CN106706555A - Milk powder determination method and system based on near infrared spectroscopy technology - Google Patents
Milk powder determination method and system based on near infrared spectroscopy technology Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 79
- 238000005516 engineering process Methods 0.000 title abstract description 16
- 238000004497 NIR spectroscopy Methods 0.000 title abstract description 4
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 89
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 81
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000001228 spectrum Methods 0.000 claims abstract description 18
- 238000003556 assay Methods 0.000 claims description 19
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- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 7
- 238000002512 chemotherapy Methods 0.000 claims description 6
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- 235000008476 powdered milk Nutrition 0.000 claims description 4
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention relates to a milk powder determination method and system based on near infrared spectroscopy technology. The method includes establishment of a melamine determination model and determination of to-be-detected milk powder. The establishment of the melamine determination model includes: preparing at least one milk powder sample; utilizing a near infrared spectral acquisition apparatus to acquire a near infrared spectrum of the milk powder sample; pretreating the near infrared spectrum of the milk powder sample; and establishing the melamine determination model with chemometrics software. Determination of to-be-detected milk powder consists of the steps of: utilizing the near infrared spectral acquisition apparatus to acquire the near infrared spectrum of the to-be-detected milk powder; and predicting the content of melamine in the to-be-detected milk powder on the basis of the melamine determination model. The method and the system provided by the invention carry out multiple milk powder determination on the basis of near infrared spectroscopy technology, only need a spectrum of the sample, have no need for destruction of the sample's characters, and no need of a chemical agent, avoid generation of hazardous substances, are green and environment-friendly, and improve the analysis speed, thus being suitable for large-scale popularization and application.
Description
Technical field
The present invention relates to spectral measurement methodses field, more particularly to infrared spectrometry technical field, one kind is specifically referred to
Milk powder assay method and system based on near-infrared spectrum technique.
Background technology
With developing rapidly for food industry technology, milk powder market is prosperous without obstacle always in recent years, and special milk powder sells well market, disappears
Expense colony expands day by day.Milk powder is primary raw material from fresh milk, adds high-quality calcium source, forced for vitamins, using advanced
Production equipment, forms through the advanced technologies such as sterilization, concentration, spray drying, spraying lecithin are refined.Milk powder enters in process
Row reinforcing modulation, lactoprotein is moderately denatured in making milk, is absorbed so as to be easy to human consumption, and can supplement certain type and quantity
Trace element and other nutrients, make its nutritional ingredient than fresh milk more comprehensively, more reasonably adapt to different crowd the need for, at present
Milk powder has turned into an important trend of Dairy Industry development.But along with the fast development of Dairy Processing industry, dairy products
The guarantee of quality but turns into abnormal distinct issues.Under the ordering about of tremendous economic interests, the adulteration of milk and milk productses is got over
Come more serious, the phenomenon that melamine is added wherein in milk powder is particularly acute, received because consumer is healthy caused by adulterated
Event to injury happens occasionally.Thus it is necessary to set up simple and efficient, reliable detection method, the trimerization in monitoring dairy products
Cyanamide content, it is ensured that dairy products safety.
At present, the detection method of melamine is used for both at home and abroad, mainly there is high performance liquid chromatography, liquid chromatography-mass spectrography
Combination method, immunoassay, capillary electrophoresis, gas chromatography mass spectrometry method, fluorimetry etc..
Red, orange, green, blue, yellow (ROGBY)：It is currently most popular detection method, it is few with quick, good separating effect, consumption, and not
The features such as being limited by sample, is particularly well-suited to the analysis of the compound that higher boiling, macromolecular, polarity are strong and heat endurance is poor.
With the precipitation method first by the protein precipitation in milk powder, the melamine in milk powder is extracted afterwards, extract solution is consolidated with cation exchange
Mutually extraction column purification, is detected with high performance liquid chromatography, and quantified by external standard method, minute is about 10min.
