CN106970039A - A kind of pipeline blending quantitative detecting method based on terahertz time-domain spectroscopy - Google Patents
A kind of pipeline blending quantitative detecting method based on terahertz time-domain spectroscopy Download PDFInfo
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Abstract
The invention discloses a kind of pipeline blending quantitative detecting method based on terahertz time-domain spectroscopy, the contaminated product quantitative detecting method comprises the following steps：The linear fit model expression of contaminated product volume fraction and ten groups of parameters, i.e., ten kinds contaminated product component volume fraction Quantitative Analysis Models are obtained by linear fit；Using the method for the optimization of co sinus vector included angle, the weights of ten groups of parameters are solved；The time domain impulse waveform of unknown volume fraction contaminated product sample is measured using terahertz time-domain spectroscopy instrument, and extracts ten kinds of parameter values of time domain impulse waveform；According to the weights of ten kinds of contaminated product component volume fraction Quantitative Analysis Models, and ten groups of parameters, ten kinds of parameter values of unknown volume fraction contaminated product sample are substituted into, contaminated product constituent concentration is obtained.This invention simplifies analysis process, detection difficulty is reduced, terahertz time-domain waveform analysis and utilization effect is improved, oil product time domain waveform parameter is enriched, improves accuracy of detection.
Description
Technical field
The present invention relates to terahertz time-domain spectroscopic technology field, more particularly to a kind of pipeline based on terahertz time-domain spectroscopy
Contaminated product quantitative detecting method.
Background technology
Oil is undoubtedly the important pillars of the national economy energy, is also main national strategy stockpile.With China
The steady lifting of international economy status, China's petroleum consumption steady growth in recent years.China consumes oil 4.55 hundred million within 2010
Ton, China in 2012 has turned into the maximum net import of oil state in the whole world, 5.43 hundred million tons of oil of consumption in 2015, it is contemplated that the year two thousand thirty stone
Oily demand reaches 6.7 hundred million tons.Therefore loss and accident during reducing petroleum transportation as far as possible and storing, with great warp
Ji and strategic importance.The major way that oil product over long distances, is in high volume transported is pipeline sequentially-fed, as improves pipeline using effect
Rate and a variety of delivery requirements of reply, oil products are conveyed into batch consecutive order according to plan.Different oil products are in same pipeline
Middle alternating sequence conveying, causes forward oil product and trailing oil product junction to produce the mixed contamination plug that can not ignore.Single sequential is conveyed,
It can produce up to several kilometers of long mixed contamination plugs.A large amount of mixed contamination plugs of constant flow must be detected accurately in pipeline.One
Aspect, the testing result of contaminated product core dumped can cause the incorrect processing of mixed contamination plug, cause the waste of oil product；On the other hand, it is wrong
Testing result more likely causes the mistake cutting of oil product in pipeline by mistake, causes different oil products in pipeline and oil storage tank to adulterate and dirty
Dye, produces huge economic losses and security incident.Therefore, the accurate detection of pipeline blending has great practical significance.
The method of common pipeline blending detection domestic and international at present includes：Densitometry, optical detecting method, ultrasound
Determine method, labelled atom determination method, capacitance detecting method, spectral chromatography detection method and THz wave detection method etc..
1st, densitometry is tracked detection to oil product in pipeline, is the main method implemented in actual production, but
The oil product of similar density is difficult to differentiate between, detection resolution is low.
2nd, optical detecting method determines the transparency and refractive index of oil product using the conventional optical region such as infrared, and sensitivity is high,
But easily by oil product impurity effect, it is very badly suited for the relatively low actual conditions of domestic oil product quality, at home in actual use
More problems, stability is poor, and maintenance difficulties are high.
3rd, ultrasonic measuring method detects the spread speed of ultrasonic wave in oil product, is highly prone to the influence of ultrasonic noise, detects
Precision is not high.
4th, labelled atom determination method carries out oil product detection, technology door by mixing radioisotopic method in oil product
Sill are high, and safety requirements is high, and can cause oil pollution.
