CN105021747B - The method being made up of proton nmr spectra prediction diesel oil race - Google Patents
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Abstract
A kind of method being made up of proton nmr spectra prediction diesel oil race, comprises the following steps：（1）Various diesel samples are collected, and race's composition of diesel samples is determined with standard method,（2）Determine the proton nmr spectra for each diesel samples collected, spectrogram is subjected to differential process, take chemical shift associated with the race's composition measured with standard method for the peak intensity in 7.4~8.0ppm and 0~4.0ppm spectrums area, calibration model is established with PLS（3）The proton nmr spectra of diesel samples to be measured is determined, spectrogram is subjected to differential process, takes chemical shift to compose the peak intensity in area for 7.4~8.0ppm and 0~4.0ppm and substitutes into calibration model, obtain race's composition of diesel samples to be measured.This method analyze speed is fast, and test is accurate, easy to operate.
Description
Technical field
The present invention is a kind of method being made up of diesel oil nuclear magnetic resoance spectrum prediction diesel oil race, is a kind of utilization specifically
The method that the proton nmr spectra of diesel samples predicts its race composition.
Background technology
With the development of World Economics, more the coming of diesel applications the more, causes diesel oil demand increasing, and diesel oil is made
For a kind of important oil product, its quality well directly affects its burning and performance soon.Diesel oil is that had not by various
With the mixture of the hydro carbons composition of C-H groups, the height of arene content directly affects diesel cetane-number and its burning in diesel oil
Performance, and different degrees of influence, the especially heavy aromatics in diesel oil are produced to environment.The content of cycloalkane in diesel oil
It has impact on the low temperature flow of diesel oil.In addition, having the content of research and utilization cycloalkane to associate the property of diesel oil, such as viscosity, incline
Point, flash-point etc..Therefore, while other quality index of diesel oil are improved, arene content is all included in by many countries and regions
The quality control index of diesel product.Domestic and international widely used detection means mainly has column chromatography chromatogram method, solid phase extraction at present
Take-gas chromatography and high performance liquid chromatography etc..
These methods generally determine cumbersome, it is necessary to take a long time, and are adapted to lab analysis, such as column chromatography chromatogram
Method（LC）, i.e., classical liquid chromatography, this method GRR is all poor, and needs to consume substantial amounts of rinse solvent,
Analytical cycle is grown, therefore can not meet the needs of Fast Evaluation, when occurring abnormal in especially producing at the scene, conventional method
It is difficult to provide data in time, cause process units to adjust in time, made troubles to production.Therefore, it is necessary to establish one kind
The method for quick and precisely analyzing diesel oil race composition.
" exploration of analysis method of arene content in diesel oil "（《Petroleum refining and chemical industry》, 4 phases in 2011, page 60~62）
In one text, several analysis methods of arene content in diesel oil are described, but the analysis method complex operation mentioned in text is numerous
It is trivial, take longer.
" arene content near infrared spectroscopy measure diesel oil " text（《Petrochemical industry》, Vol.28No.4 1999,263
~265）In, the arene content in diesel oil is determined using near infrared spectroscopy, establishes quick measure aromatic content of diesel oil
Analysis method.Prediction result is coincide very well with standard method measurement result, but the model that this method is established use only 30
Individual diesel oil sample, can not accurate evaluation model quality.
" adsorption chromatography/mass spectrography qualitative analysis diesel oil hydro carbons composition "（《Petrochemical industry》, 1999 volume 28,835-
Page 838）In one text, diesel oil is divided into by saturated hydrocarbons and aromatic hydrocarbons two parts using sloid-liq-uid adsorption post filling gel, then in conjunction with GC/
MS combined instruments are analyzed, and determine naphthene content in diesel oil.But when being separated to diesel component, need to use largely has
Machine reagent such as pentane and dichloromethane etc., and separation and continuous mode are cumbersome, and the duration is longer.
The content of the invention
It is an object of the invention to provide a kind of method being made up of proton nmr spectra prediction diesel oil race, this method analysis
Speed is fast, and test is accurate, easy to operate.