Capillary Electrophoresis（CE）It is also called HPCE（HPCE）：It is one kind with capillary as split tunnel,
High-voltage dc is driving force, according to the skill that the electrophoretic mobility of each component in sample and the difference of distribution behavior are separate
Art.CE has the advantages that amount of samples is few, analysis cost is low, separative efficiency is high and matrix interference low degree.
Immunoassay：It is widely used in food safety detection, is often used as screening technique.Immunological Method is a kind of fast
The method of speed detection melamine, its principle is the melamine in extracting sample by way of homogeneous and concussion using extract
Amine carries out immunoassays.
Colorimetric method：Melamine contains 3 amino, the weak base for being a rich electricity, it can with containing 3 nitros, lack
The acid (2,4,6 one trinitrophenols, picric acid) of electricity forms compound.Picric acid is yellow, forms color after compound
Deepen to turn into rufous.The compound of formation is more, and color is deeper, therefore can be by the change of color and the depth of color
To have detected whether melamine and its content.
Said determination method in traditional chemical analysis method be mostly leading, exist detection speed slowly, high cost, destructiveness
By force, the degree of accuracy is low, poor real the shortcomings of.Wherein red, orange, green, blue, yellow (ROGBY) high cost, test period is long, and instrument price is expensive, uses
It is relatively costly, so as to also limit the popularization of the method, can only be used as verification method in part Experiment room；Capillary Electrophoresis
, because the internal diameter of capillary is small, light path is short, so as to limit its sensitivity for method；Other are based on the method for chemical reagent addition,
Test sample proterties in itself can be destroyed, operation is comparatively laborious, time-consuming more long, resultant error is big.
In recent years, the technology of a kind of infrared spectrum or ultraviolet spectroscopy milk powder is also occurred in that in the prior art, is mainly had
The following two kinds scheme：
1st, there is provided a kind of method of quick measure testing melamine content in milk powder, comprise the following steps：A, prepare testing sample
Press sheet compression；B, preparation standard press sheet compression：Weigh respectively analysis pure melamine 0.1g, 0.15g, 0.2g, 0.25g,
0.3g, is placed in the qualified milk powder of 100g, is made press sheet compression；C, using infrared spectrum measurement standard press sheet compression in 1551cm-1
The triazine ring stretching vibration infrared absorption spectroscopy of ~ 1436cm-1, goes out infrared absorption spectroscopy standard bent according to the spectrum-based rendering for measuring
Line, obtains regression equation；D, determine press sheet compression infrared absorption spectroscopy to be measured under certain condition using infrared spectrometer, then
The content of the melamine of testing sample is obtained from standard curve.
2nd, a kind of application ultra-violet absorption spectrum-chemometric techniques are quick, easy, sensitive, accurate detection milk powder and liquid
The method of melamine, cyanamid dimerization in state milk.The pre-treating method of sample substrate is removed in acidic aqueous solution using silica gel,
With reference to ultra-violet absorption spectrum and the method for Chemical Measurement, the content of melamine, dicyandiamide is finally given.Before the method sample
Treatment is easy quick, and measurement process only uses ultraviolet specrophotometer, by PLS or SVMs method or
The regressing calculation of the chemometrics algorithms such as least square-algorithm of support vector machine, can obtain correlation model, and then can be with
With the melamine in the model prediction unknown sample of gained, cyanamid dimerization content.
1st kind of scheme needs test sample is tabletted, and the 2nd kind of scheme is carried out using centrifugal settling method to testing sample
Pretreatment, these methods are both needed to carry out sample pre-treatment, and complex steps can destroy the proterties of sample itself, for existing side
The defect of method, mode measured directly is taken present invention employs to sample dress, neither destroys sample itself, does not also pre-process step
Suddenly, method is simple, and using portable near infrared spectrometer, cost is relatively low, and sensitivity is high, carries out with reference to chemometrics method
The research of near-infrared spectral analysis technology qualitative analysis, it is intended to for quick, the Non-Destructive Testing of powder quality provide new reference.