5th, capacitance detecting method measurement oil product dielectric constant, measurement accuracy is low, electrification device is installed in product pipeline, safety
Property is poor.
6th, spectral chromatography detection method measurement oil product absorption spectrum and chromatographic fingerprint figure, precision are high, but pretreatment is complicated, measurement
Time is long, it is impossible to realize on-line monitoring.
7th, THz wave detection method has optical penetration strong, and photon energy is low, the features such as detection resolution is high, Neng Gouke
The problem of optical detecting method is easily by oil product impurity effect, probe vulnerable to pollution is taken, detection degree of safety is high, detects accuracy potentiality
Greatly.But Terahertz pipeline blending detection at present relies primarily on quantitative point of the traditional refractive index in Terahertz field, absorption coefficient etc.
Analysis method, calculates complicated, the petrol and diesel oil quantitative analysis degree of accuracy is low.
The content of the invention
The invention provides a kind of pipeline blending quantitative detecting method based on terahertz time-domain spectroscopy, this invention simplifies
Analysis process, reduces detection difficulty, improves terahertz time-domain waveform analysis and utilization effect, enriches oil product time domain waveform ginseng
Number, improves accuracy of detection, described below：
A kind of pipeline blending quantitative detecting method based on terahertz time-domain spectroscopy, the contaminated product quantitative detecting method includes
Following steps：
The linear fit model expression of contaminated product volume fraction and ten groups of parameters, i.e., ten kinds contaminated products are obtained by linear fit
Component volume fraction Quantitative Analysis Model；
Using the method for the optimization of co sinus vector included angle, the weights of ten groups of parameters are solved；
The time domain impulse waveform of unknown volume fraction contaminated product sample is measured using terahertz time-domain spectroscopy instrument, and extracts time domain
Ten kinds of parameter values of impulse waveform；
According to the weights of ten kinds of contaminated product component volume fraction Quantitative Analysis Models, and ten groups of parameters, unknown volume is substituted into
Ten kinds of parameter values of fraction contaminated product sample, obtain contaminated product constituent concentration.
Described ten groups of parameters are specially：
The time delay and amplitude of the Mintrop wave paddy of pulse in the terahertz time-domain spectroscopy of sample, Mintrop wave peak and secondary trough are big
It is small, totally six groups of parameter values；
By four sections of fluctuations of sample terahertz pulse：Descending branch a, ascent stage b, descending branch c and ascent stage d each enter line
Property fitting, and extract respective slope, totally four groups of parameters.
Described ten kinds of contaminated product component volume fraction Quantitative Analysis Models are specially：
Wherein, T1, A1The corresponding time delay of time domain waveform Mintrop wave paddy, amplitude size are represented respectively；T2, A2Represent respectively
The corresponding time delay in time domain waveform Mintrop wave peak, amplitude size；T3, A3Represent that the time domain waveform time trough corresponding time prolongs respectively
Late, amplitude size；With K1, K2, K3, K4Time domain waveform pulse descending branch a, ascent stage b, descending branch c and ascent stage d are represented respectively
Linear fit slope；V is volume fraction, m1......m10For the constant term of contaminated product component volume fraction Quantitative Analysis Model；
n1......n10For the coefficient of volume fraction in contaminated product component volume fraction Quantitative Analysis Model.
The beneficial effect for the technical scheme that the present invention is provided is：
1st, relative to other Terahertz contaminated product quantitative analysis detection methods, this method is independent of Bill's Lambert Law, no
The oil product Terahertz frequency range refractive index and absorption coefficient of complexity are calculated, but makes full use of terahertz time-domain impulse waveform, is extracted
The time delay and amplitude of all Wave crest and wave troughs of time domain waveform (such as Mintrop wave paddy, Mintrop wave peak and secondary trough) are joined as quantitative analysis
Number；
2nd, the linear fit slope for extracting all fluctuation sections is used as quantitative analysis parameter；It is maximum according to co sinus vector included angle value
Condition, the respective weights of ten kinds of parameter models are determined using optimization；
3rd, sensitivity of the Terahertz waveform to oil product concentration is improved, the analysis result of contaminated product, reduction detection is improved
The error of analysis.
