CN1534292A - Method of predicting oil product quality using chromatography mass spectrometry combined method - Google Patents
Method of predicting oil product quality using chromatography mass spectrometry combined method Download PDFInfo
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Abstract
A method for predicting the properties of crude oil's fraction by using the combination of gas-phase chromatography and mass-spectrography includes collecting various predicted fraction specimens, filling in gas-phase chromatography, separating, filling in mass-spectrography to obtain total ion stream chromatomap, determining retention time range, choosing the analytic range of mass charge ratio, using the peak with 57 of mass charge ration as reference to find out the relative abundance of other peaks, confiquring the x array of relative abundances and the Y array of relative measured property values, association analysis to find out relation array, creating predicting model, and predicting.
Description
Technical field
The present invention is the method for a kind of look-matter coupling prediction oil property, specifically, is to utilize chromatograph and mass spectrometer coupling, by the method for mass spectrogram prediction oil property.
Background technology
Petroleum products is very complicated potpourri, and it promptly includes hydrocarbon compound, includes the compound of non-hydrocarbons again, and its character generally all is to adopt the mode assay determination of independent measurement.Though this metering system precision is very high, and is consuming time more, and the sample size that needs is also bigger, can not satisfy the needs of express-analysis under many occasions.
The analytical approach of look-matter coupling (GC/MS) was mainly used in the analysis of petroleum products hydrocarbon composition in the past, but the also advantage that can utilize chromatogram to combine with mass spectrum, obtain the characteristic of oil product, utilize the mass spectrogram data to set up model, analyze the character of oil product, set up the method for fast prediction oil property.As USP5,699,269 disclose a kind of method of the GC/MS of utilization prediction oil property, and this method is measured the physics or the chemical property of crude oil or its cut earlier with standard method, collect different samples and form reference set.Sample in the reference set is injected chromatographic column, pass through mass spectrometer again, obtain each sample by the mass spectrogram that chromatographic retention decomposes, choose a series of molecules and/or fragment ion in each boiling point fraction, described fragment is represented the feature of related compound or type of compounds.All ionic strengths of each characterization compound or type of compounds in the record mass spectrogram, also the used weight mark multiply by ionic strength and obtains percent by weight or percent by volume.The characterization compound fragment that in mass spectrogram, choose or form the X matrix by the ionic strength percentage that fragment is tried to achieve, character data with crude oil is the Y matrix, with comprising partial least square method multiple correlation methods analyst, obtain a series of coefficients, can set up forecast model.But this method modeling obtaining value method is comparatively loaded down with trivial details.
Summary of the invention
The purpose of this invention is to provide a kind of method by look-matter coupling (GC/MS) method prediction oil property, this method value is easy, the model prediction precision height of foundation, and predicted value and measured value are approaching.
Relative abundance in the mass spectrogram that the present invention obtains with the GC/MS method is an independent variable, is dependent variable with the oil property of independent variable correspondence, sets up the oil property forecast model with partial least square method.Modeling method is simple, and highly versatile is suitable for the property analysis of various oil products.In addition, predict oil property with this method, used sample size is few, and Measuring Time is short, and the particularly measurement of a plurality of samples after the GC/MS analysis, can be predicted these samples simultaneously, has shortened analysis time more.The model prediction accuracy is better, and precision is very high.
Description of drawings
The process flow diagram that Fig. 1 sets up for forecast model of the present invention.
The virgin kerosene mass spectrum average ion intensity distribution of Fig. 2 for recording with GC/MS.
Embodiment
The method of gas chromatography provided by the invention and mass spectrometer coupling prediction crude oil fractions character comprises the steps:
(1) the crude oil fractions sample of the various pre-mensuration of collection, with the character of standard method working sample, the character of institute's working sample is identical with prediction character,
(2) as follows the cut sample of collecting is set up forecast model:
A) to the sample of each collection, get in the injector of 0.05～0.5 microlitre injection gas chromatography, after chromatographic resolution, enter mass spectrometer,
B) total ions chromatogram that provides according to chromatograph, determine the retention time scope of prediction cut, choose the mass-to-charge ratio analyst coverage of mass spectrogram again according to the retention time scope, and in this scope, be that 57 peak is a reference peaks with mass-to-charge ratio, obtain the relative abundance at other relative datum peak, peak
C) the relative abundance value of each mass-to-charge ratio in the mass spectrogram of each sample is formed the X matrix,
D) the property testing value of each sample correspondence is formed the Y matrix,
E) with partial least square method with Y matrix and the interrelated analysis of X matrix, obtain the relational matrix with X matrix Y matrix, set up forecast model,
(3) with crude oil fractions sample to be measured by (2) step a, b method try to achieve the relative abundance value, the substitution forecast model obtains the property prediction value of sample.
