CN109507145A - A kind of method of near infrared detection industrial liquid thiocarbamide content - Google Patents
A kind of method of near infrared detection industrial liquid thiocarbamide content Download PDFInfo
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- CN109507145A CN109507145A CN201811617517.XA CN201811617517A CN109507145A CN 109507145 A CN109507145 A CN 109507145A CN 201811617517 A CN201811617517 A CN 201811617517A CN 109507145 A CN109507145 A CN 109507145A
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 title claims abstract description 324
- 239000007788 liquid Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 64
- 238000001514 detection method Methods 0.000 title claims abstract description 34
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 55
- 238000001228 spectrum Methods 0.000 claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000004458 analytical method Methods 0.000 claims description 10
- 230000003595 spectral effect Effects 0.000 claims description 9
- 238000012937 correction Methods 0.000 claims description 8
- 238000010606 normalization Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000011156 evaluation Methods 0.000 claims description 7
- 238000012795 verification Methods 0.000 claims description 7
- 230000005856 abnormality Effects 0.000 claims description 6
- 238000000556 factor analysis Methods 0.000 claims description 6
- 238000010238 partial least squares regression Methods 0.000 claims description 6
- 238000007781 pre-processing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000010812 external standard method Methods 0.000 claims description 5
- 230000009466 transformation Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- PMUIBVMKQVKHBE-UHFFFAOYSA-N [S].NC(N)=O Chemical compound [S].NC(N)=O PMUIBVMKQVKHBE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004422 calculation algorithm Methods 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000006193 liquid solution Substances 0.000 claims description 3
- 238000012821 model calculation Methods 0.000 claims description 3
- 238000001320 near-infrared absorption spectroscopy Methods 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 238000004445 quantitative analysis Methods 0.000 abstract description 4
- 238000004566 IR spectroscopy Methods 0.000 abstract description 3
- 238000004587 chromatography analysis Methods 0.000 abstract description 3
- 238000005259 measurement Methods 0.000 abstract description 2
- 239000012452 mother liquor Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000008396 flotation agent Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000010829 isocratic elution Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 238000004497 NIR spectroscopy Methods 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002790 cross-validation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000021 stimulant Substances 0.000 description 1
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 description 1
- 229960001544 sulfathiazole Drugs 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
-
- 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
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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
- G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/12—Circuits of general importance; Signal processing
- G01N2201/121—Correction signals
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The present invention provides a kind of methods of near infrared detection industrial liquid thiocarbamide content, its main feature is that this method provides a kind of prediction models based on near-infrared spectrum technique measurement thiocarbamide content, the near-infrared original spectrum of sample is acquired on the basis of known a large amount of sample real contents, establish the Quantitative Analysis Predictive Model of thiocarbamide content in the liquid thiocarbamide feed liquid based on near-infrared spectrum technique and liquid-phase chromatography method, it only needs that its atlas of near infrared spectra will be acquired after the preprocessed filtering of sample to be measured when detection, it can be carried out detecting after acquiring infrared spectroscopy, it is short to realize spectra collection process time, simply, fast, detection efficiency is high, the high feature of detection accuracy, it is suitble to apply in the production of industrial thiocarbamide and use process.
Description
Technical field
The present invention relates to the detection method of certain component content in mixture more particularly to a kind of near infrared detection industry liquid
The method of body thiocarbamide content.
Background technique
Thiocarbamide is frequently as the flotation agent for manufacturing drug, dyestuff, resin, moudling powder, the vulcanization accelerator of rubber, metalliferous mineral
Deng raw material, it is also possible to using the raw material as the drugs such as synthesis sulphathiazole, methionine and hog piece.The conduct in organic synthesis
The raw material of dyestuff and dyeing assistant, resin and moudling powder.Also be used as the vulcanization accelerator of rubber, the flotation agent of metalliferous mineral,
The catalyst of phthalic anhydride and fumaric acid processed and metal antirusting agent.In terms of photographic material, can be used as developer and
Toner, it may also be used for electroplating industry.Thiocarbamide be also used to make diazo sensitized paper, synthetic resin coating, anion exchange resin,
Germination stimulants, fungicide etc..