The content of the invention
The purpose of the present invention is the shortcoming for overcoming above-mentioned prior art, there is provided a kind of based on near-infrared spectrum technique
Whether milk powder assay method and system, contain melamine, with reference to change using Hadamard transform type near infrared spectrum detection milk powder
The research that metrology method has carried out near-infrared spectral analysis technology qualitative analysis is learned, is quick, the Non-Destructive Testing of powder quality
New reference is provided.
To achieve these goals, the present invention has following composition：
This is based on the milk powder assay method of near-infrared spectrum technique, and described method includes that melamine rating model is set up and treated
Survey milk powder to determine, the melamine rating model is set up and comprised the following steps：
（1-1）Prepare at least one milk powder sample；
（1-2）The near infrared spectrum of the milk powder sample is obtained using near infrared spectra collection equipment；
（1-3）Near infrared spectrum to the milk powder sample carries out pre-processing the data for obtaining associating with melamine property；
（1-4）Melamine rating model is set up using chemo metric software；
The milk powder identification to be measured comprises the following steps：
（2-1）The near infrared spectrum of milk powder to be measured is obtained using near infrared spectra collection equipment；
（2-2）The content of melamine in milk powder to be measured is predicted based on the melamine rating model.
It is preferred that the utilization near infrared spectra collection equipment obtains the near infrared spectrum of the milk powder sample, including such as
Lower step：
（1-2-1）Filled respectively using rotary attachment and take the milk powder sample, using near infrared spectra collection equipment in the milk powder
Multi collect data on sample.
More preferably, the utilization near infrared spectra collection equipment obtains the near infrared spectrum of the milk powder sample, also includes
Following steps：
（1-2-2）It is divided into pure milk powder and the major class of milk powder containing melamine two by the milk powder sample is qualitative, each sample is selected at random
A part is taken as calibration set, it is remaining to collect as checking.
It is preferred that the near infrared spectrum to the milk powder sample is pre-processed, specially：
Wavelength to the near infrared spectrum of the milk powder sample is intercepted, and selection can substantially characterize whether milk powder contains trimerization
The wave band of cyanamide is used as modeling wave band.
More preferably, the interception scope of the near infrared spectrum of the milk powder sample is 1392-1518nm, using Savitzky-
Golay smoothing algorithms carry out the disposal of gentle filter to the near infrared spectrum of the milk powder sample.
It is preferred that when setting up melamine rating model using chemo metric software, using PCA dimension-reduction algorithms and
Fisher sorting algorithms set up the melamine rating model.
More preferably, the step（1-4）Afterwards, also comprise the following steps：
（1-5）The melamine rating model is corrected.
Further, it is described that the melamine rating model is corrected, including model checking, the model tests
Card is specially：
The calibration set is respectively adopted and the checking collection sets up the melamine rating model, and compare using the correction
Collect whether consistent with the melamine rating model that the checking collection is set up, judge that the melamine is determined according to comparative result
Whether model is accurate.
Yet further, described that the melamine rating model is corrected, including experimental verification, the experiment is tested
Card is specially：
Choose new milk powder sample, and new milk powder sample with modeling when the milk powder sample that uses it is consistent, based on milk powder survey
The milk powder type of the new milk powder sample of sample predictions is determined, according to predicting the outcome and melamine described in the multilevel iudge of concrete class
Whether rating model is accurate.
The invention further relates to a kind of milk powder measurement system based on near-infrared spectrum technique, for described based on near-infrared
The milk powder assay method of spectral technique, the milk powder measurement system includes：
Near infrared spectra collection equipment, is used to obtain the near infrared spectrum of powdered milk sample and milk powder to be measured；
Pretreated spectra module, is used to the near infrared spectrum is carried out to pre-process the number for obtaining associating with melamine property
According to；
Milk powder determines MBM, is used to set up the melamine rating model using stechiometry；
Melamine prediction module, is used to the prediction of the near infrared spectrum based on the melamine rating model and milk powder to be measured and treats
Survey the content of melamine in milk powder.
