CN100425975C - Method for measuring character data of gasoline from near infrared light spectrum - Google Patents

Method for measuring character data of gasoline from near infrared light spectrum Download PDF

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CN100425975C
CN100425975C CNB2004100711194A CN200410071119A CN100425975C CN 100425975 C CN100425975 C CN 100425975C CN B2004100711194 A CNB2004100711194 A CN B2004100711194A CN 200410071119 A CN200410071119 A CN 200410071119A CN 100425975 C CN100425975 C CN 100425975C
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gasoline
value
numerical value
character data
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许育鹏
褚小立
袁洪福
陆婉珍
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The present invention relates to a method for measuring the property data of gasoline by a near infrared spectrum, which comprises the following steps: (1) the near infrared spectrum of a gasoline sample to be measured is measured to calculate the corresponding spectral peak areas of the following absorption wavebands in a spectrogram: 1, the C-H absorption band of a benzene ring of 872.8 to 879.8 nm, 2. the C-H absorption band of methyl of 904.8 to 907.8 nm and 909.8 to 916.8 nm, 3. the C-H absorption band of methylene of 931.8 to 934.8 nm, 4. the C-H absorption band of alkenyl of 894.8 to 898.8 nm; the encoding value of the sample is obtained by calculating the peak area value of each band. (2) the encoding value of the sample to be measured is compared with the encoding value of a sample in a sample database, and the property data of the sample to be measured is obtained by the property data of the database sample corresponding to the sample to be measured. In the method, a calibration model of the sample doesn't need to be established, and property data such as an octane value, etc. of the gasoline sample is analyzed and predicted precisely and rapidly; the method is suitable for online analysis and control in production.

Description

Method by the near infrared ray character data of gasoline
Technical field
The present invention is the assay method of character data of gasoline, specifically, is the method that a kind of characteristic parameter of the near infrared spectrogram that utilizes gasoline sample is measured character data of gasoline, particularly octane value.
Background technology
Octane number is the index of the tolerance gasoline capability of antidetonance, and its size directly affects the performance of motor petrol.Increase octane number with the method for economical rationality and will produce huge economic benefit in oil refining process, people are from raw material, catalyzer, and aspects such as technology are constantly explored and are studied, and attempt to find the optimal path of raising octane number.Therefore, the measuring method of research octane number to the production of gasoline with use all with significant.
At present, octane value standard determination method ASTM D adopts ASTM-CFR octane number testing machine stand assay method, China adopts the standard method of test with ASTM D equivalence: GB/T 5487-1995 has stipulated the determination method of organon octane number, and GB/T 503-1995 has stipulated the determination method of motor method octane number.But, ASTM-CFR octane number testing machine stand assay method the production control of gasoline with use in be subjected to certain limitation: (1) test speed is slow, and an octane value is measured and needed more than 1 hour at least, can not in time feed back and carry out the production optimal control; (2) because the ASTM-CFR octane number testing machine is bulky, need special laboratory, be unfavorable for that on-the site analysis uses; (3) operation and maintenance expense height, the cost of equipment height needs continuous maintenance in the use; (4) feature of environmental protection is poor, and the sample consumption of test is big, needs the 500ml gasoline sample approximately, and measuring process exists volatilization loss and severe contamination.
Advantages such as it is fast that near-infrared spectral analytical method has speed, and precision height and expense are low have been widely used in measuring the octane value of gasoline, and have produced good social benefit and economic benefit thus.The spectrum of near-infrared spectral analysis technology by known sample is related with composition or character, sets up calibration model with the multivariate calibration methods in the Chemical Measurement, predicts the composition or the character of unknown sample then according to the spectrum of model and unknown sample.Disclose a kind of productive unit optimal control method as US5490085, this method is selected wave number 4800～4000cm -1The near infrared absorption wave spectrum of scope working sample, by its spectral data by setting up multiple regression analysis, the near infrared spectral data of working sample is associated with its octane value, obtain the octane value of sample, and have the production run of predetermined octane value product by the sample octane value control of prediction.