Thiocarbamide in production and use process often with the presence of liquid solution state, need to the concrete content of wherein thiocarbamide into
Row quantitative analysis is mostly now chemical titration and high performance liquid chromatography, the detection tool of these methods to the detection of thiocarbamide content
Have the shortcomings that complicated for operation, time-consuming and laborious.Near infrared light is electromagnetic wave of the wavelength between visible region and middle infrared,
Near infrared spectrum is defined as the region of (780-2526) nm by U.S. material detection association (ASTM).Near infrared spectrum is mainly
Since the anharmonicity of molecular vibration makes molecular vibration from ground state to generation when high energy order transition, hydric group (C-H, N- are recorded
H, O-H) vibration sum of fundamental frequencies and frequency multiplication absorb.There is stronger sound near infrared spectrum section containing hydric group (N-H) in thiocarbamide
It answers.
According to the literature, the detection method of thiocarbamide mainly has chemical analysis, electrochemical process, photometry, ion color at present
Spectrometry etc..Though wherein chemical analysis, electrochemical process are fairly simple, time-consuming, it is believed that error is big, and by-product is to thiocarbamide
Quantitative result generates interference, cannot carry out quickly and effectively quantitative analysis to it.Near infrared detection technology is in thiocarbamide content at present
Detection in there are no relevant applications.
Summary of the invention
In view of the above-mentioned problems, the present invention provides one kind can quickly measure thiocarbamide content in industrial liquid thiocarbamide feed liquid
Measuring method is determined by establishing thiocarbamide content in liquid thiocarbamide feed liquid based on near-infrared spectrum technique and liquid-phase chromatography method
Amount analysis prediction model, will acquire its atlas of near infrared spectra after the preprocessed filtering of sample to be measured, after acquiring infrared spectroscopy
Can be carried out detecting, have the characteristics that simple, quick, detection efficiency is high, detection accuracy is high, be suitble to produce in industrial thiocarbamide and
Application in use process.
The present invention first establishes the prediction straightening die of industrial liquid thiocarbamide feed liquid thiocarbamide content by the way of two modelings
Type, then the original near infrared spectrum by importing industrial liquid thiocarbamide feed samples to be verified in the prediction calibration model of foundation
It with thiocarbamide content, evaluates by analysis, the sample of rejecting abnormalities, so that optimum prediction model is obtained, the industry that this method is established
The prediction model of liquid thiocarbamide feed liquid thiocarbamide content has higher accuracy.
Specific steps of the invention are as follows:
(1) the near-infrared prediction model of thiocarbamide content is established；The thiocarbamide content near-infrared prediction model uses such as lower section
Method is established, and is specifically comprised the following steps:
A, industrial liquid thiocarbamide feed liquid, filtering pretreatment are obtained at random；
B, the filtered sample that step A is obtained is subjected near infrared spectra collection respectively and obtains each industrial liquid thiocarbamide
Original atlas of near infrared spectra；
C, it is analyzed using near-infrared original spectrum of the PCA algorithm to all industrial liquid thiocarbamide feed liquids, rejecting has
The industrial liquid thiocarbamide sample of similar spectral, remaining industry thiocarbamide feed samples are representative industrial thiocarbamide feed liquid sample
Product；
D, using thiocarbamide content in the above-mentioned representative industrial thiocarbamide feed samples of liquid phase external standard method；
E, the maximum sample with the smallest thiocarbamide content is selected according to gained thiocarbamide content；Concentration is denoted as C respectivelymax, Cmin；
Using thiocarbamide content highest and minimum sample as standard sample, make n parts withThe mark for being C ' for gradient concentration
Quasi- sample, wherein n >=60；
F, the sample that step E is prepared is subjected near infrared spectra collection respectively and obtains the original of each industrial liquid thiocarbamide feed liquid
Beginning atlas of near infrared spectra；
