CN107085059A - A kind of method and device for determining octane number - Google Patents
A kind of method and device for determining octane number Download PDFInfo
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- CN107085059A CN107085059A CN201710336831.XA CN201710336831A CN107085059A CN 107085059 A CN107085059 A CN 107085059A CN 201710336831 A CN201710336831 A CN 201710336831A CN 107085059 A CN107085059 A CN 107085059A
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 89
- 150000003254 radicals Chemical class 0.000 claims description 42
- 239000004215 Carbon black (E152) Substances 0.000 claims description 41
- 229930195733 hydrocarbon Natural products 0.000 claims description 41
- 150000002430 hydrocarbons Chemical class 0.000 claims description 41
- 238000002485 combustion reaction Methods 0.000 claims description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 29
- 229910052717 sulfur Inorganic materials 0.000 claims description 29
- 239000011593 sulfur Substances 0.000 claims description 29
- 230000007246 mechanism Effects 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 17
- 238000004817 gas chromatography Methods 0.000 claims description 17
- 238000005259 measurement Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 241001372564 Piona Species 0.000 claims description 13
- 238000011160 research Methods 0.000 claims description 13
- 238000004364 calculation method Methods 0.000 claims description 12
- 238000005481 NMR spectroscopy Methods 0.000 claims description 9
- 238000001069 Raman spectroscopy Methods 0.000 claims description 9
- 238000004497 NIR spectroscopy Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 7
- 230000027734 detection of oxygen Effects 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 150000001924 cycloalkanes Chemical class 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 238000002329 infrared spectrum Methods 0.000 claims description 2
- 238000004611 spectroscopical analysis Methods 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 6
- 238000012937 correction Methods 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 241001269238 Data Species 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 206010061218 Inflammation Diseases 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- -1 isoparaffin Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 208000031639 Chromosome Deletion Diseases 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Combined Controls Of Internal Combustion Engines (AREA)
- Electrical Control Of Air Or Fuel Supplied To Internal-Combustion Engine (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention discloses a kind of method for determining octane number, the step of constituting the octane number for calculating the gasoline sample comprising the molecular composition for determining gasoline sample and according to petrol molecule.Using the method for the present invention, the octane number of gasoline sample can quickly, be accurately and efficiently determined, and cost is very low.
Description
Technical field
The invention belongs to oil refining industry gasoline production and blending field.
Background technology
Gasoline production is an important step of oil refining industry.Country has strict index will to quality of gasoline
Ask, wherein octane number is the first term quality index of specification gasoline.Octane number is the antiknock for representing to light piston-mode motor fuel
The index of performance.Octane number point research octane number (RON)（RON）And motor octane number（MON）Two kinds of measuring methods.The mark of gasoline
Number, including 92#, 95#, 98# etc., numeral therein represents the research octane number (RON) of gasoline.
Current octane number is generally directly determined using single-cylinder engine.Wherein research octane number (RON) is in engine speed
600rpm, the capability of antidetonance of the fuel air under room temperature environment simulates the situation run at a low speed.Motor octane number is to start
Machine rotating speed 900rpm, the capability of antidetonance of fuel air in high temperature environments simulates the situation run at high speed.Both of which be
Carried out in standard single-cylinder engine, all have that equipment is expensive, required sample size is big, environmental noise is high, residue is more, time-consuming and
The shortcomings of complex operation, it is difficult to meet the conventional requirement for producing and examining.
Occur in that in recent years some using modern instrumental analysis detect octane number methods, first determine gasoline composition or
Structure, then component and the relation of octane number are analyzed, so as to calculate the octane number of gasoline.This current class method includes gas phase color
Spectrometry, near infrared spectroscopy, sensor method, nuclear magnetic resonance spectroscopy, Raman spectroscopy, topological Indices etc..Using these sides
Method can be with simple and quick measure octane number.But these methods using mathematical modeling by the composition or structured data of gasoline with it is pungent
Alkane value, which is associated, carrys out calculated octane number, haves the shortcomings that error is big, and especially when gasolene ingredient is varied widely, error is outstanding
To be obvious.The main cause for causing error is burning essence of this class method not based on petrol molecule to calculate octane
Value.Because octane number is the capability of antidetonance of gasoline in combustion, its essence is a kind of ignition quality.In combustion,
With air violent oxidation reaction occurs for petrol molecule, produces substantial amounts of free radical, occurs very exothermic, is a complicated change
Process, therefore be only difficult accurately to calculate its octane number in itself from gasoline composition.This class method causes another original of error
Because being the non-linear blending effect of octane number.Different gasoline constitutes the octane number in the presence of respectively as separate constituent, with
Its octane number in a mixture is different.And gasoline is a kind of mixture being made up of large number of petrol molecule,
Therefore from the octane number of the composition of gasoline or Structure Calculation gasoline when in the presence of complicated nonlinear effect, cause calculation error.