Crude oil fractions of the present invention is selected from gasoline fraction, diesel oil distillate, kerosene distillate or heavy distillate.The crude oil fractions character of prediction comprises density, viscosity, index of refraction, aniline point and/or pour point.
Described gasoline fraction comprises straight-run gasoline, catalytic gasoline, reformed gasoline, isomerization gasoline; Kerosene distillate comprises virgin kerosene, aviation kerosene, illuminating kerosene; Diesel oil distillate comprises straight-run diesel oil, catalytic diesel oil, hydrogenated diesel oil and blended diesel.The boiling range of heavy distillate is 350～540 ℃.
The preferred capillary chromatography of gas chromatograph in the described method, the preferred quadrupole mass spectrometer of mass spectrometer.
B in the described method) relative abundance of the mass-to-charge ratio of addressing is meant in mass spectrogram, is that 57 peak is a benchmark with mass-to-charge ratio, the ratio that the intensity that has the peak under other mass-to-charge ratio is obtained by comparison.
Method that analyze to determine the mass-to-charge ratio relative abundance of prediction cut with GC/MS is: sample is injected look-matter combined instrument, by chromatographic column each component of described cut sample is separated, and then it is sent in the mass spectrometer detect.The peak that solvent that uses when getting rid of stratographic analysis in the total ions chromatogram that look-the matter combined instrument obtains and hangover produce, with determine the retention time scope of the cut of being surveyed on total ions chromatogram.According to the retention time scope of selecting, can in mass spectrogram, find the mass-to-charge ratio distribution range of prediction cut, in this scope, calculate the mass-to-charge ratio relative abundance, can obtain the independent variable corresponding with cut character.When described crude oil fractions is selected from gasoline fraction, the mass-to-charge ratio distribution range of choosing is 41.0～200.0 atomic mass units (amu), when described crude oil fractions is selected from kerosene distillate, the mass-to-charge ratio distribution range of choosing is 41.0～250.0amu, when described crude oil fractions was selected from diesel oil distillate, the mass-to-charge ratio distribution range of choosing was 41.0～350.0amu.
Among Fig. 1, solid line represents that forecast model of the present invention sets up flow process, dotted line representation model checking flow process.To be divided into two groups after the sample determination character of collecting among the figure, one group is the calibration set sample, and another group is checking collection sample.The GC/MS chromatogram characteristic and the character of unknown sample after the GC/MS chromatogram characteristic of calibration set sample and character should be able to contain, and the property distribution of sample should be even as far as possible.Checking collection sample can be from the sample of collecting random choose.
The ultimate principle that forecast model of the present invention is set up is: the ion relative abundance under each mass-to-charge ratio of calibration set various kinds product mass spectrogram correspondence is formed the X matrix, again the character data of each sample correspondence is formed the Y matrix.The relation of setting up X and Y according to partial least square method is as follows:
In the formula (1), y
nRepresent the prediction character data of n sample, x
NmIt is the relative abundance of m fragmention of n sample.
Formula (1) can be reduced to Y=XB
Wherein B is a matrix of coefficients.
Can try to achieve matrix of coefficients B by X matrix data and character data Y matrix.B substitution formula (1) is promptly obtained the oil property forecast model.
The method of trying to achieve matrix of coefficients B with partial least square method (PLS) is as follows:
At first with X, Y as matrix decomposition is
X＝TP+E
Y＝UQ+F
T and U are respectively the sub matrix that gets of X matrix and Y matrix in the following formula, and P and Q are respectively load (the being major component) matrix of X matrix and Y matrix, the error that E, F are introduced when being respectively with partial least square method match X and Y.
Then, T and U are done linear regression with the following method,
U＝TB
B=(T ' T)
-1T ' U wherein T ' is the transposed matrix of matrix T.
When prediction, by the matrix X of unknown sample
UnknownThe P that obtains with correction
UnknownObtain the T of unknown sample X matrix
Unknown, obtain then:
Y
Unknown=T
UnknownBQ
Said process is the process of a validation-cross, removes by the sample that validation-cross is strange with numerical value, makes the residual sum of squares (RSS) of each sample that calibration set keeps reach minimum, to set up the better prediction model.