The milk powder assay method based on near-infrared spectrum technique and system in the invention are employed, with following beneficial effect
Really：
（1）Data acquisition is fast：In the state of preparation of samples is improved, acquisition mode need to only match somebody with somebody milk powder mounted near infrared spectrometer
In the rotary attachment of set, 10 datas are gathered per 8s using portable near infrared spectrometer, then average out 1 result, this is adopted
Collection process sample it is convenient, quickly on the basis of, moreover it is possible to ensure the validity and reliability of data；
（2）Analyze speed is fast：Using the spectroscopic data after collection, calculated using pretreatment integrated in chemo metric software platform
Method, parser, matched combined is used, construct 5 minutes average time for model, then on this basis regulation algorithm and
Parameter, finally selectes optimal models；
（3）Analysis efficiency is high：After the completion of Construction of A Model, when the scene of carrying out is applied, it is only necessary to put determinand after reference is gathered
At near infrared spectrometer detecting head, 1s can show analysis result in mobile phone terminal or computer platform；
（4）Analysis cost is low：Near-infrared spectrum analysis only have some electricity of autophage during analysis, with conventional standard
Method is compared, and testing expense has significantly to be reduced；
（5）Without reagent, environmental protection：Near-infrared spectral analysis technology only needs the spectrum of sample, without destroying sample property, no
Need to add any chemical agent, it is to avoid the generation of harmful substance, environmental protection.
Brief description of the drawings
Fig. 1 is the operating diagram of the milk powder assay method based on near-infrared spectrum technique of the invention；
Fig. 2 is the structural representation of the milk powder measurement system based on near-infrared spectrum technique of the invention.
Specific embodiment
In order to more clearly describe technology contents of the invention, carried out with reference to specific embodiment further
Description.
Present invention employs near infrared absorption detection method, employ and mode measured directly is taken to sample dress, neither destroy
Sample itself, also without pre-treatment step, method is simple, and using portable near infrared spectrometer, cost is relatively low, sensitivity
Height, the research of near-infrared spectral analysis technology qualitative analysis has been carried out with reference to chemometrics method, it is intended to be powder quality
Quickly, Non-Destructive Testing provides new reference.In the molecular structure of melamine, 3 carbon atoms respectively with two N atoms and 1
NH2 is connected.Although the spectral peak of C-N keys is difficult identification, NH2Fluctuation be but to be exactly near infrared region, therefore can be with
Near-infrared analysis are carried out to melamine.The know-why is to irradiate test sample, root with a kind of near infrared ray of specific wavelength
The strong and weak real-time monitoring to realize its content is absorbed to ultrared according to melamine in sample, the method is a kind of contactless, nothing
Damage the detection method with non-hazardous.
Near-infrared spectrum technique of the present invention is introduced below：
The principle of absorption of near infrared spectrum：Near-infrared (Near Infrared, NIR) region refers to that wavelength exists by ASTM definition
Electromagnetic wave in the range of 780 ~ 2526 nm.Near infrared spectrum (Near-Infrared Spectroscopy, NIRS) belongs to point
Sub- vibrational spectrum, results from the vibration of covalent chemical bond anharmonic energy level, is the frequency multiplication and combination frequency of anharmonic vibration, positioned at visible ray and
Between mid-infrared light area, it is adaptable to determine the material for containing the groups such as C-H, N-H, O-H, because the spectrum that different groups are produced is inhaled
Receive peak position and intensity is all different, according to Lambert-Beer absorption laws, absorption spectrum can be constituted or tied with sample composition
The change of fruit and produce change.
Near-infrared spectrum technique：Near-infrared spectrum technique, is according to the transmission near infrared band and reflectance spectrum, to grinding
The modern analytical technique of object and quantitative analysis is studied carefully, because it has the features such as efficient, quick, low cost and environmental protection, own quilt
It is widely used in the fields such as food, medicine, forestry, agricultural, is the high-new analysis skill of analytical chemistry field fast development in recent years
Art.
Near infrared spectrum number technological maheup：Near-infrared spectrum technique mainly includes that near infrared spectrometer, Chemical Measurement are soft
Part and multivariate calibration model etc..Near infrared spectrometer is the equipment for gathering sample near infrared spectrum, Chemical Measurement
Software is the instrument for associating spectrum and properties of samples, and calibration model is corresponding between sample spectra and property for reflecting
The quantitatively or qualitatively working curve of relation.
