parameters in the octane number prediction model can be corrected by utilizing the finished oil data, and finally, a complete octane number prediction model based on detailed composition is obtained.
Three examples of establishing octane number prediction model mathematical expressions by the present invention are given below.
Example one
For the three parts of the combination, a model 1A, a model 2A and a model 3A are respectively selected, the pure hydrocarbon octane number is substituted, the intermediate parameters are simplified, and an octane number prediction model expression 1A-2A-3A based on the detailed composition of gasoline is obtained:
wherein the content of the first and second substances,
p represents the component considered to participate in the modification of the active nuclear conversion rate of model 2,
where ρ isiIs the relative density of the i component, MiIs the relative molecular weight of the i component. ONiIs a known parameter, upsilon, for the octane number of the pure componentsiIs the volume fraction of the i component, betaiAnd a is a parameter of the model needing regression, wherein, betaiThe initial value of (b) can be determined from the density and molecular weight of the i component.
The model expression obtained by the combination is similar to the formula obtained by Exxon company through experiments, but each parameter of the formula obtained by the method has practical significance, and the key parameter beta is giveniThe initial value obtaining method comprises the following steps: according to the octane number test method, the beta of n-heptane and isooctaneiIs 1 and the density and molecular weight are also known, in terms of betaiMeaning of parameters, interpolation to obtain other components betaiAnd (5) initial value.
The mathematical expression has better prediction precision on the octane number by using 194 finished oil samples and 67 component oil sample data obtained by us for verification. As shown in fig. 3, the abscissa is the octane number actually measured for the sample, the ordinate is the octane number calculated by the model, "+" is the training set of model parameters, and "+" is the test set of model parameters, and the result shows a standard deviation of 0.513.
Example two
For the three parts of the combination, a model 1A, a model 2B and a model 3A are respectively selected, the pure hydrocarbon octane number is substituted, the intermediate parameters are simplified, and an octane number prediction model expression 1A-2B-3A based on the detailed composition of gasoline is obtained:
wherein, Imix＝∑ijtijninj，
tijModel regression was performed to account for the interaction parameters of the i and j components involved in the modification of the active nuclear conversion of model 2.
The parameter β is likewise obtained by the method of example oneiInitial value, using dataAnd (5) regressing parameters, and verifying the prediction effect of the expression. As shown in fig. 4, the abscissa is the octane number actually measured by the sample, the ordinate is the octane number calculated by the model, "+" is the training set of model parameters, and "+" is the testing set of model parameters, and the result shows a standard deviation of 0.488.
EXAMPLE III
For the three parts of the combination, a model 1A, a model 2A and a model 3B are respectively selected, the pure hydrocarbon octane number is substituted, the intermediate parameters are simplified, and an octane number prediction model expression 1A-2A-3B based on the detailed composition of gasoline is obtained:
the parameters in the formula are the same as those in the first embodiment.
The parameter β is likewise obtained by the method of example oneiAnd (3) an initial value, using the data regression parameters, and verifying the prediction effect of the expression, as shown in fig. 5, wherein the abscissa is the octane number actually measured by the sample, the ordinate is the octane number calculated by the model, "+" is the model parameter training set, "+" is the model parameter testing set, and the result shows that the standard deviation is 0.532.
Example four
Models 1A and 3A may be chosen, respectively, and when for pure hydrocarbons, model 1A may be expressed as:
Qac＝Ki (1)
the left available i-component pure hydrocarbon octane number ON of model 3AiInstead, it becomes:
ONi＝aQac+b (2)
by substituting formula (1) into formula (2), the octane number ON of pure hydrocarbon can be establishediAnd KiThe relationship of (1):
substituting the models 1A and (3) into the model 3A again can eliminate most unknown parameters in the model, so as to achieve the purpose of simplifying the model, and the final octane number model is as follows:
wherein is ONiV is the octane number of the respective pure component as a known parameteriIs the volume fraction of the i component, betaiThe blending factor, which is a component i, is a parameter for which the model requires regression. Training the model through a small amount of composition and octane number fact data to obtain betaiParameters, the octane number can be predicted from the gasoline composition.
For the combination of models 1A and 3A, the following two examples can be performed to verify the validity thereof.
Example 1), the model was validated using 194 finished oil samples and 67 component oil sample data, 20 of which were used as the training set and the remaining data were used as the validation set. After the model parameters are regressed by using the data, the model has better prediction precision on the octane number of the sample. As shown in fig. 6A, the abscissa is the octane number actually measured by the sample, the ordinate is the octane number calculated by the model, "+" is the training set of model parameters, and "+" is the testing set of model parameters, and the result shows that the standard deviation is 0.663.
Example 2), the model is used for predicting 6 groups of reforming component oil and 7 groups of catalytic cracking component oil, the model parameters adopt the parameters obtained by regression in the above example 1), and the model has better prediction accuracy on the octane number of a sample. As shown in fig. 6B, the abscissa is the octane number actually measured by the sample, the ordinate is the octane number calculated by the model, "+" is the training set of model parameters, and "+" is the test set of model parameters, and the result shows that the standard deviation thereof is 0.371.
EXAMPLE five
The models 1C and 3A can be selected respectively, the models are combined and subjected to mathematical calculation, intermediate parameters are simplified, and the final octane number prediction expression model is obtained as follows:
wherein n isiIs the molar fraction of radicals, n, produced by the i component in the low-temperature pre-flame reaction stageiIs the molar fraction of the i component, θiIs the reaction rate, ON, of the formation of free radicals of the component i in the low-temperature pre-flame reaction stageiThe octane number of each pure component is a known parameter.