The predicted data of sample and the difference of test data are residual error E, by the residual error of each sample, try to achieve standard deviation (SE) and related coefficient (R) by following formula, can be obtained the precision of forecast model by its size.
In formula (2) and (3), y
iBe the standard method measured value of i sample of calibration set,
Be its predicted value, m is the sample number.
With the X matrix substitution forecast model that the ion relative abundance under each mass-to-charge ratio of each sample of checking collection is formed, be verified collection sample predicted value, and compare with the property detection data of verifying each sample of collection, model is estimated.Estimate used standard deviation and related coefficient computing method and formula (2), (3) are identical.
Used inspection t value of testing is calculated by following formula:
In the formula, S
dBe checking collection sample standard deviation;
D is checking collection sample residual error average;
M is checking collection sample number;
U is the residual error expectation value, and value is 0 here.
This method needs to collect some representative same type oil products before setting up model, and general 40～80 samples get final product, but sample collection is many more, and modelling is sane more.Can set up the property prediction model of various oil products according to different demands.
This method is predicted the used sample size of properties of samples seldom, generally is no more than 0.5 microlitre.In addition, if after having set up the SOME PROPERTIES forecast model of same type oil sample, this method single injected sampling can be predicted SOME PROPERTIES simultaneously.
Below by example in detail the present invention, but the present invention is not limited to this.
Used instrument is as follows in the example: HP 6890 GC/HP, 5973 MS and HP GC-MSD workstation; HP 7673 liquid automatic samplers; HP 1MS type capillary chromatographic column (30.0m * 250um * 0.25um).Experiment condition: sample size: 0.1 microlitre; Chromatogram temperature of vaporization chamber: 310 ℃; Total flow: 152ml/min; Split ratio: 150: 1; EI source temperature: 250 ℃; Ionization voltage: 70eV.
Example 1
Set up straight-run diesel oil aniline point forecast model.
(1) setting up diesel samples collection and aniline point character measures
With boiling spread is that 200～350 ℃ of straight-run diesel oils are sample, collects 68 typical samples as aniline point model sample, and aniline point adopts the GB/T262-88 method to measure.Wherein the calibration set sample is 56,12 in checking collection sample.
(2) set up forecast model and verifying
The chromatograph temperature programme is controlled to be: initial 50 ℃, rise to 280 ℃ with 10 ℃/min then; 0.1 microlitre calibration set sample is injected chromatic spectrum sample feeder, after chromatographic resolution, feed mass spectrometer.Determine the retention time scope of diesel oil distillate by look-matter combined instrument total ions chromatogram.Distribution range by the selected mass-to-charge ratio of retention time scope is 41.0～350.0aum, obtains average ion intensity spectrogram as shown in Figure 2.
By each matter lotus (m/z) of Fig. 2 than under peak height and the ratio of the peak height of m/z=57, obtain the relative abundance value of this sample under each m/z.Relative abundance value under each m/z ratio of mass spectrogram of each sample of calibration set is formed the X matrix, and the aniline point test data of sample correspondence is formed the Y matrix, sets up diesel oil aniline point forecast model according to partial least square method.The calibration set that obtains by the validation-cross method predicts the outcome and sees Table 1.
Will checking collection sample obtain mass spectrogram relative abundance value by same method of testing and form the X matrix, the substitution forecast model is verified collection and predicts the outcome and see Table 2.
As shown in Table 2, in given level of signifiance α=0.05, checking collection sample is carried out to the check to t, the result shows, t＜t
(0.05,11), model method and standard method no significant difference are described, the accuracy of model is reliable.In addition, checking collection standard deviation (SEP) is less, illustrates under given degree of confidence 95% condition and can accurately measure the diesel oil aniline point.
(3) rating model precision
Get the checking collection and test sample survey diesel oil model precision No. 6.Sample is carried out 3 times continuously measure under similarity condition, obtain the relative abundance value of MS spectrogram, predict aniline point with model then, the result is respectively: 77.3 ℃ for the first time, and 77.2 ℃ for the second time, 77.5 ℃ for the third time, 77.4 ℃ of three mean values, 0.2 ℃ of standard deviation.Hence one can see that, the diesel oil aniline point property prediction model precision height that this method is set up, and model is sane, and measuring repeatability and repeatability have reached the precision that standard method is measured.