（1）Near infrared spectrometer：The essential structure of nearly external spectrum instrument is identical with conventional spectrograph, all mainly by light source system
System, beam splitting system, test sample device, detector, control and data handling system and record display system this 6 most of constitute.Pass
Analyzer unite because volume is big, sample preparation is cumbersome, detection speed is slow, costly, with MEMS (Micro-Electro-
Mechanical System, MEMS) technology rise, occurred in that some were based on the new near of MEMS technology in the world in recent years
Infrared spectrometer, with lightweight, small volume, fast speed, long lifespan, integrability and low cost and other advantages, has promoted light
The miniaturization of spectrometer, portability, what is used in this research is namely based on the miniature near infrared spectrometer of MEMS technology.
（2）Chemical Measurement：Change meterological（Chemometrics）It is an applied mathematics statistics and computer science
Instrument, design or select optimal measuring program and test method, and obtain to greatest extent by parsing chemical metric data
The chemical subdiscipline of information.Near-infrared Spectral Absorption intensity is weak, and spectral signal-noise ratio is low, tend to have some with sample to be tested property without
The interference that the information of pass is caused, therefore, near-infrared spectrum analysis are carried out to this sample of such as milk powder and is accomplished by from overlap, changed
Spectrum in extract Weak Information, chemometrics method is indispensable, and its Main Function is to set up near infrared spectrum and component
Mathematics bridge between (property), sets up calibration model and unknown sample is realized to predict.Therefore, the chemistry of near-infrared spectrum technique
Metrology method relates generally to three aspect contents：One is preprocessing procedures research, and sample spectrum is pre-processed, and is reduced
So that eliminating the influence that various Aimless factors are caused to spectrum；Two is the selection and extraction of spectral signature wavelength, there is selection
Property ground extract the information relevant with class object and suppress the influence of irrelevant feature and noise；Three is near infrared spectrum correction side
Method research, the calibration model high to set up sane, reliability, sensitivity.
As shown in figure 1, the milk powder assay method based on near-infrared spectrum technique of the invention, mainly surveys including melamine
Cover half type is set up and milk powder to be measured is determined, and the melamine rating model is set up and comprised the following steps：
（1-1）Prepare at least one milk powder sample；
（1-2）The near infrared spectrum of the milk powder sample is obtained using near infrared spectra collection equipment；
（1-3）Near infrared spectrum to the milk powder sample carries out pre-processing the data for obtaining associating with melamine property；
（1-4）Melamine rating model is set up using chemo metric software；
The milk powder identification to be measured comprises the following steps：
（2-1）The near infrared spectrum of milk powder to be measured is obtained using near infrared spectra collection equipment；
（2-2）The content of melamine in milk powder to be measured is predicted based on the melamine rating model.
As shown in Fig. 2 the present invention also provides a kind of milk powder measurement system based on near-infrared spectrum technique, including：
Near infrared spectra collection equipment, is used to obtain the near infrared spectrum of powdered milk sample and milk powder to be measured；
Pretreated spectra module, is used to the near infrared spectrum is carried out to pre-process the number for obtaining associating with melamine property
According to；
Milk powder determines MBM, is used to set up the melamine rating model using stechiometry；
Melamine prediction module, is used to the prediction of the near infrared spectrum based on the melamine rating model and milk powder to be measured and treats
Survey the content of melamine in milk powder.
Specifically introduce what the milk powder based on near-infrared spectrum technique of the invention was determined with a specific embodiment below
Process：
Facility information：Portable near infrared spectrometer（Model, principle, technical parameter, wave-length coverage, resolution ratio etc. are according to reality
Border needs to be selected）；Rotary attachment.