The content of the invention
To solve, equipment costliness present in existing octane number determination technology, complex operation, error are big, tackle gasolene ingredient
The technical problem such as inaccurate during change, the invention provides a kind of octane number determination system of combination petrol molecule combustion mechanism.
The invention provides a kind of octane number determination system of combination petrol molecule combustion mechanism.The system is made up of gasoline
Analytical instrument, octane number computing module two large divisions composition.
Wherein gasoline composition analysis instrument can use gas chromatography, near infrared spectroscopy, sensor method, nuclear magnetic resonance
One or more in the methods such as spectral method, Raman spectroscopy, topological Indices, determine detailed hydrocarbon molecular composition or the race of gasoline
Composition（That is PIONA is constituted）.
It is preferred that, wherein gasoline composition analysis instrument includes the gas chromatograph of particular configuration, determines the detailed hydrocarbon of gasoline
Molecular composition or race's composition.Gas-chromatography configuration of the present invention is installed additional certainly using pre-cut post, two pillars of analytical column
Dynamic switching ten-way valve realizes the automatic switchover of pre-cut post, analytical column.Flame ionisation detector is installed after pre-cut post, analytical column
（FID）, carry out hydrocarbon molecules, the detection of oxygen-containing molecules.Sulfur chemiluminescent detector is installed after fid detector（SCD）, by post
The sulfur-containing compound that son is eluted is burnt in SCD combustion chambers, then with ozone reaction, detects the content of sulfur-containing molecules.
By the gas chromatographic detection instrument of above-mentioned configuration, the hydrocarbon molecules, oxygen-containing molecules, the monomer hydrocarbon molecule of sulfur-containing molecules of gasoline are determined
Composition or race's composition（That is PIONA is constituted）.
Octane number computing module includes two parts：
（1）Constituted first according to petrol molecule composition or race, with reference to the combustion mechanism of petrol molecule, calculate different molecular and lighting
During produced by intermediate product free radical, especially wherein trigger vigorous combustion peroxide radical species and number
Amount.Because peroxide radical can trigger chain reaction, trigger burning, therefore quantity and the generation of peroxide radical
Speed directly determines the knock characteristic of gasoline.Kinds of Free Radicals and concentration according to produced by different molecular ignition procedures, really
Determine the time lag of inflammation of gasoline；
（2）Octane number is calculated by model interaction according to the time lag of inflammation of gasoline.
The cardinal principle and structure of the present invention is as shown in Figure 1.
Based on above-mentioned thinking, on the one hand, the invention provides a kind of method for determining octane number, methods described is included
Following steps：
（1）Determine the molecular composition of gasoline sample；
（2）According to step（1）The petrol molecule composition of measure, calculates the octane number of the gasoline sample.
In some embodiments, the step（1）Specially determine detailed hydrocarbon molecular composition and/or the race of gasoline
Composition, wherein detailed hydrocarbon molecular composition include the content of each individual molecule in gasoline, and race's composition is included in gasoline composition just
Structure alkane, isoparaffin, alkene, cycloalkane, the content of aromatic hydrocarbons.
In some embodiments, the step（1）In can use gas chromatography, near infrared spectroscopy, biography
One or more in the instruments such as sensor method, nuclear magnetic resonance spectroscopy, Raman spectroscopy, topological Indices determine gasoline sample
Molecular composition.