G, the atlas of near infrared spectra for preparing sample and thiocarbamide content C ' are directed into quantitative spectrochemical analysis software, are existed first
The near infrared spectrum of sample is pre-processed in full spectral limit, then uses partial least-squares regression method combination validation-cross pair
Sample establishes prediction calibration model, is evaluated according to near-infrared quantitative calibration models parameter quantitative calibration models:
Parameter to the near-infrared quantitative calibration models that quantitative calibration models are evaluated includes coefficient of determination R2, interactive to test
Root-mean-square error RMSECV is demonstrate,proved, optimal spectrum preprocess method and optimal spectrum section are determined, according to geneva in evaluation procedure
The industrial liquid thiocarbamide material of distance, THE PRINCIPAL FACTOR ANALYSIS figure, spectrum residual plot and chemical analysis value residual plot result rejecting abnormalities
Liquid sample, to obtain the prediction calibration model of optimal industrial liquid thiocarbamide feed liquid thiocarbamide content；
H, industrial liquid thiocarbamide feed samples to be verified are filtered pretreatment, and collect the original of sample to be verified
Atlas of near infrared spectra uses its thiocarbamide content of liquid chromatography for measuring；
I, the original near infrared spectrum of industrial liquid thiocarbamide feed samples to be verified and thiocarbamide content are imported into the pre- of foundation
It surveys in calibration model and obtains prediction verifying model, resulting prediction is verified followed by the parameter of near-infrared quantitative verification model
Model is evaluated:
The parameter that the near-infrared quantitative verification model that model is evaluated is verified to prediction includes the external certificate coefficient of determination
R2Ev, and verifying root-mean-square error RMSEP, in evaluation procedure according to mahalanobis distance, THE PRINCIPAL FACTOR ANALYSIS figure, spectrum residual plot with
And the industrial liquid thiocarbamide feed samples of chemical analysis value residual plot result rejecting abnormalities, to obtain optimal industrial liquid sulphur
The prediction model of urea feed liquid thiocarbamide content；
(2) industrial liquid thiocarbamide feed liquid to be determined is filtered；
(3) the progress near infrared spectra collection of industrial liquid thiocarbamide feed liquid obtained in step (2) is obtained into industrial liquid to be measured
The original atlas of near infrared spectra of body thiocarbamide feed liquid；
(4) by industry obtained in the original atlas of near infrared spectra of industrial liquid thiocarbamide feed liquid to be measured and step (1)-I
The prediction model of liquid thiocarbamide feed liquid is imported into quantitative spectrochemical analysis software, is analyzed by model calculation, can be obtained to be measured
The content of thiocarbamide in industrial liquid thiocarbamide.
Industrial liquid thiocarbamide feed liquid described in step (1)-A includes all in entire thiocarbamide production process involving a need to examine
Survey the liquid solution of thiocarbamide content.
The method of the original atlas of near infrared spectra of acquisition industrial liquid thiocarbamide feed liquid to be measured described in step (1) are as follows: tool
Body, suitable filtered industrial liquid thiocarbamide feed samples are taken, being put into Fourier transformation N IRS instrument cuvette, (light path is
In 1mm), Instrument working parameter is set, sample near infrared spectrum is acquired under the conditions of 25 DEG C ± 0.5 DEG C of temperature, obtains the sample
First near infrared light spectrum raw sample is then poured into after sample is poured out in cuvette again, again acquire sample near infrared light
Spectrum, obtains second near infrared light spectrum of the sample, is then averaged, obtains to first and second near infrared light spectrum
To the original near infrared spectrum of the industrial liquid thiocarbamide feed samples.
Described in step (1)-G in full spectral limit to the sample near infrared spectrum of correction be respectively adopted first derivative,
Second dervative, subtract straight line, first derivative+MSC (multiplicative scatter correction), first derivative+subtract straight line, single order is led
The normalization of number+vector, without Pretreated spectra, min-max normalization, vector normalization, eliminate constant offset and polynary
Scatter correction, totally 11 kinds of preprocessing procedures.