Model is set up：
（1）Preparation of samples：Five kinds of different brands milk powder of selection, every kind of brand respectively takes 30g, and portion is pure sample sheet, is added in another
The melamine for entering 1% is mixed；
（2）Spectra collection：Fill sampling respectively using rotary attachment originally, use near infrared spectra collection equipment respectively 20 numbers of collection
According to, i.e., pure milk powder and each 100 containing 1% melamine milk powder；
（3）Data screening：Qualitative to be divided into pure milk powder and the major class of milk powder containing melamine two, each sample randomly selects 70 conducts
Calibration set, it is remaining to collect as checking；
（4）Pretreated spectra：Wavelength is intercepted first, selection can substantially characterize milk powder whether the ripple containing melamine
Duan Zuowei models wave band, and interception scope is 1392-1518nm；Preprocessing algorithms are selected：（Savitzky-Golay puts down
Sliding, smooth window number is 15）+（Savitzky-Golay first differentials, window number is 15, and the degree of polynomial is 3）；
（5）Algorithms selection：Dimension-reduction algorithm selects PCA, number of principal components to choose 10；Sorting algorithm selects Fisher；
Model is verified：
Model is verified：Calibration set and checking collection are classified by above-mentioned modeling procedure, gained calibration set is sentenced with checking collection
Other accuracy rate is 100%；
Actual measurement checking：
41 kinds of milk powder on the market is collected in addition, and applicable the range of age is related to baby, teenager, Ms, person in middle and old age, with same system
Sample and sample mode, gather each pure milk powder spectrum and the spectrum of milk powder containing melamine, using the model energy of above-mentioned construction respectively
Enough accurately to tell whether test sample contains melamine, accuracy rate is 100%.Additionally, in addition to being filled with annex and taking measurement, this
Model also 100% can verify whether it contains melamine to the powdered milk sample that is taken with capsule, sealed transparent plastic bag（Three
Poly cyanamid is mixed than needing >=1%）；
The milk powder assay method based on near-infrared spectrum technique and system in the invention are employed, is had the advantages that：
（1）Data acquisition is fast：In the state of preparation of samples is improved, acquisition mode need to only match somebody with somebody milk powder mounted near infrared spectrometer
In the rotary attachment of set, 10 datas are gathered per 8s using portable near infrared spectrometer, then average out 1 result, this is adopted
Collection process sample it is convenient, quickly on the basis of, moreover it is possible to ensure the validity and reliability of data；
（2）Analyze speed is fast：Using the spectroscopic data after collection, calculated using pretreatment integrated in chemo metric software platform
Method, parser, matched combined is used, construct 5 minutes average time for model, then on this basis regulation algorithm and
Parameter, finally selectes optimal models；
（3）Analysis efficiency is high：After the completion of Construction of A Model, when the scene of carrying out is applied, it is only necessary to put determinand after reference is gathered
At near infrared spectrometer detecting head, 1s can show analysis result in mobile phone terminal or computer platform；
（4）Analysis cost is low：Near-infrared spectrum analysis only have some electricity of autophage during analysis, with conventional standard
Method is compared, and testing expense has significantly to be reduced；
（5）Without reagent, environmental protection：Near-infrared spectral analysis technology only needs the spectrum of sample, without destroying sample property, no
Need to add any chemical agent, it is to avoid the generation of harmful substance, environmental protection.
In this description, the present invention is described with reference to its specific embodiment.But it is clear that can still make
Various modifications and alterations are without departing from the spirit and scope of the present invention.Therefore, specification and drawings are considered as illustrative
And it is nonrestrictive.
Claims (10)
1. a kind of milk powder assay method based on near-infrared spectrum technique, it is characterised in that described method includes melamine
Rating model is set up and milk powder to be measured is determined, and the melamine rating model is set up and comprised the following steps：
（1-1）Prepare at least one milk powder sample；
（1-2）The near infrared spectrum of the milk powder sample is obtained using near infrared spectra collection equipment；
（1-3）Near infrared spectrum to the milk powder sample carries out pre-processing the data for obtaining associating with melamine property；
（1-4）Melamine rating model is set up using chemo metric software；
The milk powder identification to be measured comprises the following steps：
（2-1）The near infrared spectrum of milk powder to be measured is obtained using near infrared spectra collection equipment；
（2-2）The content of melamine in milk powder to be measured is predicted based on the melamine rating model.
