CN104730029B - Method for detecting solvent and moisture in spandex production solvent recovering system simultaneously - Google Patents
Method for detecting solvent and moisture in spandex production solvent recovering system simultaneously Download PDFInfo
- Publication number
- CN104730029B CN104730029B CN201510109451.3A CN201510109451A CN104730029B CN 104730029 B CN104730029 B CN 104730029B CN 201510109451 A CN201510109451 A CN 201510109451A CN 104730029 B CN104730029 B CN 104730029B
- Authority
- CN
- China
- Prior art keywords
- sample
- dmac
- near infrared
- solvent
- infrared spectrum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The present invention relates to a kind of method for detecting solvent and moisture in spandex production solvent recovering system simultaneously, the method is comprised the following steps：One) a series of various concentrations DMAC and H are prepared2The standard liquid of O, selects enough representational calibration set samples；Two) the near infrared spectrum spectrogram of calibration set sample is determined, 12000~4000cm of spectrogram is taken‑1After wave band carries out Pretreated spectra, respectively with DMAC in standard sample and H2O content is associated, and DMAC contents and H are set up using PLS2The calibration model of O content；Three) determine testing sample near infrared spectrum spectrogram, using with step 2 identical preprocess method treatment gained spectrogram in 12000~4000cm‑1Wave band, the absorbance that will be obtained after pretreatment substitutes into the calibration model of step 2, obtains DMAC contents in testing sample.The present invention has analysis process simple and quick, strong antijamming capability, nondestructive analysis, the advantages of sampling amount is small.
Description
Technical field
The present invention relates to one kind for DMAC and H in detection spandex production solvent DMAC recovery systems simultaneously2O content it is near
Method of infrared spectrophotometry, belongs to Industrial Analysis field.
Background technology
Spandex (polyurethanes) fiber is a kind of synthetic fibers of current most high resilience, is stretched with excellent fracture
Rate long and ultimate strength, are the production indispensable special textile fabrics of high-grade elastic textiles, with application value very high
With good development prospect.DMAC is can to reduce life using a kind of at most most wide solvents, the recovery of DMAC during spandex is produced
Cost is produced, environmental protection and sustainable development is conducive to again, DMAC and H in recovery system2O content is the weight for characterizing organic efficiency
Parameter is wanted, therefore rapidly and accurately determines DMAC and H2O content turns into an important technology in spandex production process.
At present, the assay method of DMAC contents is mainly gas chromatography, H2The assay method of O content is mainly card
Er Feixiu volumetric methods.Due in DMAC recovery systems tower charging and a tower to distillate water content higher, using gas chromatography point
Need to carry out pre-treatment to sample during analysis DMAC contents, extract the DMAC in sample, remove the large quantity of moisture contained in sample,
The interference to fid detector is prevented, but extraction process can cause the reduction of the rate of recovery.One tower distillate water content be up to 95% with
On, when surveying moisture using karl Fischer volumetric method, resultant error uses karl Fischer reagent generation 3% or so
Waste liquid can cause environmental problem.Another kind it is conventional for DMAC and H2The analysis method of O content detection is reflected according to sample
Standard curve is set up in the change of rate, but this kind of method is easily by impurity effect in environment epidemic disaster and sample, thus result is accurate
Degree is inadequate.Therefore, solvent dimethylacetylamide is returned during research one kind can in time, accurately be rapidly used for detecting spandex production simultaneously
The method of dimethylacetylamide and water content in receipts system, the stability control of pair determination DMAC recovery systems has important actual meaning
Justice.
The main information of near infrared spectrum shows as material internal composition hydric group (including O-H, C-H, N-H and S-H
Deng) to the frequency multiplication of near infrared light with combine frequency and absorb, the composition of most organic matters and the information of molecular structure can be characterized,
The composition and property for being very suitable for carbon-hydrogen organic is determined.Therefore, in recent years, Near Infrared Spectroscopy Detection Technology is in agricultural, doctor
With many with the numerous areas application such as chemistry.
Determine DMAC and H in spandex DMAC recovery systems simultaneously using near infrared spectroscopy2The research of O content does not appear in the newspapers
Road.
The content of the invention
Technical problem：Deficiency it is an object of the invention to solve currently available technology, there is provided one kind is for detecting simultaneously
The method of solvent and moisture in spandex production solvent recovering system.The implementation process of the detection method is easy, high precision, repeatability
Good, detection range is wide.