The method provided by the invention being made up of proton nmr spectra prediction diesel oil race, comprises the following steps：
（1）Various diesel samples are collected, and race's composition of diesel samples is determined with standard method,
（2）The proton nmr spectra for each diesel samples collected is determined, spectrogram is subjected to differential process, takes chemical potential
Move composed for 7.4~8.0ppm and 0~4.0ppm area peak intensity it is associated with the race's composition measured with standard method, with partially most
Small square law establishes calibration model,
（3）The proton nmr spectra of diesel samples to be measured is determined, spectrogram is subjected to differential process, it is 7.4 to take chemical shift
The peak intensity in~8.0ppm and 0~4.0ppm spectrums area substitutes into calibration model, obtains race's composition of diesel samples to be measured.
The inventive method, which uses, operates relatively simple magnetic nuclear resonance method, by selecting suitable characteristic spectrum area to predict
Diesel oil race forms（Including alkane, the cycloalkane of different number of rings, different number of rings arene content）, can be the processing of diesel oil, adjust
With quickly and accurately race's predicted composition data are provided.
Brief description of the drawings
Fig. 1 is the proton nmr spectra for 5 diesel samples that the present invention measures.
Fig. 2 concentrates monocyclic naphthenes measured value figure related to predicted value for present invention checking.
Fig. 3 concentrates total cycloalkane measured value figure related to predicted value for present invention checking.
Fig. 4 concentrates polycyclic aromatic hydrocarbon measured value figure related to predicted value for present invention checking.
Fig. 5 concentrates mononuclear aromatics measured value figure related to predicted value for present invention checking.
Fig. 6 is the comparing result of the straight-run diesel oil race composition of the inventive method and mass spectrometric determination.
Fig. 7 is the comparing result of the hydrofining diesel oil race composition of the inventive method and mass spectrometric determination.
Fig. 8 is the comparing result of the finished diesel fuel race composition of the inventive method and mass spectrometric determination.
Fig. 9 is the comparing result of the straight run Cui Chai mixed diesels race composition of the inventive method and mass spectrometric determination.
Figure 10 is the comparing result for being hydrocracked diesel oil race composition of the inventive method and mass spectrometric determination.
Embodiment
The inventive method is made up of the characteristic spectrum area of the larger proton nmr spectra of correlation selection with diesel oil race, will
The peak intensity of characteristic spectrum area and the different hydrocarbon in the diesel oil race composition that standard method measures（The cycloalkanes of alkane, different number of rings
The aromatic hydrocarbons of hydrocarbon, different number of rings）Content is associated, and the calibration model of above-mentioned hydrocarbon is established by multiple regression analysis, then passes through correction
Model, predict that its race forms by the peak intensity of characteristic spectrum area in the proton nmr spectra of diesel samples to be measured.
Proton nmr spectra reflection is in the presence of external magnetic field, and resonance jump occurs between magnetic energy level for proton in sample
The phenomenon moved.There is one-to-one relationship in nmr spectrum signal and molecular structure, the spike in different sections is main on spectrogram
There are the proton peaks such as methyl, methylene, cycloalkanes, aromatic hydrocarbons in the functional group of representative.
In above-mentioned spectrogram, signal intensity（Peak intensity）It is stronger with concentration direct proportionality, concentration more high RST.This hair
The peak intensity in bright method selected characteristic spectrum area is associated with race's composition that diesel samples are determined with standard method, establishes straightening die
Type.Institute's positive model for school building has preferable reliability.
It is more to establish the quantity of sample selected by calibration model, institute's established model is more accurate, reliable.In practical operation, to reduce
Workload, it is general to choose right quantity and the sample of be possible to predicted value be covered, preferably represent different types of diesel oil
Sample size be 200~400.
The inventive method, it is excellent when establishing calibration model and predicting that its race forms using testing sample proton nmr spectra
Choosing pre-processes to spectrogram, and the method that differential process is carried out to spectrogram is preferably first differential, second-order differential or first differential
And second-order differential.
The present invention uses PLS（PLS）Calibration model is established, i.e., by diesel samples after processing in spectrogram
The peak intensity composition X matrix of characteristic spectrum area, the race that standard method is measured form to form Y matrixes（Concentration matrix）, by Y matrixes
With X matrix PLS（PLS）It is associated, establish calibration model.