2. the milk powder assay method based on near-infrared spectrum technique according to claim 1, it is characterised in that the utilization
Near infrared spectra collection equipment obtains the near infrared spectrum of the milk powder sample, comprises the following steps：
（1-2-1）Filled respectively using rotary attachment and take the milk powder sample, using near infrared spectra collection equipment in the milk powder
Multi collect data on sample.
3. the milk powder assay method based on near-infrared spectrum technique according to claim 2, it is characterised in that the utilization
Near infrared spectra collection equipment obtains the near infrared spectrum of the milk powder sample, also comprises the following steps：
（1-2-2）It is divided into pure milk powder and the major class of milk powder containing melamine two by the milk powder sample is qualitative, each sample is selected at random
A part is taken as calibration set, it is remaining to collect as checking.
4. the milk powder assay method based on near-infrared spectrum technique according to claim 1, it is characterised in that described to institute
The near infrared spectrum for stating milk powder sample is pre-processed, specially：
Wavelength to the near infrared spectrum of the milk powder sample is intercepted, and selection can substantially characterize whether milk powder contains trimerization
The wave band of cyanamide is used as modeling wave band.
5. the milk powder assay method based on near-infrared spectrum technique according to claim 4, it is characterised in that the milk powder
The interception scope of the near infrared spectrum of sample is 1392-1518nm, and using Savitzky-Golay smoothing algorithms to the milk
The near infrared spectrum of powder sample carries out the disposal of gentle filter.
6. the milk powder assay method based on near-infrared spectrum technique according to claim 1, it is characterised in that using chemistry
When meterological software sets up melamine rating model, the trimerization is set up using PCA dimension-reduction algorithms and Fisher sorting algorithms
Cyanamide rating model.
7. the milk powder assay method based on near-infrared spectrum technique according to claim 3, it is characterised in that the step
（1-4）Afterwards, also comprise the following steps：
（1-5）The melamine rating model is corrected.
8. the milk powder assay method based on near-infrared spectrum technique according to claim 7, it is characterised in that described to institute
Melamine rating model is stated to be corrected, including model is verified, the model checking is specially：
The calibration set is respectively adopted and the checking collection sets up the melamine rating model, and compare using the correction
Collect whether consistent with the melamine rating model that the checking collection is set up, judge that the melamine is determined according to comparative result
Whether model is accurate.
9. the milk powder assay method based on near-infrared spectrum technique according to claim 8, it is characterised in that described to institute
State melamine rating model to be corrected, including experimental verification, the experimental verification is specially：
Choose new milk powder sample, and new milk powder sample with modeling when the milk powder sample that uses it is consistent, based on milk powder survey
The milk powder type of the new milk powder sample of sample predictions is determined, according to predicting the outcome and melamine described in the multilevel iudge of concrete class
Whether rating model is accurate.
10. a kind of milk powder measurement system based on near-infrared spectrum technique, it is characterised in that for any in claim 1 to 9
The milk powder assay method based on near-infrared spectrum technique described in, the milk powder measurement system includes：
Near infrared spectra collection equipment, is used to obtain the near infrared spectrum of powdered milk sample and milk powder to be measured；
Pretreated spectra module, is used to the near infrared spectrum is carried out to pre-process the number for obtaining associating with melamine property
According to；
Milk powder determines MBM, is used to set up the melamine rating model using stechiometry；
Melamine prediction module, is used to the prediction of the near infrared spectrum based on the melamine rating model and milk powder to be measured and treats
Survey the content of melamine in milk powder.
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| CN109557014A (en) * | 2019-01-24 | 2019-04-02 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | A kind of method of lactic acid bacteria number in quick detection acidified milk |
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| CN110907392A (en) * | 2019-11-15 | 2020-03-24 | 光钙(上海)高科技有限公司 | Melamine detection system based on infrared spectroscopic analysis and application and method thereof |
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