The Fourier transformation NIRS Instrument working parameter setting are as follows: spectrum section is 4000-12500cm-1, resolution ratio
16cm-1(≤16cm-1Also can), scanning times 32 (>=32 also can) are secondary, and the spectrogram not place any article is joined as background work
Than.
The method of sample is prepared described in step (1)-E are as follows: by the sample concentration of maximum concentration and minimum concentration sample
Concentration be denoted as C respectivelymax, CminUsing thiocarbamide content highest and minimum sample as standard sample, make n parts withFor the sample (n >=60) of gradient, the minimum sample of content is calculated as the 1st sample, then the concentration of i-th of sample
For Ci,Minimum content sample quality needed for preparing i-th of sample is m1, then needed for highest
Quality needed for content sample is m2,According to gained quality weighing sample is calculated, record lower-weighing is minimum
Sample quality m1', highest sample quality m2', then prepare the final actual content of the sample
Required sample is made according to the method.
The method using liquid chromatography for measuring industrial liquid thiocarbamide content are as follows: weigh 0.3g sample respectively
100mL water is added into 500mL volumetric flask in 0.01g standard sample, and 10mL (10%) acetic acid solution is added, shakes up constant volume, liquid phase
Chromatographic condition: C-18 chromatographic column (4.6 × 250mm, 5um), using methanol and 0.4% acetic acid water as mobile phase, isocratic elution, flowing
Phase Proportion is 5:95；Flow velocity is 0.5mL/min, and detector is UV detector, and Detection wavelength 236nm, sample volume 10uL pass through
The content of thiocarbamide in obtained thiocarbamide sample peak area external standard method sample.
Near-infrared spectrum technique and liquid-phase chromatography method are based in conclusion establishing using above-mentioned technical proposal of the invention
Liquid thiocarbamide feed liquid in thiocarbamide content Quantitative Analysis Predictive Model, then only need the preprocessed filtering of sample to be measured
After acquire its atlas of near infrared spectra, can be carried out detecting after acquiring infrared spectroscopy, it is short to realize spectra collection process time,
Simply, fast, the feature that detection efficiency is high, detection accuracy is high, be suitble to produce in industrial thiocarbamide and use process in apply.
Detailed description of the invention
Fig. 1 is the atlas of near infrared spectra of 60 parts of thiourea solutions in the embodiment of the present invention 1；
Fig. 2 is that thiocarbamide feed liquid passes through the elimination pretreated atlas of near infrared spectra of constant offset in the embodiment of the present invention 1；
Fig. 3 is that thiocarbamide feed liquid passes through the best pretreatment pretreated near infrared light of first derivative in the embodiment of the present invention 1
Spectrogram；
Fig. 4 is the dependency graph between model predication value of the present invention and liquid chromatographic detection value；
Fig. 5-Fig. 7 is the atlas of near infrared spectra in correcting sample of the present invention best modeled section after optimal spectrum pretreatment；
Fig. 8 is cross validation root-mean-square error RMSECV in the embodiment of the present invention 1, validation-cross coefficient of determination R2Ev is with master
At the variation diagram of fractal dimension.
Specific embodiment
Specific embodiments of the present invention will be further explained below.It should be noted that for these implementations
The explanation of mode is used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, invention described below
Each embodiment involved in technical characteristic can be combined with each other as long as they do not conflict with each other.