In the inventive method, the diesel oil race composition surveyed is saturated hydrocarbons and arene content, and wherein saturated hydrocarbons includes alkane
With each number of rings cycloalkane, aromatic hydrocarbons is the aromatic hydrocarbons of each number of rings.Described each number of rings cycloalkane and the number of rings of each number of rings aromatic hydrocarbons refer to list
Ring, bicyclic and three rings.By surveyed diesel oil race composition for alkane, each number of rings cycloalkane, each number of rings arene content, it is every kind of
Hydro carbons is both needed to establish single calibration model.Establishing model method is：By the X matrix that characteristic spectrum area peak intensity forms with it is a certain
The Y matrix correlations connection of hydrocarbon content composition, establish the calibration model of the hydrocarbon content, such as matrix correlation with alkane composition
Connection, obtain predicting the calibration model of alkane, join with the matrix correlation of bicyclic cycloalkane composition, obtain predicting bicyclic cycloalkane
Calibration model, by that analogy, establish the prediction calibration model of various hydro carbons respectively, including alkane, monocyclic naphthenes, double
Ring cycloalkane, tricyclic naphthenes hydrocarbon, total cycloalkane, mononuclear aromatics, double ring arene, thrcylic aromatic hydrocarbon, polycyclic aromatic hydrocarbon, total aromatic hydrocarbons it is pre-
Survey calibration model.
For examine calibration model accuracy, typically by with standard method measure race form sample be divided into calibration set and
Checking collection.Calibration set sample size is more, and representative, i.e. race's composition of calibration set sample should cover all predictions
Race composition.And verify that collection is then randomly selected, and the accuracy of calibration model is verified using its sample as unknown sample.Test
Card collection sample size is less.
In the inventive method, preferably with the core for the nmr determination diesel samples that resonant frequency is 58 ± 0.5MHz
Magnetic resonance hydrogen is composed.
The NMR that resonant frequency is 58 ± 0.5MHz is low-field nuclear magnetic resonance analyzer, can directly to crude oil or
Diesel samples carry out adopting spectrum, are not required to be pre-processed with diluents such as deuterochloroforms, without addition tetramethylsilane（TMS）
Internal standard compound is done, and selects peak intensity highest peak as thing is calibrated, methylene peak is generally in diesel samples, other peaks are successively
Distribution.
In order to match with modeling software, when stored, abscissa identifies scale and replaces chemical potential with data points spectrogram
Shifting value, ordinate are peak intensity.Spectrogram abscissa identifies preferably 700~1000 points of the maximum of scale, i.e., is divided into abscissa
700~1000 parts.
Conversion relation such as formula between points and chemical displacement value（1）It is shown：
Formula（1）In, δ is the chemical displacement value at unknown peak, and X is that point value, A corresponding to unknown peak peak are tetramethyl
Silane（Chemical shift is 0）Corresponding point value, B are point value corresponding to a chemical shift.
In the inventive method, the hydrogen nuclear magnetic resonance time spectrum of organic sample is determined, the sum of preferred acquisition sample spot is 2000
~8000, sample rate is 2174~4346Hz.
The sum of the collection sample spot refers to the free induction decay FID that NMR uses（Free
Induction Decay）The sampling number of signal.Its size is merely able to reflect the signal validity for catching sample, collection
Sample spot sum is more much truer, but too much, the noise signal brought is also more.Sample rate is per second from continuous signal
Extract and form the number of samples of discrete signal, unit is hertz（Hz）.
Diesel samples are preferably preheated to 20~40 DEG C by the inventive method, then determine its proton nmr spectra.During measure,
The amount of diesel samples used is preferably 2~5mL.
The standard method of the inventive method measure diesel oil race composition is SH/T0606 standard methods.
With PLS（PLS）After establishing calibration model, pass through calibration standard deviation（RMSEC）With pre- mark
Quasi- deviation（RMSEP）Calibration model is evaluated.
Wherein RMSEC, RMSEP are respectively by formula（2）With（3）Calculate
yi,actualIn-calibration set, the standard method measured value of i-th of sample,
yi,predicted- positive model for school building to the predicted value of i-th of sample in calibration set,
The sample number of n-calibration set.
yj,actual- checking is concentrated, the standard method measured value of j-th of sample,
yj,predicted- checking is concentrated, the predicted value that j-th of sample is obtained by calibration model,
The sample number of m-checking collection.
The present invention is further described below by example, but the present invention is not limited thereto.