In some embodiments, the step（1）The gas chromatograph of middle use particular configuration, determines gasoline
Detailed hydrocarbon molecular composition or race's composition；Gas-chromatography configuration is installed additional and cut automatically using pre-cut post, two pillars of analytical column
Change the automatic switchover that ten-way valve realizes pre-cut post, analytical column；Flame ionisation detector is installed after pre-cut post, analytical column（FID）,
Carry out hydrocarbon molecules, the detection of oxygen-containing molecules；Sulfur chemiluminescent detector is installed after fid detector（SCD）, pillar is eluted
The sulfur-containing compound gone out is burnt in SCD combustion chambers, then with ozone reaction, detects the content of sulfur-containing molecules；By upper
State the gas chromatographic detection instrument of configuration, determine the hydrocarbon molecules of gasoline, oxygen-containing molecules, the detailed hydrocarbon molecular composition of sulfur-containing molecules or
Race constitutes（That is PIONA is constituted）, for follow-up octane number calculation procedure.
In some embodiments, the step（2）In further comprise the steps of：
（i）According to step（1）In petrol molecule composition, with reference to the combustion mechanism of petrol molecule, calculate petrol molecule and lighting
During the free radical that generates produce quantity and speed；
（ii）According to step（i）Middle calculated free radical produces the ignition lag that quantity calculates gasoline with speed；
（iii）According to step（ii）The gasoline ignition lag calculated, calculates the octane number of gasoline；
（iv）Export octane number.
In some embodiments, above-mentioned steps（i）Middle petrol molecule composition or race according in step 1 is constituted,
With reference to the detailed combustion mechanism of petrol molecule, free radical generation quantity and speed that petrol molecule is generated in ignition procedures are calculated
Degree.In the combustion mechanism of petrol molecule, peroxide radical can trigger chain reaction, trigger burning, therefore peroxidating
The quantity and generation speed of thing free radical directly determine the knock characteristic of gasoline.The change of typical peroxide radical generation
Learn equation as shown in Figure 2.
Wherein the combustion mechanism of petrol molecule can be known in the art, typical combustion mechanism such as M. Mehl,
H. J. Curran, W. J. Pitz and C. K. Westbrook, "Chemical kinetic modeling of
component mixtures relevant to gasoline," European Combustion Meeting,
Vienna, Austria, 2009；Or H. J. Curran, P. Gaffuri, W. J. Pitz and C. K.
Westbrook, "A Comprehensive Modeling Study of iso-Octane Oxidation," Combust.
Flame 129 (2002) 253-280；Or the combustion mechanism disclosed in other any known references.
In some embodiments, above-mentioned steps（ii）In, ignition lag is calculated according to below equation：
IG = m0/SUM(dmi/ dt), i=1 ..., n（1）
In formula：
IG represents the ignition delay time of gasoline；
m0Represent the free radical quantity needed for instancy of ignition in gasoline ignition procedures；
SUM represents summation；
dmi/ dt represents the speed that i-th of free radical is produced；
N represents the Kinds of Free Radicals quantity that petrol molecule composition is produced.
Typical gasoline ignition delay time is as shown in Figure 3.
In some embodiments, above-mentioned steps（iii）In, the octane number of calculating includes research octane number (RON)
（RON）With motor octane number（MON）, its calculation formula is distinguished as follows：
log(RON) = A1 + B1 x log(IG700) （2）
log(MON) = A2 + B2 x log(IG1000) （3）
In formula：
A1、B1、A2、B2For model parameter；
IG700Ignition lag when for gasoline ignition temperature being 700K；
IG1000It is the ignition lag that 1000K is for gasoline ignition temperature.