Embodiment 1
Near infrared spectroscopy measures the thiocarbamide content of mother liquor in industrial thiocarbamide production process, specific steps are as follows:
(1) the near-infrared prediction model for establishing thiocarbamide content, specifically comprises the following steps:
A, the mother liquor sample in 60 batches of industrial thiocarbamide production processes, filtering nothing into sample the preparation of sample: are randomly selected
Obvious solid impurity, it is spare；
B, the MPA type Fourier transformation for filtered sample obtained in step A being put into the production of Bruker company is closely red
Outer analysis instrument light path is in 1mm cuvette, and liquid level to 2/3 or more colorimetric cylinder sets Instrument working parameter: Spectral range 4000-
12500cm-1, resolution ratio 16cm-1, scanning times 32 times, in the spectrum for not placing any sample as background, at 25 DEG C of room temperature
Near infrared spectra collection is carried out under the conditions of ± 0.5 DEG C respectively, obtains the original atlas of near infrared spectra of each industrial thiocarbamide mother liquor；
C, it is analyzed using near-infrared original spectrum of the PCA algorithm to all industrial thiocarbamide mother liquors, is checked after factorization
The score of each point rejects 2, similar spectral sample to flock together, and remaining 58 industrial thiocarbamide mother liquor samples are with generation
The industrial thiocarbamide mother liquor sample of table；
D, using thiocarbamide content in liquid phase external standard method industry thiocarbamide mother liquor, method particularly includes:
0.3g sample and 0.01g standard sample are weighed respectively into 500mL volumetric flask, 100mL water is added, and 10mL is added
(10%) acetic acid solution shakes up constant volume, liquid phase chromatogram condition: C-18 chromatographic column (4.6 × 250mm, 5um), with methanol and 0.4%
Acetic acid water is mobile phase, isocratic elution, mobile phase ratio 5:95；Flow velocity is 0.5mL/min, and detector is UV detector,
Detection wavelength 236nm, sample volume 10uL are contained by thiocarbamide in the sample peak area external standard method sample of obtained thiocarbamide
Amount；
The mass fraction ω of thiocarbamide1, numerical value is indicated with %, it is calculated as follows:
In formula:
C -- the numerical value of thiocarbamide content in standard sample, unit are % (m/m)；
m1-- the quality of standard sample is weighed, unit is gram (g)；
A1-- the thiocarbamide peak area of standard sample；
m2-- the numerical value of sample mass is weighed, unit is gram (g)；
A2-- the thiocarbamide peak area of sample；
E, the maximum sample with the smallest thiocarbamide content is selected according to gained thiocarbamide content；Concentration is respectively 9.5,13.8.
Using thiocarbamide content highest and minimum sample as standard sample, make 60 parts withFor gradient, thiocarbamide is dense
Degree is C’Standard sample, the minimum sample of content is calculated as the 1st sample, then its concentration of the i-th sample be Ci,Minimum content sample quality needed for preparing i-th of sample is m1, then needed for highest content
Sample quality is m2,According to gained quality weighing sample is calculated, the minimum sample quality of lower-weighing is recorded
m1, highest sample quality m2, then the final actual content of the sample is preparedAccording to the method
Make required standard sample；
F, the atlas of near infrared spectra of standard sample is acquired；
G, the atlas of near infrared spectra of standard sample and thiocarbamide content are directed into the commercial quantitative spectrometric of Bruker OPUS 7.8
It analyzes in software, the near infrared spectrum of sample is pre-processed in full spectral limit first, to sample light in full spectral limit
Spectrum be respectively adopted first derivative, second dervative, subtract straight line, first derivative+MSC (multiplicative scatter correction), first derivative+
Straight line, first derivative+vector normalization are subtracted, normalizes, disappear without Pretreated spectra, min-max normalization, vector
Except constant offset and multiplicative scatter correction, totally 11 kinds of preprocessing procedures, then use partial least-squares regression method
(PLSR) validation-cross is combined to establish prediction calibration model to sample, according to near-infrared quantitative calibration models parameter to quantitative correction
Model is evaluated, and determines optimal spectrum preprocess method, principal component because of subnumber and best modeled section, finally with because of subnumber most
Less, predict calibration model validation-cross mean square deviation root error RMSECV minimum value correspond to optimal preprocessing procedures and
Best modeled section, Fig. 5-Fig. 7 are the atlas of near infrared spectra in correcting sample best modeled section after optimal spectrum pretreatment, table
1 is the model parameter under different preprocessing procedures, and as can be seen from Table 1, finally the pretreatment of determining optimal spectrum is one
Order derivative, best modeled section are (10000-9500) cm-1、(7500-5500)cm-1、(5000-4500)cm-1, optimum factor
Number is 6；According to mahalanobis distance, THE PRINCIPAL FACTOR ANALYSIS figure, spectrum residual plot and chemical analysis value residual plot knot in evaluation procedure
It is female to obtain optimal industrial thiocarbamide using the spectrogram of remaining 58 samples by industrial 2, thiocarbamide mother liquor sample of fruit rejecting abnormalities
The prediction calibration model of molten sulfur urea content.