Using 58 ± 0.5MHz laboratories magnetic nuclear resonance analyzer of Qualion companies of Israel production in example（Model
For NMRS230022）The proton nmr spectra of determination sample.The operating condition of measure is：The total points 2048 of sampling, sample rate are
4346Hz, scan round number 8 times, system is in the sensing deamplification that gains freedom（Free Induction Decay,FID）
Afterwards, by zero padding（Zero Fill）, phasing（Phase Correction）, eliminate direct current caused by signal skew
（Remove Direct Current）, Fourier transformation（FFT）, base wavelet（Baseline Correction）Deng automatic place
Reason process, the frequency domain spectrogram after Fourier transformation is obtained, be the proton nmr spectra of sample.Spectrogram when stored, abscissa
Mark replaces chemical displacement value with data points, and points span is 0~700, and ordinate is peak intensity.In 700 points
Abscissa in, points corresponding to tetramethylsilane are 600, i.e. chemical shift is that points are 600,1 chemical potential corresponding to 0
Points are 50 corresponding to moving, and can be counted according to following formula by diesel oil characteristic peak（X）Calculate the chemical shift of characteristic peak（δ）：
Race's composition of each diesel samples, according to SH/T0606 midbarrel hydro carbons composition measuring methods --- mass spectrography, with admittedly
Phase extraction-gas chromatography is measured.
0.15mL diesel samples are taken, instill the solid-phase extraction column using silica gel as stationary phase, is rinsed and extracted with 150mL pentanes
Post is taken to obtain saturated hydrocarbon component, including the micro mononuclear aromatics of alkane, cycloalkane and doping, then with 150mL bis-
Chloromethanes rinses, and aromatic component is obtained, wherein containing monocyclic, bicyclic, polycyclic aromatic hydrocarbon.Calculate the saturated hydrocarbons and aromatic component obtained
Mass fraction, respectively with micro syringe inject sufficient amount sample carry out mass spectroscopy, obtain race's group of diesel samples
Into.
Example 1
Spectrogram is handled with first differential, the calibration model of diesel oil race composition proton nmr spectra is established and is verified.
（1）Formed with the race of standard method measure diesel samples
Different types of diesel samples totally 286 are collected, the race that each sample is determined with SH/T0606 methods forms, each group
Point content distribution scope is shown in Table 1.Representational 246 composition calibration sets of sample are collected, randomly select 40 samples as checking
Collection.
（2）Calibration model is established with calibration set sample
Diesel samples 3mL is taken, is preheated 10 minutes in 30 DEG C, its hydrogen nuclear magnetic resonance is determined with 58MHz magnetic nuclear resonance analyzers
Spectrum, wherein the spectrogram of 5 samples is shown in Fig. 1.
By the proton nmr spectra of 246 diesel samples, after being pre-processed with first differential, it is 7.4 to take chemical shift
~8.0ppm (spectrogram abscissa points be 230~200) and chemical shift be 0~4ppm (it is 400 that spectrogram abscissa, which is counted ,~
600) the peak intensity composition X matrix in area is composed, the race determined corresponding to sample by the methods of SH/T 0606 forms content and forms Y
(concentration) matrix, X matrix is associated with PLS (PLS) with Y matrixes, each establish a school per class hydrocarbon component
Positive model.The pertinent statistical parameters for establishing each hydrocarbon composition correction model are shown in Table 1.
（3）Verify the reliability of calibration model
40 diesel samples concentrated to checking, determine its proton nmr spectra, obtained spectrogram with the method for (2) step
After being pre-processed with first differential, the peak intensity that chemical shift is 7.4~8.0ppm and chemical shift is 0~4ppm spectrums area is taken
Degree, substitutes into each calibration model, obtains race's predicted composition value of diesel samples.Checking collection pertinent statistical parameters are shown in Table 1, wherein singly
The correlation of ring cycloalkane, total cycloalkane, polycyclic aromatic hydrocarbon and mononuclear aromatics content prediction value and the method measured values of SH/T 0606
Fig. 2~5 are seen successively.
Table 1
CR（Calibration set coefficient correlation）, SEC（Calibration set standard deviation）, PR（Checking collection coefficient correlation）, SEP（Pre- mark
Quasi- deviation）
Example 2
Spectrogram is handled with second-order differential, the calibration model of diesel oil race composition proton nmr spectra is established and is verified.
Diesel oil race composition calibration model is established by the method for example 1, the difference is that the nuclear-magnetism of the diesel samples of measure is total to
The hydrogen that shakes spectrum carries out second-order differential processing, then takes the peak that chemical shift is 7.4~8.0ppm and chemical shift is 0~4ppm spectrums area
Intensity, it is associated with the sample race composition determined with standard method, the calibration model of all kinds of hydrocarbon components is established, then pass through correction
Race's composition of model prediction checking collection each sample.