Brief description of the drawings
Fig. 1 is a kind of flow chart of the pipeline blending quantitative detecting method based on terahertz time-domain spectroscopy；
Fig. 2 is the terahertz time-domain spectroscopy of one group of concentration known contaminated product sample；
Wherein, the concentration known can be 0%, 10%, 20% ... according to certain gradient proportion, such as gradient proportion
90%th, 100% or 0%, 5%, 10%, 15% ... 90%, 95%, 100%, can not also be according to gradient proportion
Design, is other numerical value, the embodiment of the present invention is without limitation.
Fig. 3 is Mintrop wave paddy A, the Mintrop wave peak B and secondary trough C and descending branch a of oil product terahertz time-domain waveform pulse, risen
Section b, descending branch c and ascent stage d schematic diagram.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, further is made to embodiment of the present invention below
It is described in detail on ground.
Embodiment 1
A kind of pipeline blending quantitative detecting method based on terahertz time-domain spectroscopy, referring to Fig. 1, the quantitative side of detection of the contaminated product
Method comprises the following steps：
101：The linear fit model expression of contaminated product volume fraction and ten groups of parameters, i.e., ten kinds are obtained by linear fit
Contaminated product component volume fraction Quantitative Analysis Model；
102：Using the method for the optimization of co sinus vector included angle, the weights of ten groups of parameters are solved；
103：The time domain impulse waveform of unknown volume fraction contaminated product sample is measured using terahertz time-domain spectroscopy instrument, and is extracted
Ten kinds of parameter values of time domain impulse waveform；
104：According to the weights of ten kinds of contaminated product component volume fraction Quantitative Analysis Models, and ten groups of parameters, substitute into unknown
Ten kinds of parameter values of volume fraction contaminated product sample, obtain contaminated product constituent concentration.
Wherein, ten groups of parameters in step 101 are specially：
The time delay and amplitude of the Mintrop wave paddy of pulse in the terahertz time-domain spectroscopy of sample, Mintrop wave peak and secondary trough are big
It is small, totally six groups of parameter values；
By four sections of fluctuations of sample terahertz pulse：Descending branch a, ascent stage b, descending branch c and ascent stage d each enter line
Property fitting, and extract respective slope, totally four groups of parameters.
In summary, the embodiment of the present invention improves terahertz time-domain waveform by above-mentioned steps 101- steps 104 and analyzed
Utilizing status, enriches oil product time domain waveform parameter, improves accuracy of detection.
Embodiment 2
With reference to Fig. 2, Fig. 3 and specific calculation formula, example is further situated between to the scheme in embodiment 1
Continue, it is described below in description by taking the contaminated product of 97# gasoline and 90# gasoline as an example：
201：The time domain impulse waveform of different proportion oil product is obtained using terahertz time-domain spectroscopy instrument, foundation and training is used as
The normal data of model；
The detailed operation of the step is：The concentration known contaminated product of certain gradient proportion is entered using terahertz time-domain spectroscopy instrument
The Terahertz frequency range time domain spectroscopy measurement of row sample, obtains the complete terahertz time-domain spectroscopy of each sample, as shown in Figure 2.
Wherein, the embodiment of the present invention is not limited to the model of terahertz time-domain spectroscopy instrument, tested oil product, to metering system
Also it is not limited, as long as the equipment and common oil product of above-mentioned functions can be completed, the terahertz time-domain spectroscopy such as transmission, reflection is surveyed
Amount mode.