Therefore, in a particularly preferred embodiment, the invention provides a kind of method for determining octane number,
Specifically comprise the following steps：
（1）Referred to using gas chromatography, near infrared spectroscopy, sensor method, nuclear magnetic resonance spectroscopy, Raman spectroscopy, topology
One or more in the instruments such as number method constitute come the detailed hydrocarbon molecular composition and/or race for determining gasoline sample, wherein detailed hydrocarbon
Molecular composition includes the content of each individual molecule in gasoline, race's composition include n-alkane during gasoline is constituted, isoparaffin,
Alkene, cycloalkane, the content of aromatic hydrocarbons；Preferably, wherein including the gas chromatograph of particular configuration in used instrument, determine
The detailed hydrocarbon molecular composition of gasoline or race's composition；The gas-chromatography configuration is installed additional using pre-cut post, two pillars of analytical column
Automatic switchover ten-way valve realizes the automatic switchover of pre-cut post, analytical column；Flame ionisation detector is installed after pre-cut post, analytical column
（FID）, carry out hydrocarbon molecules, the detection of oxygen-containing molecules；Sulfur chemiluminescent detector is installed after fid detector（SCD）, by post
The sulfur-containing compound that son is eluted is burnt in SCD combustion chambers, then with ozone reaction, detects the content of sulfur-containing molecules；
By the gas chromatographic detection instrument of above-mentioned configuration, the hydrocarbon molecules, oxygen-containing molecules, the monomer hydrocarbon molecule of sulfur-containing molecules of gasoline are determined
Composition or race's composition（That is PIONA is constituted）, for follow-up octane number calculation procedure；
（2）According to step（1）The petrol molecule composition of measure, calculates the octane number of the gasoline sample；
Wherein step（2）In specifically comprise the steps of：
（i）According to step（1）In petrol molecule composition, with reference to the combustion mechanism of petrol molecule, calculate petrol molecule and lighting
During the free radical that generates produce quantity and speed；
（ii）According to step（i）Middle calculated free radical produces the ignition lag that quantity calculates gasoline with speed, wherein calculating
The formula of ignition lag is as follows：
IG = m0/SUM(dmi/ dt), i=1 ..., n（1）
In formula：
IG represents the ignition delay time of gasoline；
m0Represent the free radical quantity needed for instancy of ignition in gasoline ignition procedures；
SUM represents summation；
dmi/ dt represents the speed that i-th of free radical is produced；
N represents the Kinds of Free Radicals quantity that petrol molecule composition is produced；
（iii）According to step（ii）The gasoline ignition lag calculated, calculates the research octane number (RON) of gasoline（RON）With motor method
Octane number（MON）, its calculation formula is distinguished as follows：
log(RON) = A1 + B1 x log(IG700) （2）
log(MON) = A2 + B2 x log(IG1000) （3）
In formula：
A1、B1、A2、B2For model parameter；
IG700Ignition lag when for gasoline ignition temperature being 700K；
IG1000It is the ignition lag that 1000K is for gasoline ignition temperature；
（iv）Export research octane number (RON)（RON）With motor octane number（MON）.
On the other hand, present invention provides the device for determining octane number, described device includes following part：
（1）Measurement module, and
（2）Computing module；
Wherein measurement module includes the instrument of measurement petrol molecule composition, and
Wherein computing module includes ignition delay time computing module and octane number computing module.
In some preferred embodiments, gas chromatography, near infrared spectroscopy, sensor are included in the measurement module
One or more in the instruments such as method, nuclear magnetic resonance spectroscopy, Raman spectroscopy, topological Indices, to determine gasoline sample
Molecular composition and/or race's composition.Preferably, and in the measurement module gas chromatograph of particular configuration is included, vapour is determined
The detailed hydrocarbon molecular composition of oil or race's composition；The gas-chromatography configuration is installed additional certainly using pre-cut post, two pillars of analytical column
Dynamic switching ten-way valve realizes the automatic switchover of pre-cut post, analytical column；Flame ionisation detector is installed after pre-cut post, analytical column
（FID）, carry out hydrocarbon molecules, the detection of oxygen-containing molecules；Sulfur chemiluminescent detector is installed after fid detector（SCD）, by post
The sulfur-containing compound that son is eluted is burnt in SCD combustion chambers, then with ozone reaction, detects the content of sulfur-containing molecules；
By the gas chromatographic detection instrument of above-mentioned configuration, the hydrocarbon molecules, oxygen-containing molecules, the monomer hydrocarbon molecule of sulfur-containing molecules of gasoline are determined
Composition or race's composition（That is PIONA is constituted）.
In some preferred embodiments, the measure octane number that the computing module can be provided according to the present invention
Method constitutes the measurement result of measurement module come calculated octane number according to petrol molecule.
The present invention using gas chromatography, near infrared spectroscopy, sensor method, nuclear magnetic resonance spectroscopy, Raman spectroscopy,
Detailed hydrocarbon composition or race's composition in one or more Instrument measuring gasoline in the instruments such as topological Indices, and further combined with
Petrol molecule combustion mechanism model, calculates free radical generation quantity and speed, and further calculate the octane number of gasoline.With biography
The octane number determination method of system is compared, and the present invention possesses following advantage.