The pertinent statistical parameters established calibration model with calibration set sample and verified with checking collection sample are shown in Table 2.
Table 2
CR（Calibration set coefficient correlation）, SEC（Calibration set standard deviation）, PR（Checking collection coefficient correlation）, SEP（Pre- mark
Quasi- deviation）
Example 3
With single order and second-order differential processing spectrogram, calibration model and progress that diesel oil race forms proton nmr spectra are established
Checking.
Diesel oil race composition calibration model is established by the method for example 1, the difference is that the nuclear-magnetism of the diesel samples of measure is total to
The hydrogen that shakes spectrum first carries out first differential processing, then carries out second-order differential processing, and it is 7.4~8.0ppm and change then to take chemical shift
Displacement study is the peak intensity that 0~4ppm composes area, associated with the sample race composition determined with standard method, establishes all kinds of hydrocarbon groups
The calibration model divided, then predict that the race of checking collection each sample forms by calibration model.
The pertinent statistical parameters established calibration model with calibration set sample and verified with checking collection sample are shown in Table 3.
Table 3
CR（Calibration set coefficient correlation）, SEC（Calibration set standard deviation）, PR（Checking collection coefficient correlation）, SEP（Pre- mark
Quasi- deviation）
Example 4
This example illustrates that the present invention builds the adaptability of prediction diesel oil race composition calibration model.
Formed with mass spectrometric determination diesel samples race：The diesel samples in five kinds of different oil refining machining processes are collected,
Bavin mixed diesel is urged for straight-run diesel oil, hydrofining diesel oil, finished diesel fuel, straight run, is hydrocracked diesel oil.With SH/T0606 side
Method determines race's composition of diesel oil respectively.
Above-mentioned straight-run diesel oil, hydrofining diesel oil, finished diesel fuel, straight run urge bavin mixed diesel, are hydrocracked diesel oil originally
Race's composition result that the predicted value that inventive method obtains measures with mass spectrography is shown in Fig. 6~10 successively.
From Fig. 6~10, for different types of diesel oil, two kinds of assay methods obtain race's composition result and coincide very well.
Compared to mass spectrography, the inventive method finding speed is fast, and sample need not pre-process, and is more suitable for the quick analysis of oil product.
Claims (7)
1. a kind of method being made up of proton nmr spectra prediction diesel oil race, comprises the following steps：
(1) various diesel samples are collected, and race's composition of diesel samples is determined with standard method,
(2) proton nmr spectra for each diesel samples that measure is collected, differential process is carried out by spectrogram, takes the chemical shift to be
The peak intensity in 7.4~8.0ppm and 0~4.0ppm spectrums area is associated with the race's composition measured with standard method, uses offset minimum binary
Method establishes calibration model,
(3) determine the proton nmr spectra of diesel samples to be measured, spectrogram be subjected to differential process, take chemical shift for 7.4~
The peak intensity in 8.0ppm and 0~4.0ppm spectrums area substitutes into calibration model, obtains race's composition of diesel samples to be measured,
The diesel oil race composition surveyed is alkane, each number of rings cycloalkane, each number of rings arene content, determines diesel samples nuclear magnetic resonance
The resonant frequency of hydrogen spectrum is 58 ± 0.5MHz, and every kind of hydro carbons in the diesel oil race composition surveyed is both needed to establish single straightening die
Type.
2. in accordance with the method for claim 1, it is characterised in that the method that differential process is carried out to spectrogram is first differential, two
Rank differential or first differential and second-order differential.
3. in accordance with the method for claim 1, it is characterised in that determine the hydrogen nuclear magnetic resonance time spectrum of organic sample, collection is set
The sum of sample spot is 2000~8000, and sample rate is 2174~4346Hz.
4. in accordance with the method for claim 1, it is characterised in that the abscissa mark scale of the proton nmr spectra of measure is most
Big value is 700~1000 points.
5. in accordance with the method for claim 1, it is characterised in that the standard method of measure diesel oil race composition is marked for SH/T 0606
Quasi- method.
6. in accordance with the method for claim 1, it is characterised in that the temperature of measure diesel samples proton nmr spectra for 20~
40℃。
7. in accordance with the method for claim 1, it is characterised in that with the accuracy of checking collection sample evaluation calibration model.
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