202：By Mintrop wave paddy A, the Mintrop wave peak B of pulse in the terahertz time-domain spectroscopy of sample and secondary trough C time delay
Totally six groups of parameter values are extracted with amplitude size；
The detailed operation of the step is：Such as Fig. 3, a typical terahertz time-domain waveform pulse includes three obvious waveforms
Structure, Mintrop wave paddy A, Mintrop wave peak B and secondary trough C are (that is, comprising first trough (Mintrop wave paddy A), first crest (Mintrop wave peak B)
With second trough (secondary trough C)).Petroleum product samples property is different, and the time delay of terahertz time-domain waveform pulse is (in x-axis
Position) it is different, the height of Wave crest and wave trough is different.By Mintrop wave paddy A, the Mintrop wave peak B of each sample terahertz time-domain waveform and secondary
Trough C time delay and amplitude size is extracted, and is used as six groups of parameters.
203：By four sections of fluctuations of sample terahertz pulse：Descending branch a, ascent stage b, descending branch c and ascent stage d each enter
Row linear fit, and extract respective slope, totally four groups of parameters；
The detailed operation of the step is：One typical terahertz time-domain waveform pulse is in Mintrop wave paddy A, Mintrop wave peak B and secondary
In trough C forming process, four sections of typical wave descending branch a, ascent stage b, descending branch c and ascent stage d are included.That is, descending branch
A and ascent stage b formation Mintrop wave paddy A；Ascent stage b and descending branch c formation Mintrop waves peak B；Descending branch c and ascent stage D-shaped
Into secondary trough C.
Petroleum product samples property is different, and the slope of every section of fluctuation of sample terahertz time-domain waveform pulse is different.By each sample
Four sections of fluctuations such as descending branch a, ascent stage b, descending branch c and ascent stage d of product terahertz time-domain waveform carry out linear fit, obtain
Each the slope of fluctuation section fitting a straight line, is used as four groups of parameters.
Wherein, the step of linear fit is known to those skilled in the art, and the embodiment of the present invention is not repeated this.
204：According to the time delay and amplitude of the actual volume fraction of contaminated product and Mintrop wave paddy A, Mintrop wave peak B and secondary trough C
The relation of size totally six groups of parameter values, actual volume fraction and descending branch a, ascent stage b, descending branch c and the ascent stage d of contaminated product
The relation of linear fit slope totally four groups of parameter values, the linear of contaminated product volume fraction and ten groups of parameters is obtained by linear fit
Kind of the contaminated product component volume fraction Quantitative Analysis Model of model of fit expression formula, i.e., ten；
The detailed operation of the step is：According to obtained Mintrop wave paddy A, Mintrop wave peak B and secondary trough C time delay and amplitude
Size totally six groups of parameters, descending branch a, ascent stage b, descending branch c and ascent stage d linear fit slope totally four groups of parameters and
Contaminated product component volume fraction, can obtain ten parameters, the fitting song with contaminated product component volume fraction by least square fitting
Line.
The corresponding match value of a certain actual ratio can be found in matched curve, such match value there will be ten groups, will
Obtained match value combines according to certain weight, will obtain final quantitative result.The key of this quantitative approach is just
It is the good and bad degree for how evaluating ten groups of match values, and provides the weights for reflecting their good and bad degree.
With T1, A1The corresponding time delays of time domain waveform Mintrop wave paddy A, amplitude size, T are represented respectively2, A2When representing respectively
The corresponding time delays of domain waveform Mintrop wave peak B, amplitude size, T3, A3Represent that the time domain waveform time trough C corresponding times prolong respectively
Late, amplitude size, with K1, K2, K3, K4Time domain waveform pulse descending branch a, ascent stage b, descending branch c and ascent stage d are represented respectively
Linear fit slope.
Using the actual volume fraction of 97# gasoline as abscissa, using ten kinds of parameter values as ordinate, the time can be obtained
Delay and the distribution map of amplitude size.It is fitted by curve linear, ten obtained linear fit curve representation formula is respectively：
Wherein, V is the volume fraction of 97# gasoline, m1......m10For contaminated product component volume fraction Quantitative Analysis Model
Constant term；n1......n10For the coefficient of volume fraction in contaminated product component volume fraction Quantitative Analysis Model.This ten expression formulas
Represent using ten kinds of parameters of time domain waveform and be used as the volume fraction model for investigating object.