Calculated octane number is constituted based on petrol molecule, robustness is significantly improved.Gasoline N-alkanes is included by setting up
Hydrocarbon, isoparaffin, alkene, cycloalkane, aromatic hydrocarbons, oxygenatedchemicals, sulfur-containing compound etc. exceed 300 detailed petrol molecule storehouses, make
The new gasoline blending component that produces under the composition transfer of any gasoline blending component, different operating mode all without departing from the library of molecules
Category.Actual production situation when therefore being changed disclosed by the invention is widely suitable to gasoline blending component.
Based on petrol molecule combustion mechanism, the degree of accuracy of model is greatly improved.Do not making the situation of any model correction
Under, the precision of prediction of octane number can reach within 1.In the case of by a small amount of actual production Data correction, to octane number
Precision of prediction can reach within 0.5.In the case of by lasting actual production Data correction, to the prediction essence of octane number
Degree can reach within 0.1.
Reduce the cost of gasoline measurement.The present invention may replace the single-cylinder engine octane number test equipment of costliness, with more
Low cost, the octane number of faster speed Accurate Determining gasoline.
It is more convenient for coming into operation.In the case of correction is used as without any rated octane number data accumulation, the present invention also may be used
Come into operation rapidly, the octane number of Accurate Determining gasoline.
It is more convenient for safeguarding.The present invention catches the burning essence of petrol molecule, is applicable to different gasoline concoction operating modes, no
Same gasoline production demand, the maintenance needs to model are greatly reduced.
Brief description of the drawings
Fig. 1 octane number determination system structure diagrams of the present invention.
Fig. 2 typical gasoline molecules peroxide radical generation chemical reaction.
Ignition lag of Fig. 3 gasoline at a temperature of different light.
The partial monosomy hydrocarbon molecule composition data of Fig. 4 Arabian light crude straight-run naphthas.
Fig. 5 naphtha molecule combustion mechanism partial reaction networks.
Free radical quantity and ignition lag in Fig. 6 Sandi Light Crude naphtha ignition procedures.
Fig. 7 northwest Chinas oil refining enterprise's atmospheric and vacuum distillation unit often pushes up oily PIONA composition datas.
Fig. 8 often push up oil molecule combustion mechanism partial reaction network.
Fig. 9 northwest Chinas oil refining enterprise's atmospheric and vacuum distillation unit often push up oil drop combustion during free radical quantity with
Ignition delay.
Embodiment
Below by embodiment, the present invention is described in further detail.
【Embodiment 1】
The present invention determines Saudi Arabia's light crude oil naphtha octane number using gas-chromatography with gasoline combustion detailed mechanism
Embodiment.
（1）The list of Sandi Light Crude straight-run naphtha is determined using the gas chromatography of particular configuration as shown in Figure 1
Body hydrocarbon molecule is constituted.Moieties composition data is as shown in Figure 4.
（2）According to the petrol molecule composition in step 1, with reference to the detailed combustion mechanism of petrol molecule, petrol molecule is calculated
The free radical generated in ignition procedures produces quantity and speed.Used mechanism includes 385 kinds of molecules and free radical, 1895
Individual chemical reaction.The reaction mechanism network of part naphtha molecule is as shown in Figure 5.
（3）The ignition lag that quantity calculates gasoline with speed is produced according to the free radical calculated in step 2.It, which catches fire, prolongs
Function such as formula is calculated late（1）It is shown.
IG = m0/SUM(dmi/ dt), i=1 ..., n（1）
In formula：
IG represents the ignition delay time of gasoline；
m0Represent the free radical quantity needed for instancy of ignition in gasoline ignition procedures；
SUM represents summation；
dmi/ dt represents the speed that i-th of free radical is produced；
N represents the Kinds of Free Radicals quantity that petrol molecule composition is produced.
The naphtha of Sandi Light Crude free radical quantity in combustion and ignition lag are as shown in Figure 6.
（4）The gasoline ignition lag calculated according to step 3, the octane number of gasoline is calculated by model.Wherein organon
Octane number（RON）With motor octane number（MON）Calculation formula respectively such as formula（2）, formula（3）It is shown：
log(RON) = A1 + B1 x log(IG700) （2）
log(MON) = A2 + B2 x log(IG1000) （3）
In formula：
A1、B1、A2、B2For model parameter, parameter value is respectively 0.32, -0.79,0.48, -0.51 in the present embodiment；
IG700Ignition lag when for gasoline ignition temperature being 700K, is in the present embodiment 0.0149 second；
IG1000It is the ignition lag that 1000K is for gasoline ignition temperature, is in the present embodiment 0.00271 second.