But the broader applications of above-mentioned near-infrared spectral analysis technology are subjected to the restriction of modelling and maintenance.When this showed with near-infrared spectrum analysis mensuration octane number, owing to be subjected to the influence of raw material variation and processing technology, gasoline composition and variation thereof be complexity very.Form when differing greatly when gasoline, need set up different models respectively, set up the workload of model and very expensive it.At present, the method for also useful non-homing method prediction product property discloses a kind of prediction product property as US6070128, as the method for octane number, vapour pressure, gum level, sulfur content and other content of material.This method adopts the various character of contiguous index method prediction product.At first set up database by collecting a large amount of samples, each storehouse sample all has the various product property data of measuring with standard method, the ir data of the sample m that measures under similarity condition in the ir data of measuring at 600～2600nm place with sample and the storehouse calculates and is close to index then, and the minimal index used with determining the prediction product property in advance compared, choose the storehouse sample of the contiguous index of those correspondences less than minimal index, the average of the product property data that it is corresponding is the predicted value of the character data of unknown sample.This method is when the prediction octane number, and the characteristic measurement wavelength of choosing is more, reaches 17 wave bands, and each about 10～20nm in wave band wavelength interval.Therefore, calculating contiguous index, when choosing the storehouse sample and carrying out the product property prediction, the characteristic peak of near infrared spectrogram of determining sample seems complicated, loaded down with trivial details especially to determine calculating parameter.
Summary of the invention
The purpose of this invention is to provide a kind of by the near infrared ray character data of gasoline, the method of octane value particularly, this method need not be set up calibration model, and directly by the character data of near infrared wave spectrum characteristic absorption section parameter prediction gasoline sample, finding speed is fast, precision is high.
The method of the near infrared ray character data of gasoline that the inventive method provides comprises the steps:
(1) measures the near infrared spectrum of gasoline sample to be measured, calculate the spectrum peak area of following each absorption bands correspondence in the spectrogram: 1. phenyl ring C-H absorber portion, 872.8-879.8nm; 2. methyl C-H absorber portion, 904.8-907.8nm, 909.8-916.8nm; 3. methylene C-H absorber portion, 931.8-934.8nm; 4. thiazolinyl C-H absorber portion, 894.8-898.8nm; And calculate the coding numerical value of sample by each section peak area value,
(2) testing sample is encoded sample in numerical value and the sample data storehouse coding numerical value relatively, obtain the character data of testing sample by the character data of corresponding with it storehouse sample.
The present invention is the coding numerical value of Parameter Calculation sample with the characteristic peak area of four near infrared absorption wave bands of gasoline sample, and this numerical value is corresponding with the character data of this sample, sets up the database of standard model thus.When unknown sample is tested, only need to calculate its coding numerical value by the near-infrared spectra diagram data of this unknown sample, can be by the character data of the properties of samples data prediction unknown sample that has corresponding encoded numerical value in the database, thereby need not set up the standard model calibration curve, saved the workload of setting up forecast model.In addition,, have the sample of corresponding encoded numerical value fast in the searching database, make the properties of samples data prediction simple, quick, accurate according to the coding numerical value that four near infrared characteristic absorption wave band spectrum peak areas are set up.
Embodiment
The spectrum peak area value that the inventive method is extracted four characteristic absorption wave bands of sample near infrared spectrum is a characteristic parameter, calculate its coding numerical value by characteristic parameter by formula, set up the corresponding relation of coding numerical value and properties of samples data, and predict the character data of specimen thus.At first, collect gasoline sample that various processing technology produces several, decide on institute's database construction design capacity size.Be generally and make prediction accurately, need choose each 200～500 of the gasoline samples that various technologies produce, amount to about 200～1000 of gasoline sample data volume.Test the character data of each sample earlier with standard method, test its near infrared spectrogram again, calculate the coding numerical value of each sample by selected four characteristic peak areas, each coding numerical value is corresponding one by one with the SOME PROPERTIES data of this sample, thus, set up the topological database of sample encoded numerical value and its character data, measure the near infrared spectrum of unknown sample then, calculate the spectrum peak area value of four characteristic absorption wave bands, try to achieve its coding numerical value thus, by character data at the properties of samples data prediction unknown sample of database retrieval and unknown sample respective coding data.