For the combination of models 1C and 3A, the following two examples can be performed to verify the validity thereof.
Example 1), the model was validated using 194 finished oil samples and 67 component oil sample data, 40 of which were used as training set and the remaining data were used as validation set. After the model parameters are regressed by using the data, the model has better prediction precision on the octane number of the sample. As shown in fig. 7A, the abscissa is the octane number actually measured by the sample, the ordinate is the octane number calculated by the model, "+" is the training set of model parameters, and "+" is the testing set of model parameters, and the result shows that the standard deviation is 0.649.
Example 2), the model is used for predicting 70 catalytic cracking component oils of a certain refinery, the model parameters adopt the parameters obtained by regression in the above example 1), and the model has better prediction accuracy on the octane number of a sample. As shown in fig. 7B, the abscissa is the octane number actually measured by the sample, the ordinate is the octane number calculated by the model, "+" is the training set of model parameters, and "+" is the test set of model parameters, and the result shows that the standard deviation is 0.412.
EXAMPLE six
The models 1B and 3A can be selected respectively, combined and subjected to mathematical calculation, intermediate parameters are simplified, and the final octane number prediction expression model is obtained as follows:
wherein is ONiAs the octane number of the respective pure component, n is a known parameteriIs the molar fraction of the i component, θiIs the reaction rate of the component i in the low-temperature flame front reaction stage to generate free radicals, and is a parameter required to be regressed by the model. Training the model through a small amount of composition and octane number fact data to obtain thetaiParameters, the octane number can be predicted from the gasoline composition.
And 194 finished oil samples and 67 component oil sample data are used for verifying that the mathematical expression has better prediction accuracy on the octane number. As shown in fig. 8, the abscissa is the octane number actually measured by the sample, the ordinate is the octane number calculated by the model, "+" is the training set of model parameters, and "+" is the test set of model parameters, and the result shows a standard deviation of 0.663.
EXAMPLE seven
The models 1A and 3B can be respectively selected, combined and mathematically calculated, so that intermediate parameters are simplified, and the final octane number prediction expression model is obtained as follows:
wherein is ONiV is the octane number of the respective pure component as a known parameteriIs the volume fraction of the i component, betaiRegression parameters are required for the model. Training the model through a small amount of composition and octane number fact data to obtain a parameter betaiThe octane number can be predicted from the gasoline composition.
And 194 finished oil samples and 67 component oil sample data are used for verifying that the mathematical expression has better prediction accuracy on the octane number. As shown in fig. 9, the abscissa is the octane number actually measured for the sample, the ordinate is the octane number calculated by the model, "+" is the training set of model parameters, and "+" is the test set of model parameters, and the result shows a standard deviation of 0.681.
Accordingly, embodiments of the present invention also provide a machine-readable storage medium having stored thereon instructions for causing a machine to execute the method for predicting gasoline octane number described above.
Although the embodiments of the present invention have been described in detail with reference to the accompanying drawings, the embodiments of the present invention are not limited to the details of the above embodiments, and various simple modifications can be made to the technical solutions of the embodiments of the present invention within the technical idea of the embodiments of the present invention, and the simple modifications all belong to the protection scope of the embodiments of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, the embodiments of the present invention do not describe every possible combination.
Those skilled in the art will understand that all or part of the steps in the method according to the above embodiments may be implemented by a program, which is stored in a storage medium and includes several instructions to enable a single chip, a chip, or a processor (processor) to execute all or part of the steps in the method according to the embodiments of the present application. And the aforementioned storage medium includes: a U-disk, a removable hard disk, a Read-Only Memory (ROM), a Random Access Memory (RAM), a magnetic disk or an optical disk, and other various media capable of storing program codes.
In addition, any combination of various different implementation manners of the embodiments of the present invention is also possible, and the embodiments of the present invention should be considered as disclosed in the embodiments of the present invention as long as the combination does not depart from the spirit of the embodiments of the present invention.
Claims (3)
1. A method for predicting the octane number of a gasoline, the method comprising:
calculating the active nuclear conversion rate according to each component in the gasoline and an active nuclear conversion rate calculation model; and
calculating the octane number of the gasoline according to the active nuclear conversion rate and an octane number calculation model,
wherein the calculation model of the active nuclear conversion rate is as follows:
model 1B:
wherein [ n ]i]Denotes the content of active nuclei formed by the i component, niIs the molar fraction of radicals generated by the i component in the low-temperature pre-flame reaction stage, niIs the molar fraction of the i component, θiIs the reaction rate of the i component to form free radicals, q, in the low-temperature pre-flame reaction stageiIs the reaction rate of the i component free radical to further generate active nucleus;
the octane number calculation model is selected from the following components:
model 3A: RON ═ aQac+b
Wherein RON is the octane number, QacIs the active nucleus conversion, and a, b are correction parameters.
2. The method of claim 1, wherein model 1B and model 3A constitute the following octane number prediction expression models:
wherein is ONiAs a known parameter, n is the octane number of the respective pure componentiIs the molar fraction of the i component, θiIs the reaction rate of the component i in the low-temperature flame front reaction stage to generate free radicals, and is a parameter required to be regressed by the model.
3. A machine-readable storage medium having stored thereon instructions for causing a machine to perform the method of any one of claims 1-2.
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