Example 2
Set up virgin kerosene viscosity (20 ℃) forecast model.
(1) sets up kerosene sample sets and measure 20 ℃ of kerosene viscosity
With boiling spread is that 150～250 ℃ of straight-run diesel oils are sample, collects 47 typical samples as 20 ℃ of Viscosity Model samples, and 20 ℃ of viscosity of each sample adopt the GB/T265-88 method to measure.Get 36 samples as calibration set, 11 samples that pick out at random are the checking collection.
(2) set up forecast model and checking
Obtain the mass spectrogram of each sample of calibration set by the method for example 1, different is that chromatographic temperature programme is controlled to be: initial 50 ℃, rise to 220 ℃ with 10 ℃/min then, and during the calculation sample relative abundance, selected MS sweep limit is 41.0～250.0aum.
Relative abundance value under each m/z ratio of mass spectrogram of each sample of calibration set is formed the X matrix, corresponding sample viscosity data is formed the Y matrix, set up kerosene viscosity (20 ℃) forecast model according to partial least square method, the calibration set that obtains by the validation-cross method predicts the outcome and sees Table 3, and the checking collection predicts the outcome and sees Table 4.
As shown in Table 4, in given level of signifiance α=0.05, checking collection sample is carried out to the check to t, the result shows, t＜t
(0.05,10), model method and standard method no significant difference are described, the accuracy of model is reliable.In addition, checking collection standard deviation (SEP) is less, can accurately measure kerosene viscosity (20 ℃) under given degree of confidence 95% condition.
(3) model precision is measured
Get No. 3 samples of checking collection and check kerosene viscosity (20 ℃) model precision.Repeat 3 GC/MS and measure, obtain the relative abundance value under the different m/z ratios of MS, predict with model that respectively the result is: the 1st 1.641mm
2/ s, the 2nd 1.642mm
2/ s, the 3rd 1.648mm
2/ s, mean value 1.644mm
2/ s, standard deviation 0.002mm
2/ s.Hence one can see that, kerosene viscosity (20 ℃) the property prediction model precision height that this method is set up, and model is sane, and measuring repeatability and repeatability have reached the precision that standard method is measured.
Example 3
Set up straight-run gasoline density (20 ℃) forecast model.
(1) sets up gasoline density sample sets and measure 20 ℃ of gasoline viscosity
With the boiling spread is that initial boiling point～200 ℃ straight-run gasoline is sample, collects 77 samples as 20 ℃ of density model samples, and each sample rate adopts the GB1884-83 method to measure.Get 53 samples as calibration set, 14 samples that pick out at random are the checking collection.
(2) set up forecast model and verifying
Obtain the mass spectrogram of each sample of calibration set by the method for example 1, different is that chromatographic temperature programme is controlled to be: initial 50 ℃, rise to 180 ℃ with 10 ℃/min then, and during the calculation sample relative abundance, selected MS sweep limit is 41.0～200.0aum.
Relative abundance value under each m/z ratio of mass spectrogram of each sample of calibration set is formed the X matrix, corresponding sample rate data are formed the Y matrix, set up gasoline density (20 ℃) forecast model according to partial least square method, the calibration set that obtains by the validation-cross method predicts the outcome and sees Table 5, and the checking collection predicts the outcome and sees Table 6.
As shown in Table 6, in given level of signifiance α=0.05, checking collection sample is carried out to the check to t respectively, the result shows, t＜t
(0.05,13), model method and standard method no significant difference are described, the accuracy of model is reliable.In addition, checking collection standard deviation S EP is 0.0033, is about 0.4% with density measured value relative deviation, and under given degree of confidence 95% condition, this model can accurately be predicted straight-run gasoline density.
(3) model precision is measured
Get No. 7 samples of checking collection and check gasoline density (20 ℃) model precision.Repeat 3 GC/MS and measure, obtain the relative abundance value under the different m/z ratios of MS, predict with model that respectively the result is: the 1st 0.7472g/cm
3, the 2nd 0.7470g/cm
3, the 3rd 0.7474g/cm
3, mean value 0.7472g/cm
3, standard deviation 0.002g/cm
3Hence one can see that, gasoline density (20 ℃) the property prediction model precision height that this method is set up, and model is sane, and measuring repeatability and repeatability have reached the precision that standard method is measured.