（5）The research octane number (RON) that obtained Sandi Light Crude naphtha is calculated in final the present embodiment is 58.0,
Motor octane number is 61.5.
The present embodiment is by using gas-chromatography and gasoline combustion mechanism model, ignition lag computation model and octane number
Computation model, the research octane number (RON) and motor octane number of Accurate Determining Sandi Light Crude naphtha.Not any
Under conditions of Data correction, measured value and the error of single-cylinder engine octane number test value are respectively 0.6 and 0.3, have reached vapour
Precision needed for oily Optimizing manufacture, can effectively instruct petroleum chemical enterprise to carry out the plan scheduling of gasoline production.Meanwhile, measurement cost
More traditional single-cylinder engine octane number test reduces 5 times.
【Embodiment 2】
The present invention determines northwest China's oil refining enterprise's Atmospheric vacuum using near-infrared and gasoline combustion reduced kinetic mechanism and filled
Put the embodiment of the oily octane number in often top.
（1）Oil is often pushed up using the oil refining enterprise of gas chromatograph for determination northwest China of particular configuration shown in Fig. 1
PIONA is constituted.Part PIONA composition datas are as shown in Figure 7.
（2）According to the normal top oil PIONA composition datas in step 1, with reference to the Reduced combustion mechanism of gasoline, calculate gasoline and exist
The free radical generated in ignition procedures produces quantity and speed.Used mechanism includes 56 kinds of molecular components and free radical, 279
Individual chemical reaction.The reaction mechanism network that oil molecule is often pushed up in part is as shown in Figure 8.
（3）The ignition lag that quantity calculates gasoline with speed is produced according to the free radical calculated in step 2.It, which catches fire, prolongs
Function such as formula is calculated late（1）It is shown.
IG = m0/SUM(dmi/ dt), i=1 ..., n（1）
In formula：
IG represents the ignition delay time of gasoline；
m0Represent the free radical quantity needed for instancy of ignition in gasoline ignition procedures；
SUM represents summation；
dmi/ dt represents the speed that i-th of free radical is produced；
N represents the Kinds of Free Radicals quantity that petrol molecule composition is produced.
The oily free radical quantity and ignition lag in combustion in the normal top of the present embodiment is as shown in Figure 9.
（4）The gasoline ignition lag calculated according to step 3, the octane number of gasoline is calculated by model.Wherein organon
Octane number（RON）With motor octane number（MON）Calculation formula respectively such as formula（2）, formula（3）It is shown：
log(RON) = A1 + B1 x log(IG700) （3）
log(MON) = A2 + B2 x log(IG1000) （4）
In formula：
A1、B1、A2、B2For model parameter, parameter value is respectively 0.46, -0.74,0.61, -0.46 in the present embodiment；
IG700Ignition lag when for gasoline ignition temperature being 700K, is in the present embodiment 0.0153 second；
IG1000It is the ignition lag that 1000K is for gasoline ignition temperature, is in the present embodiment 0.00273 second.
（5）The research octane number (RON) that obtained Sandi Light Crude naphtha is calculated in final the present embodiment is 63.6,
Motor octane number is 61.6.
The present embodiment by using near-infrared determine often top oil PIONA constitute, and with gasoline combustion mechanism model, catch fire
Delay computing model and octane number computation model be combined, and the research octane number (RON) and motor method of the normal top oil of Accurate Determining are pungent
Alkane value.Under conditions of not any Data correction, measured value and the error of single-cylinder engine octane number test value are respectively 0.7
With 0.2, the precision needed for gasoline production optimization has been reached, can effectively instruct petroleum chemical enterprise to carry out the plan row of gasoline production
Production.Meanwhile, more than 10 times are reduced than traditional single-cylinder engine octane number test on finding speed, can be complete in 15 minutes
Into measure work.Computational accuracy than traditional near infrared spectrum peak area direct correlation octane number in the degree of accuracy is higher, its
Error drops to 0.1~0.5 scope from 1~2 traditional scope.Measurement cost is surveyed than traditional single-cylinder engine octane number
Examination reduces more than 6 times.