H, to be verified 30 batches industrial thiocarbamide mother liquor samples are filtered pretreatment, and collect the original of sample to be verified
Atlas of near infrared spectra uses its thiocarbamide content of liquid chromatography for measuring.
I, the original near infrared spectrum of industrial liquid thiocarbamide feed samples to be verified and thiocarbamide content are imported into the pre- of foundation
It surveys in calibration model and obtains prediction verifying model, resulting prediction is verified followed by the parameter of near-infrared quantitative verification model
Model is evaluated, and the parameter to the near-infrared quantitative verification model that prediction verifying model is evaluated includes that external certificate determines
Coefficients R2Ev, and verifying root-mean-square error RMSEP, external certificate coefficient of determination R2Ev is 91.39, verifies root-mean-square error
RMSEP is 0.248, residual according to mahalanobis distance, THE PRINCIPAL FACTOR ANALYSIS figure, spectrum residual plot and chemical analysis value in evaluation procedure
The abnormal industrial liquid thiocarbamide feed liquid sample discrete in the poor figure result rejecting too big spectrum residual error of mahalanobis distance, assay value residual error is too big
Product 1, the prediction model of best industrial liquid thiocarbamide feed liquid thiocarbamide content is obtained using the spectrogram of remaining 29 samples；
(2) by be determined 30 batches industrial thiocarbamide mother liquor filterings；
(3) the progress near infrared spectra collection of industry thiocarbamide mother liquor obtained in step (2) is obtained into industrial thiocarbamide mother to be measured
The original atlas of near infrared spectra of liquid；
(4) by industry thiocarbamide obtained in the original atlas of near infrared spectra of industrial thiocarbamide mother liquor to be measured and step (1)-I
The prediction model of mother liquor is imported into the commercial quantitative spectrochemical analysis software of Bruker OPUS 7.8, is analyzed by model calculation, i.e.,
The content of thiocarbamide in industrial thiocarbamide mother liquor to be measured can be obtained.
Table 2 is that 30 groups of industry thiocarbamide mother liquor to be measured is examined using the result of above method measurement with using high performance liquid chromatography
The Comparative result of survey.
Table 1 is the model parameter under different preprocessing procedures
2 near infrared detection data of table and liquid chromatographic detection data comparison
As can be seen from the data in the table, using near-infrared modeling and forecasting result and using liquid chromatographic detection it is absolute partially
Poor p < 0.2%, can satisfy the demand of production.