Table 1 unit, ℃
| Sequence number measured value predicted value residual error | Sequence number measured value predicted value residual error | Sequence number measured value predicted value residual error |
| ??1????75.5????76.2???-0.7 ??2????71.1????70.7???0.4 ??3????73.7????72.9???0.8 ??4????73.6????74.1???-0.5 ??5????66.4????67.5???-1.1 ??6????67.3????66.4???0.9 ??7????65.3????64.3???1.0 ??8????69.1????68.5???0.6 ??9????79.2????78.0???1.2 ??10???73.8????74.1???-0.3 ??11???75.7????76.6???-0.9 ??12???73.0????73.7???-0.7 ??13???75.5????76.1???-0.6 ??14???78.7????78.7???0.0 ??15???82.8????82.4???0.4 ??16???66.8????66.9???-0.1 ??17???81.3????80.3???1.0 ??18???76.7????77.1???-0.4 ??19???78.6????76.9???1.7 ??20???78.3???77.5????0.8 | ??21???80.1???79.7???0.4 ??22???80.0???79.3???0.7 ??23???78.0???78.9???-0.9 ??24???68.4???68.6???-0.2 ??25???67.4???66.6???0.8 ??26???66.5???65.9???0.6 ??27???76.2???74.6???1.6 ??28???59.8???58.4???1.4 ??29???68.6???69.1???-0.5 ??30???76.8???76.0???0.8 ??31???72.4???73.5???-1.1 ??32???78.6???78.7???-0.1 ??33???74.6???75.7???-1.1 ??34???72.0???72.8???-0.8 ??35???80.2???79.3???0.9 ??36???77.0???77.0???0.0 ??37???75.6???76.4???-0.8 ??38???74.2???75.5???-1.3 ??39???72.6???72.8???-0.2 ??40???76.2???76.4??-0.2 | ??41????77.5????77.9????-0.4 ??42????74.8????75.8????-1.0 ??43????74.2????73.6????0.6 ??44????78.7????77.7????1.0 ??45????71.1????72.4????-1.3 ??46????77.9????77.7????0.2 ??47????74.4????75.1????-0.7 ??48????80.2????79.3????0.9 ??49????73.2????73.2????0.0 ??50????71.2????71.4????-0.2 ??51????71.0????71.6????-0.6 ??52????72.4????72.8????-0.4 ??53????71.3????72.3????-1.0 ??54????71.2????72.0????-0.8 ??55????72.4????71.5????0.9 ??56????77.2????76.4????0.8 |
| Standard deviation (SEC) 0.81 related coefficient (R) 0.9847 |
Table 2 unit, ℃
| Sequence number measured value predicted value residual error | Sequence number measured value predicted value residual error | Sequence number measured value predicted value residual error |
| ??1????68.4????67.7???0.7 ??2????80.5????79.3???1.2 ??3????65.2????65.5???-0.3 ??4????79.3????79.1???0.2 | ??5????75.9????75.3????0.6 ??6????78.7????77.6????1.1 ??7????71.1????72.0????-0.9 ??8????56.8????57.9????-1.1 | ??9????78.6????78.8????-0.2 ??10???72.3????71.7????0.6 ??11???73.9????74.6????-0.7 ??12???76.7????77.3????-0.6 |
| ? d??????????????????????????????????????????????????????????????????????????????????????????????????0.05 ??SEP?????????????????????????????????????????????????????????????????????????????????????????????????0.79 ??R???????????????????????????????????????????????????????????????????????????????????????????????????0.9948 | ||
| ??t???????????????????????????????????????????????????????????????????????????????????????????????????0.2182 ??t (0.05，11)??????????????????????????????????????????????????????????????????????????????????????????1.7959 | ||
The mm of table 3 unit
2/ s
| Sequence number measured value predicted value residual error | Sequence number measured value predicted value residual error | Sequence number measured value predicted value residual error |
| ??1????1.626???1.654??-0.028 ??2????1.627???1.603??0.024 ??3????1.726???1.714??0.012 ??4????1.526???1.563??-0.037 ??5????1.754???1.747??0.007 ??6????1.539???1.516??0.023 ??7????1.696???1.731??-0.035 ??8????1.732???1.750??-0.018 ??9????1.644???1.618??0.026 ??10???1.780???1.814??-0.034 ??11???1.773???1.760??0.013 ??12???1.881???1.874??0.007 ??13???2.024???2.009??0.015 | ??14???1.784??1.866???-0.082 ??15???1.773??1.761???0.012 ??16???1.723??1.741???-0.018 ??17???1.743??1.762???-0.019 ??18???1.838??1.798???0.040 ??19???1.663??1.667???-0.004 ??20???1.747??1.725???0.022 ??21???1.930??1.966???-0.036 ??22???1.817??1.800???0.017 ??23???1.762??1.761???0.001 ??24???1.927??1.929???-0.002 ??25???1.768??1.759???0.009 ??26???1.988??1.966???0.022 | ??27????1.886??1.898????-0.012 ??28????1.841??1.832????0.009 ??29????1.784??1.776????0.008 ??30????1.758??1.742????0.016 ??31????1.951??1.966????-0.015 ??32????1.970??1.984????-0.014 ??33????1.987??1.997????-0.010 ??34????1.750??1.746????0.004 ??35????1.690??1.706????-0.016 ??36????1.692??1.705????-0.013 |