For the terahertz time-domain spectroscopy of the 97# and 90# gasoline contaminated product samples of any unknown component ratio and volume fraction
Waveform, as long as bringing ten kinds of parameters of its time domain waveform into, you can solve under the V for obtaining every kind of parameter, i.e., every kind of parameter model
Component volume fraction.
205：Using the method for the optimization of co sinus vector included angle, the weights of ten kinds of parameters are solved；
The principle of the step is：The good and bad degree of ten kinds of approximating methods it needs to be determined that weights characterize.And vector angle
The method of cosine can evaluate a kind of prediction effect of method to actual value.The basic thought of this method is obtained using not
Included angle cosine value between the predicted value vector and actual value vector that are obtained with species Forecasting Methodology, this value is every kind of not Tongfang
The function of method weights.When angle is smaller between two vectors, its cosine value just closer to 1, also just explanation predicted value vector with
Actual value vector is closer to prediction effect is better.
The detailed operation of the step is：Assuming that in the contaminated product that 97# gasoline and 90# gasoline are constituted, the actual body of 97# gasoline
Integrated value is xt, t=1,2 ..., N (t is sample number, here t=1,2 ..., 9).Assuming that there is m kinds method to determine contaminated product
Amount analysis (having 10 kinds of methods here, so m=10).
The match value of t-th of sample of i-th kind of method is xit, i=1,2 ..., m；T=1,2 ..., N (in this example, has
10 kinds of methods, 9 kinds of samples).xtIt is xtCombined basis weight estimate.According to the definition of weighted average, have(t
=1,2 ..., N).Wherein l1,l2,…,lmIt is the weights of m kind quantitative approach in combined basis weight analysis.They meet following formula,li>=0, i=1,2 ..., m.
Assuming that X=[x1,x2,...,xN]T, Xi=[xi1,xi2,...,xiN]T, i=1,2 ..., m, X=[x1,x2,...,
xN]T.So X represents the volume fraction actual value vector of contaminated product, XiRepresent the volume fraction estimate that i-th kind of approximating method is obtained
Vector, X represents combined basis weight assay value vector.The cosine value of angle can be expressed as between so X and X：
WillBring above formula into, abbreviation can be obtained：
Wherein, L represents weight vector, L=(l1,l2,...,lm)T, F represents m × m square formation, referred to as information square
Battle array, and have F=(Fij)m×m,I, j=1,2 ..., m.Apparent η is l1,l2,…,lmFunction, be denoted as η
(l1,l2,...,lm).In order that combined basis weight value and actual volume fractional value are closest, that is, wish angle between X and X
It is the smaller the better, also imply that the cosine value of angle between X and X is the bigger the better.Therefore, as η (l1,l2,...,lm) reach maximum
During value, combined basis weight value is best.So, the combined basis weight model based on co sinus vector included angle can just be attributed to it is following most
Optimization problem：
Solve the constrained optimization problem, you can obtain L=(l1,l2,l3,l4,l5,l6,l7,l8,l9,l10), i.e., more than ten
Plant the weight vector of quantitative approach.
206：The time domain impulse waveform of unknown volume fraction contaminated product sample is measured using terahertz time-domain spectroscopy instrument, and is extracted
Ten kinds of parameter values of time domain impulse waveform；
The detailed operation of the step is：Using terahertz time-domain spectroscopy instrument to unknown concentration 97# and 90# gasoline contaminated product sample
Terahertz frequency range time domain spectroscopy measurement is carried out, the complete terahertz time-domain spectroscopy of sample is obtained, and extract time domain waveform pulse
Mintrop wave paddy A, Mintrop wave peak B and secondary trough C time delay and amplitude size, descending branch a, ascent stage b, descending branch c and ascent stage d
Ten kinds of parameters such as linear fit slope value.