Claims (11)
1. a kind of method for determining octane number, it is characterised in that comprise the following steps：
（1）Determine the molecular composition of gasoline sample；
（2）According to step（1）The petrol molecule composition of measure, calculates the octane number of the gasoline sample.
2. the method for octane number is determined described in claim 1, it is characterised in that the step（1）Specially determine gasoline
Detailed hydrocarbon molecular composition and/or race's composition, wherein detailed hydrocarbon molecular composition includes the content of each individual molecule in gasoline, race
Constitute the n-alkane included in gasoline composition, isoparaffin, alkene, cycloalkane, the content of aromatic hydrocarbons.
3. the method for octane number is determined described in claim 1 or 2, it is characterised in that the step（1）Middle use gas phase color
One kind in the instruments such as spectrometry, near infrared spectroscopy, sensor method, nuclear magnetic resonance spectroscopy, Raman spectroscopy, topological Indices
Or a variety of molecular compositions to determine gasoline sample.
4. the method for octane number is determined described in claim 1 or 2, it is characterised in that the step（1）It is middle to be matched somebody with somebody using specific
The gas chromatograph put, determines detailed hydrocarbon molecular composition or the race's composition of gasoline；The gas-chromatography configuration uses pre-cut post, divided
Two pillars of post are analysed, and install the automatic switchover that automatic switchover ten-way valve realizes pre-cut post, analytical column additional；In pre-cut post, analytical column
After flame ionisation detector is installed（FID）, carry out hydrocarbon molecules, the detection of oxygen-containing molecules；Sulfur chemistry is installed after fid detector
Luminescence detector（SCD）, the sulfur-containing compound that pillar is eluted is burnt in SCD combustion chambers, then with ozone reaction,
Detect the content of sulfur-containing molecules；By the gas chromatographic detection instrument of above-mentioned configuration, determine the hydrocarbon molecules of gasoline, oxygen-containing molecules,
The detailed hydrocarbon molecular composition of sulfur-containing molecules or race's composition（That is PIONA is constituted）, for follow-up octane number calculation procedure.
5. the method for octane number is determined described in claim 1, it is characterised in that the step（2）In specifically comprising following
Step：
（i）According to step（1）In petrol molecule composition, with reference to the combustion mechanism of petrol molecule, calculate petrol molecule and lighting
During the free radical that generates produce quantity and speed；
（ii）According to step（i）Middle calculated free radical produces the ignition lag that quantity calculates gasoline with speed；
（iii）According to step（ii）The gasoline ignition lag calculated, calculates the octane number of gasoline；
（iv）Export octane number.
6. the method for octane number is determined according to claim 5, it is characterised in that the step（ii）In, according to
Lower formula calculates ignition lag：
IG = m0/SUM(dmi/ dt), i=1 ..., n（1）
In formula：
IG represents the ignition delay time of gasoline；
m0Represent the free radical quantity needed for instancy of ignition in gasoline ignition procedures；
SUM represents summation；
dmi/ dt represents the speed that i-th of free radical is produced；
N represents the Kinds of Free Radicals quantity that petrol molecule composition is produced.
7. the method for octane number is determined according to claim 5, it is characterised in that the step（iii）In, calculate
Octane number include research octane number (RON)（RON）With motor octane number（MON）, its calculation formula is distinguished as follows：
log(RON) = A1 + B1 x log(IG700) （2）
log(MON) = A2 + B2 x log(IG1000) （3）
In formula：
A1、B1、A2、B2For model parameter；
IG700Ignition lag when for gasoline ignition temperature being 700K；
IG1000It is the ignition lag that 1000K is for gasoline ignition temperature.