| Standard deviation (SEC) 0.024 related coefficient (R) 0.9808 |
The mm of table 4 unit
2/ s
| Sequence number measured value predicted value residual error | Sequence number measured value predicted value residual error | Sequence number measured value predicted value residual error |
| ??1?????1.789????1.800???-0.011 ??2?????1.800????1.799???0.001 ??3?????1.665????1.644???0.021 ??4?????1.516????1.526???-0.010 | ??5????1.769??1.745???0.024 ??6????1.889??1.915???-0.026 ??7????1.664??1.683???-0.019 ??8????1.982??2.005???-0.023 | ?9?????1.696????1.702???-0.006 ?10????1.749????1.737???0.012 ?11????1.691????1.708???-0.017 |
| ? d???????????????????????????????????????????????????????????????????????????????????????????????????-0.005 ??SEP??????????????????????????????????????????????????????????????????????????????????????????????????0.018 ??R????????????????????????????????????????????????????????????????????????????????????????????????????0.9916 | ||
| ??t????????????????????????????????????????????????????????????????????????????????????????????????????1.0189 ??t (0.05，10)???????????????????????????????????????????????????????????????????????????????????????????????????????1.8125 | ||
The g/cm of table 5 unit
3
| Sequence number density actual density prediction residual | Sequence number density actual density prediction residual |
| ???1????0.7312????0.7317?????-0.0005 ???2????0.7507????0.7456?????0.0051 ???3????0.7413????0.7365?????0.0048 ???4????0.7480????0.7488?????-0.0008 ???5????0.7354????0.7387?????-0.0033 ???6????0.7360????0.7354?????0.0006 ???7????0.7504????0.7457?????0.0047 ???8????0.7448????0.7421?????0.0027 ???9????0.7441????0.7431?????0.0010 ???10???0.7521????0.7530?????-0.0009 ???11???0.7485????0.7473?????0.0012 ???12???0.7471????0.7484?????-0.0013 ???13???0.7334????0.7366?????-0.0032 ???14???0.7481????0.7493?????-0.0012 ???15???0.7541????0.7537?????0.0004 ???16???0.7569????0.7534?????0.0035 ???17???0.7434????0.7422?????0.0012 ???18???0.7406????0.7423?????-0.0017 ???19???0.7572????0.7558?????0.0014 ???20???0.7635????0.7623?????0.0012 ???21???0.7413????0.7418?????-0.0005 ???22???0.7438????0.7463?????-0.0025 ???23???0.7365????0.7404?????-0.0039 ???24???0.7433????0.7460?????-0.0027 ???25???0.7523????0.7557?????-0.0034 ???26???0.7442????0.7455?????-0.0013 ???27???0.7480????0.7487?????-0.0007 ???28???0.7432????0.7413?????0.0019 | ????29????0.7424?????0.7456????-0.0032 ????30????0.7481?????0.7487????-0.0006 ????31????0.7415?????0.7411????0.0004 ????32????0.7476?????0.7459????0.0017 ????33????0.7444?????0.7421????0.0023 ????34????0.7600?????0.7559????0.0041 ????35????0.7671?????0.7708????-0.0037 ????36????0.7637?????0.7609????0.0028 ????37????0.7608?????0.7574????0.0034 ????38????0.7505?????0.7505????0.0000 ????39????0.7601?????0.7583????0.0018 ????40????0.7544?????0.7541????0.0003 ????41????0.7520?????0.7505????0.0015 ????42????0.7483?????0.7467????0.0016 ????43????0.7393?????0.7412????-0.0019 ????44????0.7495?????0.7480????0.0015 ????45????0.7467?????0.7457????0.0010 ????46????0.7474?????0.7482????-0.0008 ????47????0.7437?????0.7460????-0.0023 ????48????0.7469?????0.7503????-0.0034 ????49????0.7432?????0.7422????0.0010 ????50????0.7510?????0.7504????0.0006 ????51????0.7735?????0.7727????0.0008 ????52????0.7850?????0.7899????-0.0049 ????53????0.7820?????0.7833????-0.0013 |
| ????SEC?????????????????????????0.0024 ????R???????????????????????????0.9753 |
The g/cm of table 6 unit
3
Sequence number measured value predicted value residual error
1???????????0.7318?????????0.7272???????0.0046
2???????????0.7428?????????0.7438???????-0.0010
3???????????0.7601?????????0.7565???????0.0036