In the inventive method, the formula of (1) described calculation sample coding numerical value of step (CODE) is:
CODE(i)＝(α i-1)×500 3+(Z i-1)×500 2+(Y i-1)×500+X i
In the formula, X i, Y i, Z i, α iRespectively be sample i at 1.～4. spectrum peak area value of absorption bands.
When the coding numerical value of a certain sample in the sample data storehouse was identical with testing sample coding numerical value, then the character data of this sample was the character data of testing sample.
When not having the sample not identical in the sample data storehouse with testing sample coding numerical value, then getting search length is 1～3, retrieval and the contiguous sample of testing sample coding numerical value in the sample data storehouse, again by contiguous sample at 1.～4. spectrum peak area value of absorption bands, calculate the character data of testing sample by following formula:
Pi = Σ i = 1 n ( P i × d i ) / Σ i = 1 n d i
Wherein d i = ( X i - X u ) 2 + ( Y i - Y u ) 2 + ( Z i - Z u ) 2 + ( α i - α u ) 2
In the formula, n is the contiguous storehouse sample number that searches, P iIt is the character data of i contiguous storehouse sample;
X i, Y i, Z i, α iBe i contiguous storehouse sample at 1.～4. spectrum peak area value of absorption bands, X u, Y u, Z u, α uFor testing sample at 1.～4. spectrum peak area value of absorption bands.
Described search length r is the contiguous storehouse sample chosen and the testing sample absolute value in the spectrum peak area difference of same absorbent wave band.Promptly
r＝|M j-M u|
In the formula, M jFor contiguous storehouse sample j at 1.～4. spectrum peak area value of absorption bands, M jBe X j, Y j, Z jOr α j, M uBe the spectrum peak area value of testing sample at the absorption bands identical, M with j uBe X u, Y u, Z uOr α u
The suitable gasoline sample of measuring of the inventive method is reformed gasoline or catalytically cracked gasoline, also can be the gasoline component that other technology produces, as gasoline alkylate, coker gasoline etc.
When the gasoline of measuring is reformed gasoline or gasoline alkylate because wherein the content of alkene is few, during calculation sample coding numerical value, but the 4. the spectrum peak area assignment of wave band be zero, to simplify calculation procedure.
The sample size that is used to set up the sample data storehouse in the inventive method can be 100～10000, and preferred 200～1000, sample should comprise the gasoline sample that various technologies produce in the storehouse, and the quantity of every kind of gasoline sample needs 100～500 approximately.
Coding method of the present invention is applicable to the various character datas of measuring gasoline sample, as octane number, density, vapour pressure, sulfur content, gum level or arene content.
Below by example in detail the present invention, but the present invention is not limited to this.
Set up the sample data storehouse: adopt NIR-3000 near-infrared analyzer (production of the virtuous instrument of Beijing English Industrial Co., Ltd.), with the air is reference, under 22 ± 5 ℃ condition, measure the near infrared spectrum of 208 reformed oil samples and 476 catalytically cracked gasoline samples, again by the research octane number (RON) (RON) of GB/T 5487 method working samples, by the motor octane number of GB/T 503 method working samples.Calculating the coding numerical value of each sample by the inventive method by the spectrum peak area value of described four absorption bandses, is that record data are set up database by coding numerical value and its corresponding octane value, the octane value of unknown sample is predicted being used for.
Example 1
This example is predicted the octane value that generates oil samples of reforming by institute's database construction, measure the near infrared spectrum of each reformed oil sample to be measured earlier, wherein the 4. the peak area assignment of wave band be zero, by 1. described～3. the spectrum peak area value of absorption bands calculates the coding numerical value of each sample.Retrieval has the sample of corresponding encoded numerical value in database then, and search length is 3, and the octane value of the formula prediction testing sample that is provided by the present invention by the octane value of sample the results are shown in Table 1 again.
As shown in Table 1, t check numbers illustrated between the result that the inventive method and GB/T 5487-1995 actual measurement obtains does not have significant difference between the two, and the difference between the inventive method and standard testing method is better than the repeatability of GB/T 5487-1995 gasoline research method octane number determination law regulation.