8. a kind of method for determining octane number, it is characterised in that comprise the following steps：
（1）Referred to using gas chromatography, near infrared spectroscopy, sensor method, nuclear magnetic resonance spectroscopy, Raman spectroscopy, topology
One or more in the instruments such as number method constitute come the detailed hydrocarbon molecular composition and/or race for determining gasoline sample, wherein detailed hydrocarbon
Molecular composition includes the content of each individual molecule in gasoline, race's composition include n-alkane during gasoline is constituted, isoparaffin,
Alkene, cycloalkane, the content of aromatic hydrocarbons；The gas chromatograph of particular configuration is included in wherein used instrument, gasoline is determined
Detailed hydrocarbon molecular composition or race's composition；Gas-chromatography configuration is installed additional and cut automatically using pre-cut post, two pillars of analytical column
Change the automatic switchover that ten-way valve realizes pre-cut post, analytical column；Flame ionisation detector is installed after pre-cut post, analytical column（FID）,
Carry out hydrocarbon molecules, the detection of oxygen-containing molecules；Sulfur chemiluminescent detector is installed after fid detector（SCD）, pillar is eluted
The sulfur-containing compound gone out is burnt in SCD combustion chambers, then with ozone reaction, detects the content of sulfur-containing molecules；By upper
State the gas chromatographic detection instrument of configuration, determine the hydrocarbon molecules of gasoline, oxygen-containing molecules, the detailed hydrocarbon molecular composition of sulfur-containing molecules or
Race constitutes（That is PIONA is constituted）, for follow-up octane number calculation procedure；
（2）According to step（1）The petrol molecule composition of measure, calculates the octane number of the gasoline sample；
Wherein step（2）In specifically comprise the steps of：
（i）According to step（1）In petrol molecule composition, with reference to the combustion mechanism of petrol molecule, calculate petrol molecule and lighting
During the free radical that generates produce quantity and speed；
（ii）According to step（i）Middle calculated free radical produces the ignition lag that quantity calculates gasoline with speed, wherein calculating
The formula of ignition lag is as follows：
IG = m0/SUM(dmi/ dt), i=1 ..., n（1）
In formula：
IG represents the ignition delay time of gasoline；
m0Represent the free radical quantity needed for instancy of ignition in gasoline ignition procedures；
SUM represents summation；
dmi/ dt represents the speed that i-th of free radical is produced；
N represents the Kinds of Free Radicals quantity that petrol molecule composition is produced；
（iii）According to step（ii）The gasoline ignition lag calculated, calculates the research octane number (RON) of gasoline（RON）With motor method
Octane number（MON）, its calculation formula is distinguished as follows：
log(RON) = A1 + B1 x log(IG700) （2）
log(MON) = A2 + B2 x log(IG1000) （3）
In formula：
A1、B1、A2、B2For model parameter；
IG700Ignition lag when for gasoline ignition temperature being 700K；
IG1000It is the ignition lag that 1000K is for gasoline ignition temperature；
（iv）Export research octane number (RON)（RON）With motor octane number（MON）.
9. the device for determining octane number, it is characterised in that include following part：
（1）Measurement module, and
（2）Computing module；
Wherein measurement module includes the instrument of measurement petrol molecule composition, and
Wherein computing module includes ignition delay time computing module and octane number computing module.
10. claim 9 described device, it is characterised in that gas chromatography, near infrared spectrum are included in the measurement module
One or more in the instruments such as method, sensor method, nuclear magnetic resonance spectroscopy, Raman spectroscopy, topological Indices, to determine vapour
The molecular composition of oil samples and/or race's composition；And the gas chromatograph of particular configuration is included in the measurement module, vapour is determined
The detailed hydrocarbon molecular composition of oil or race's composition；The gas-chromatography configuration is installed additional certainly using pre-cut post, two pillars of analytical column
Dynamic switching ten-way valve realizes the automatic switchover of pre-cut post, analytical column；Flame ionisation detector is installed after pre-cut post, analytical column
（FID）, carry out hydrocarbon molecules, the detection of oxygen-containing molecules；Sulfur chemiluminescent detector is installed after fid detector（SCD）, by post
The sulfur-containing compound that son is eluted is burnt in SCD combustion chambers, then with ozone reaction, detects the content of sulfur-containing molecules；
By the gas chromatographic detection instrument of above-mentioned configuration, the hydrocarbon molecules, oxygen-containing molecules, the monomer hydrocarbon molecule of sulfur-containing molecules of gasoline are determined
Composition or race's composition（That is PIONA is constituted）.
11. the described device of claim 9 or 10, it is characterised in that the computing module can be any one according to claim 4-7
The method that item is limited constitutes the measurement result of measurement module come calculated octane number according to petrol molecule.
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