4???????????0.7459?????????0.7476???????-0.0017
5???????????0.7621?????????0.7649???????-0.0028
6???????????0.7414?????????0.7364???????0.0050
7???????????0.7500?????????0.7472???????0.0028
8???????????0.7393?????????0.7425???????-0.0032
9???????????0.7443?????????0.7478???????-0.0035
10??????????0.7453?????????0.7446???????0.0007
11??????????0.7697?????????0.7641???????0.0056
12??????????0.7632?????????0.7613???????0.0019
13??????????0.7533?????????0.7525???????0.0008
14??????????0.7759?????????0.7735???????0.0024
d??????????????????????????????????????0.0011
SEP?????????????????????????????????????0.0033
R???????????????????????????????????????0.9693
t???????????????????????????????????????1.2233
T
(0.05，13)??????????????????????????????1.7709
Claims (8)
1, the method for a kind of gas chromatography and mass spectrometer coupling prediction crude oil fractions character comprises the steps:
(1) the crude oil fractions sample of the various pre-mensuration of collection, with the character of standard method working sample, the character of institute's working sample is identical with prediction character,
(2) as follows the cut sample of collecting is set up forecast model:
A) to the sample of each collection, get in the injector of 0.05～0.5 microlitre injection gas chromatography, after chromatographic resolution, enter mass spectrometer,
B) according to total ions chromatogram that look-the matter combined instrument provides, determining the retention time scope of prediction cut, again according to the mass-to-charge ratio analyst coverage of the selected mass spectrogram of retention time scope, and is that 57 peak is a reference peaks with mass-to-charge ratio in this scope, obtain the relative abundance at other relative datum peak, peak
C) the relative abundance value of each mass-to-charge ratio in the mass spectrogram of each sample is formed the X matrix,
D) the property testing value of each sample correspondence is formed the Y matrix,
E) with partial least square method with Y matrix and the interrelated analysis of X matrix, obtain the relational matrix with X matrix Y matrix, set up forecast model,
(3) with crude oil fractions sample to be measured by (2) step a, b method try to achieve the relative abundance value, the substitution forecast model obtains the property prediction value of sample.
2, in accordance with the method for claim 1, it is characterized in that described crude oil fractions is selected from gasoline fraction, diesel oil distillate, kerosene distillate or heavy distillate.
3, in accordance with the method for claim 1, it is characterized in that the crude oil fractions character of predicting comprises density, viscosity, index of refraction, aniline point and/or pour point.
4, in accordance with the method for claim 1, it is characterized in that the forecast model described in (2) step is set up is finished by computing machine.
5, in accordance with the method for claim 1, it is characterized in that described gas chromatograph is selected from capillary chromatography, mass spectrometer is selected from quadrupole mass spectrometer.
6, in accordance with the method for claim 1, when it is characterized in that described crude oil fractions is selected from gasoline fraction, the mass-to-charge ratio distribution range of choosing is 41.0～200.0 atomic mass units.
7, in accordance with the method for claim 1, when it is characterized in that described crude oil fractions is selected from kerosene distillate, the mass-to-charge ratio distribution range of choosing is 41.0～250.0 atomic mass units.
8, in accordance with the method for claim 1, when it is characterized in that described crude oil fractions is selected from diesel oil distillate, the mass-to-charge ratio distribution range of choosing is 41.0～350.0 atomic mass units.
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