Example 2
This example is predicted the octane value of catalytically cracked gasoline sample by institute's database construction.Measure earlier the near infrared spectrum of each catalytically cracked gasoline sample to be measured, by 1. described～4. the spectrum peak area value of absorption bands calculates the coding numerical value of each sample.Retrieval has the sample of corresponding encoded numerical value in database then, and search length is 3, and the octane value of the formula prediction testing sample that is provided by the present invention by the octane value of sample the results are shown in Table 2 again.
As shown in Table 2, do not have significant difference between the t check numerical value between the result that the inventive method and GB/T 5487-1995 and GB/T 503-1995 actual measurement obtain, and the difference between the inventive method and standard testing method is better than the repeatability of GB/T 5487-1995 gasoline research method knock rating method and GB/T 503-1995 gasoline motor octane number determination method regulation.
Example 3
Under the same measured condition, to catalytically cracked gasoline and reformed oil sample, METHOD FOR CONTINUOUS DETERMINATION is 6 times respectively, and by institute's database construction the octane value of sample is predicted, the results are shown in Table 3.
As known from Table 3, the sample octane value that gets of the inventive method forecasting institute has better repeatability.
Table 1
Figure C20041007111900081
Table 2
Table 3
Figure C20041007111900092

Claims (7)

1, a kind of method by the near infrared ray character data of gasoline comprises the steps:
(1) measures the near infrared spectrum of gasoline sample to be measured, calculate the spectrum peak area of following each absorption bands correspondence in the spectrogram: 1. phenyl ring C-H absorber portion, 872.8-879.8nm; 2. methyl C-H absorber portion, 904.8-907.8nm, 909.8-916.8nm; 3. methylene C-H absorber portion, 931.8-934.8nm; 4. thiazolinyl C-H absorber portion, 894.8-898.8nm; And calculate the coding numerical value of sample by each section peak area value, the formula of described calculation sample coding numerical value is:
CODE(i)＝(α i-1)×500 3+(Z i-1)×500 2+(Y i-1)×500+X i
In the formula, X i, Y i, Z i, α iRespectively be sample i at 1.～4. spectrum peak area value of absorption bands,
(2) testing sample is encoded sample in numerical value and the sample data storehouse coding numerical value relatively, obtain the character data of testing sample by the character data of corresponding with it storehouse sample.
2, in accordance with the method for claim 1, it is characterized in that then the character data of this sample is the character data of testing sample when the coding numerical value of a certain sample in the sample data storehouse is identical with testing sample coding numerical value.
3, in accordance with the method for claim 1, it is characterized in that when not having the sample not identical in the sample data storehouse with testing sample coding numerical value, then getting search length is 1～3, retrieval and the contiguous sample of testing sample coding numerical value in the sample data storehouse, again by contiguous sample at 1.～4. spectrum peak area value of absorption bands, calculate the octane value of testing sample by following formula:
Pi = Σ i = 1 n ( P i × d i ) / Σ i = 1 n d i
Wherein d i = ( X i - X u ) 2 + ( Y i - Y u ) 2 + ( Z i - Z u ) 2 + ( α i - α u ) 2
In the formula, n is the contiguous storehouse sample number that searches, P iIt is the character data of i contiguous storehouse sample;
X i, Y i, Z i, α iRespectively be i contiguous storehouse sample at 1.～4. spectrum peak area value of absorption bands, X u, Y u, Z u, α uRespectively be testing sample at 1.～4. spectrum peak area value of absorption bands.
4, in accordance with the method for claim 1, it is characterized in that described gasoline sample is reformed gasoline or catalytically cracked gasoline.
5, in accordance with the method for claim 1, when it is characterized in that described gasoline is reformed gasoline, during calculation sample coding numerical value, the 4. wave band spectrum peak area assignment be zero.
6, in accordance with the method for claim 1, the quantity that it is characterized in that sample in the described sample data storehouse is 100～10000.
7, in accordance with the method for claim 1, it is characterized in that described character data of gasoline is octane value, density, vapour pressure, sulfur content, gum level or the arene content of gasoline.
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