Comparative example 1
It is commercial that the atlas of near infrared spectra of representative sample in embodiment and thiocarbamide content are directed into Bruker OPUS 7.8
In quantitative spectrochemical analysis software, in best modeled region (10000-9500) cm-1、(7500-5500)cm-1、(5000-4500)
cm-1Sample spectra is pre-processed using first derivative in range, validation-cross is combined using partial least-squares regression method (PLSR)
Prediction calibration model is established to sample, then using the original near-infrared of industrial liquid thiocarbamide feed samples to be verified in embodiment
Spectrum and thiocarbamide content, which import in the prediction calibration model established, obtains prediction verifying model, followed by near-infrared quantitative verification
The external certificate coefficient of determination R of model2Ev, and verifying root-mean-square error RMSEP, parameter carry out resulting prediction verifying model
Evaluation, forecast result of model are as shown in table 3:
Table 3 prepares the established model of sample and hand representative sample model built parameter comparison
| Parameter | Prepare standard sample model built | Representative sample model built |
| R2 | 99.97 | 85.62 |
| RMSEC | 0.0207 | 0.32 |
| R2ev | 91.39 | 77.53 |
| RMSEP | 0.248 | 0.356 |
As known to table 3, established using identical optimization process section and optimal spectrum preprocess method first derivative
Near-infrared model its external related coefficient it is maximum and verifying root-mean-square error is minimum, prepare standard sample model built and relatively represent
Property sample model built have optimal prediction effect.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of method of near infrared detection industrial liquid thiocarbamide content, which is characterized in that steps are as follows:
(1) the near-infrared prediction model of thiocarbamide content is established；The thiocarbamide content near-infrared prediction model is built with the following method
It is vertical, specifically comprise the following steps:
A, industrial liquid thiocarbamide feed liquid, filtering pretreatment are obtained at random；
B, the filtered sample that step A is obtained is subjected near infrared spectra collection respectively and obtains the original of each industrial liquid thiocarbamide
Beginning atlas of near infrared spectra；
C, it is analyzed, is rejected with similar using near-infrared original spectrum of the PCA algorithm to all industrial liquid thiocarbamide feed liquids
The industrial liquid thiocarbamide sample of spectrum, remaining industry thiocarbamide feed samples are representative industrial thiocarbamide feed samples；
D, using thiocarbamide content in the above-mentioned representative industrial thiocarbamide feed samples of liquid phase external standard method；
E, the maximum sample with the smallest thiocarbamide content is selected according to gained thiocarbamide content；Concentration is denoted as C respectivelymax, Cmin；With sulphur
Urea content highest and minimum sample are standard sample, make n parts withThe standard sample for being C ' for gradient concentration
Product, wherein n >=60；
F, the sample of the obtained preparation of step E is subjected near infrared spectra collection respectively and obtains each industrial liquid thiocarbamide feed liquid
Original atlas of near infrared spectra；
G, the atlas of near infrared spectra for preparing sample and thiocarbamide content C ' are directed into quantitative spectrochemical analysis software, are being composed entirely first
The near infrared spectrum of sample is pre-processed in range, then using partial least-squares regression method combination validation-cross to sample
Prediction calibration model is established, quantitative calibration models are evaluated according to near-infrared quantitative calibration models parameter:
Parameter to the near-infrared quantitative calibration models that quantitative calibration models are evaluated includes coefficient of determination R2, validation-cross is equal
Square error RMSECV determines optimal spectrum preprocess method and optimal spectrum section, in evaluation procedure according to mahalanobis distance,
The industrial liquid thiocarbamide feed liquid sample of THE PRINCIPAL FACTOR ANALYSIS figure, spectrum residual plot and chemical analysis value residual plot result rejecting abnormalities
Product, to obtain the prediction calibration model of optimal industrial liquid thiocarbamide feed liquid thiocarbamide content；
H, industrial liquid thiocarbamide feed samples to be verified are filtered pretreatment, and collect the original close red of sample to be verified
External spectrum figure uses its thiocarbamide content of liquid chromatogram measuring；
I, the original near infrared spectrum of industrial liquid thiocarbamide feed samples to be verified and thiocarbamide content are imported into the prediction school established
Prediction verifying model is obtained in positive model, and model is verified to resulting prediction followed by the parameter of near-infrared quantitative verification model
It is evaluated:
The parameter that the near-infrared quantitative verification model that model is evaluated is verified to prediction includes external certificate coefficient of determination R2Ev,
With verifying root-mean-square error RMSEP, according to mahalanobis distance, THE PRINCIPAL FACTOR ANALYSIS figure, spectrum residual plot and change in evaluation procedure
The industrial liquid thiocarbamide feed samples for learning assay value residual plot result rejecting abnormalities, to obtain optimal industrial liquid thiocarbamide material
The prediction model of molten sulfur urea content；
(2) industrial liquid thiocarbamide feed liquid to be determined is filtered；
(3) the progress near infrared spectra collection of industrial liquid thiocarbamide feed liquid obtained in step (2) is obtained into industrial liquid sulphur to be measured
The original atlas of near infrared spectra of urea feed liquid；
(4) by industrial liquid obtained in the original atlas of near infrared spectra of industrial liquid thiocarbamide feed liquid to be measured and step (1)-I
The prediction model of thiocarbamide feed liquid is imported into quantitative spectrochemical analysis software, is analyzed by model calculation, and industry to be measured can be obtained
The content of thiocarbamide in liquid thiocarbamide.