207：Using the weights of the volume fraction model of fit of ten kinds of parameters, and ten kinds of parameters, unknown volume point is substituted into
Ten kinds of parameter values of number contaminated product sample, obtain contaminated product constituent concentration.
The detailed operation of the step is：The value of ten kinds of parameters of unknown volume fraction contaminated product sample is substituted into
Component ratio result under ten kinds of quantitative models can be obtained：
Utilize 97# gasoline and the weight vectors of ten kinds of time domain waveform parameter models of 90# gasoline
L=(l1,l2,l3,l4,l5,l6,l7,l8,l9,l10)
The contaminated product component quantifying analysis result based on ten kinds of time domain waveform parameters can be obtained
The quantitative analysis results of another composition are 1-Vfinal。
In summary, the embodiment of the present invention improves terahertz time-domain waveform by above-mentioned steps 201- steps 207 and analyzed
Utilizing status, enriches oil product time domain waveform parameter, improves accuracy of detection.
The embodiment of the present invention is to the model of each device in addition to specified otherwise is done, and the model of other devices is not limited,
As long as the device of above-mentioned functions can be completed.
It will be appreciated by those skilled in the art that accompanying drawing is the schematic diagram of a preferred embodiment, the embodiments of the present invention
Sequence number is for illustration only, and the quality of embodiment is not represented.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (3)
1. a kind of pipeline blending quantitative detecting method based on terahertz time-domain spectroscopy, it is characterised in that the contaminated product is quantitatively examined
Survey method comprises the following steps：
The linear fit model expression of contaminated product volume fraction and ten groups of parameters, i.e., ten kinds contaminated product compositions are obtained by linear fit
Volume fraction Quantitative Analysis Model；
Using the method for the optimization of co sinus vector included angle, the weights of ten groups of parameters are solved；
The time domain impulse waveform of unknown volume fraction contaminated product sample is measured using terahertz time-domain spectroscopy instrument, and extracts time domain impulse
Ten kinds of parameter values of waveform；
According to the weights of ten kinds of contaminated product component volume fraction Quantitative Analysis Models, and ten groups of parameters, unknown volume fraction is substituted into
Ten kinds of parameter values of contaminated product sample, obtain contaminated product constituent concentration.
2. a kind of pipeline blending quantitative detecting method based on terahertz time-domain spectroscopy according to claim 1, its feature
It is, described ten groups of parameters are specially：
Mintrop wave paddy, the time delay at Mintrop wave peak and secondary trough and the amplitude size of pulse in the terahertz time-domain spectroscopy of sample, altogether
Six groups of parameter values；
By four sections of fluctuations of sample terahertz pulse：Descending branch a, ascent stage b, descending branch c and ascent stage d each carry out Linear Quasi
Close, and extract respective slope, totally four groups of parameters.
3. a kind of pipeline blending quantitative detecting method based on terahertz time-domain spectroscopy according to claim 1, its feature
It is, described ten kinds of contaminated product component volume fraction Quantitative Analysis Models are specially：
Wherein, T1, A1The corresponding time delay of time domain waveform Mintrop wave paddy, amplitude size are represented respectively；T2, A2Time domain ripple is represented respectively
The corresponding time delay in shape Mintrop wave peak, amplitude size；T3, A3The corresponding time delay of time domain waveform time trough, amplitude are represented respectively
Size；With K1, K2, K3, K4Time domain waveform pulse descending branch a, ascent stage b, descending branch c and ascent stage d Linear Quasi are represented respectively
Close slope；V is volume fraction, m1......m10For the constant term of contaminated product component volume fraction Quantitative Analysis Model；
n1......n10For the coefficient of volume fraction in contaminated product component volume fraction Quantitative Analysis Model.
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| CN109374568A (en) * | 2018-05-25 | 2019-02-22 | 广东工业大学 | A kind of sample recognition methods using terahertz time-domain spectroscopy |
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