2. a kind of method of near infrared detection industrial liquid thiocarbamide content according to claim 1, it is characterised in that: step
(1) the industrial liquid thiocarbamide feed liquid obtained at random described in-A include in entire thiocarbamide production process it is all involve a need to detection sulphur
The liquid solution of urea content.
3. a kind of method of near infrared detection industrial liquid thiocarbamide content according to claim 1, it is characterised in that: described
Industrial liquid thiocarbamide feed liquid nearly red spectral acquisition method are as follows: take suitable filtered industrial liquid thiocarbamide feed samples,
It is put into Fourier transformation NIRS instrument cuvette, sets Instrument working parameter, acquire sample under the conditions of 25 DEG C ± 0.5 DEG C of temperature
Near infrared spectrum obtains first near infrared light spectrum of the sample, then, after sample is poured out in cuvette pours into again as former state
Product acquire sample near infrared spectrum again, second near infrared light spectrum of the sample are obtained, then to first and second
Near infrared light spectrum is averaged, and the original near infrared spectrum of the industrial liquid thiocarbamide feed samples is obtained.
4. a kind of method of near infrared detection industrial liquid thiocarbamide content according to claim 1, it is characterised in that: described
Fourier transformation NIRS Instrument working parameter setting are as follows: spectrum section is 4000-12500cm-1, resolution ratio 16cm-1, scanning times
32 times, the spectrogram not place any article makees reference as background.
5. a kind of method of near infrared detection industrial liquid thiocarbamide content according to claim 1, it is characterised in that: step
(1) method of sample is prepared described in-E are as follows: remember the concentration of the sample concentration of maximum concentration and minimum concentration sample respectively
For CmaxAnd Cmin, using thiocarbamide content highest and minimum sample as standard sample, make n parts withFor gradient
The minimum sample of content is calculated as the 1st sample by sample, n >=60, then the concentration of i-th of sample is Ci,Minimum content sample quality needed for preparing i-th of sample is m1, required highest content sample
Quality is m2,According to gained quality weighing sample is calculated, the minimum sample quality of lower-weighing is recorded
m1', highest sample quality m2', then prepare the final actual content of the sampleAccording to the method
Make required sample.
6. a kind of method of near infrared detection industrial liquid thiocarbamide content according to claim 1, it is characterised in that: step
(1) first derivative is respectively adopted to the sample near infrared spectrum of correction in full spectral limit described in-G, second dervative, subtracts one
Straight line, first derivative+MSC, first derivative+subtract straight line, first derivative+vector normalization, without Pretreated spectra,
Min-max normalization, eliminates constant offset and multiplicative scatter correction at vector normalization, totally 11 kinds of preprocessing procedures.
7. a kind of method of near infrared detection industrial liquid thiocarbamide content according to claim 1, it is characterised in that: due to
It is modeled using the artificial method for preparing standard sample, its coefficient of determination of model built is 99.97, and validation-cross root mean square misses
Difference is 0.0207, external certificate coefficient of determination R2Ev is 91.39, and verifying root-mean-square error RMSEP is 0.248.
8. a kind of method of near infrared detection industrial liquid thiocarbamide content according to claim 1, it is characterised in that: described
Industrial liquid thiocarbamide feed liquid model used in modeling section and spectrogram preprocess method are as follows: first derivative, most preferably
Modeling section is 10000-9500cm-1、7500-5500cm-1、5000-4500cm-1, optimum factor number is 6.
9. a kind of method of near infrared detection industrial liquid thiocarbamide content according to claim 1, it is characterised in that: built
The vertical model sample of thiocarbamide content in 5%-24% suitable for industrial liquid thiocarbamide.
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