Technical scheme：To achieve the above object, the present invention provides a kind of for while detecting solvent DMAC in spandex production
DMAC and H in recovery system2The near-infrared spectrum method of O content, the method comprises the following steps：
1) a series of various concentrations N, N '-dimethyl acetamide DMAC and water H are prepared2The standard liquid of O, selection is enough to be had
Representational calibration set sample；
2) after sample spectra pretreatment, the near infrared spectrum spectrogram of measure calibration set sample, sweep limits 12000~
4000cm-1Wave band, and after carrying out Pretreated spectra, with DMAC in standard sample and H2O content is associated, using offset minimum binary
Method sets up calibration model respectively；
3) determine testing sample near infrared spectrum spectrogram, using with step 2) in identical preprocess method treatment gained
Spectrogram, the near infrared spectrum spectrogram of sample is carried out using calibration model through ABB AB's Horizon MB analysis softwares after pretreatment
Analysis, obtains DMAC and H in testing sample2O content.
The preprocessing procedures are preheated to 50 DEG C to sample loading 8mm colorimetric cylinders after mixing sample.
Enough representational calibration set sample numbers are more than 100.
The H of the sample for infrared diaphanoscopy2O mass percents are 2.0%-100%, and DMAC mass percents are
0-98%.
The assay method of described atlas of near infrared spectra is to use ABB AB's MB3600 Fourier Transform Near Infrareds
Instrument, using transmission mode, liquid cell dedicated test passage, each Sample Scan is averaged for 64 times and obtains.
The method of the pretreatment of described near infrared spectrum spectrogram is：Normalization, standardization.
The optimal wave band for being used to set up calibration model of the near infrared spectrum spectrogram of sample is confirmed as after described pretreatment
5508-6534cm-1、7143-7976cm-1、8092-9273cm-1、9751-11602cm-1Four spectral detection scopes.
Beneficial effect：DMAC and H in solvent DMAC recovery systems in this method selection spandex production2O content is detection mesh
Mark, sets up quantitative model, and method RMSECV is small, R2=0.99994 (H2O)、R2=0.99996 (DMAC) correlation is good.And to not
Know that sample is predicted, acquired results are satisfactory.Illustrating can be simultaneously to spandex using near-infrared spectrum technique combination PLS methods
DMAC and H in solvent recovering system in production2The content of O carries out quantitative analysis, and method is accurate, takes than gas chromatography and karr
Not volumetric method saves the plenty of time, and specific refractivity method is more accurate, is remarkably improved quality control efficiency, shortens detection cycle, is
Real-time analytical technology opens a new way in industrial production.
Brief description of the drawings
Fig. 1 is that near-infrared spectroscopy is set up and application process；
Fig. 2 is the original atlas of near infrared spectra of sample；
Fig. 3 is DMAC normalizations model main cause subnumber and RMSECV graphs of a relation；
Fig. 4 is H2O content calibration model main cause subnumber and RMSECV graphs of a relation；
Fig. 5 is DMAC normalization collection spectral predicted values and true value correlation curve；
Fig. 6 is H2O content calibration set spectral predicted value and true value correlation curve；
Fig. 7 is DMAC content predictions collection sample spectra predicted value and true value correlation curve；
Fig. 8 is H2O content forecast set sample spectra predicted value and true value correlation curve.
Specific embodiment
1) a series of various concentrations DMAC and H are prepared2The standard liquid of O, selects enough representational calibration set samples；
2) after sample pretreatment, the near infrared spectrum spectrogram of calibration set sample, 12000~4000cm of sweep limits are determined-1
Wave band, and after carrying out Pretreated spectra, with DMAC in standard sample and H2O content is associated, and is distinguished using PLS
Set up calibration model；
3) the near infrared spectrum spectrogram of testing sample is determined, gained is processed using with identical preprocess method in step 2
Best modeled wave band in spectrogram, the spectrum that will be obtained after pretreatment is analyzed using calibration model, in obtaining recovery system to be measured
DMAC and H2O content.
In methods described, near infrared spectrum data is gathered with transmission mode, and spandex prepolymer solution is imported into quartzy liquid
Chi Zhong, liquid cell designated lane measurement, carries out sample spectral data collection, and each sample is scanned 64 times at 50 DEG C and is averaged
Arrive.The spectral range of scanning is 12000~4000cm-1。
Step 2 in methods described) before spectrogram and data correlation, suitable preprocessing procedures are used to spectrogram,
To eliminate the interference of baseline and other backgrounds, described optimal preprocess method is normalization, standardization.Step 3) treat test sample
The preprocess method and step 2 of the near-infrared spectrogram of product) it is identical.
Step 2 in methods described) after Pretreated spectra is carried out, with cross validation root-mean-square deviation (RMSECV), phase
It is index to deviation (RSECV), Optimization Modeling parameter sets up quantitative calibration models using offset minimum binary (PLS) Return Law.
Step 3 in the present invention) spectrum of the measure and the applicability criterion of calibration model be：Forecast set sample is built
Vertical quantitative model, carries out cross-validation, with cross validation error root mean square (RMSECV) as index, it is determined that optimal PLS
Number of principal components, then set up final mask by parameter of optimal number of principal components and the best band of selection；Checking collection sample is entered
Row assay, by predicted root mean square error (RMSEP) and coefficient correlation (R2) evaluate the quality of final mask.With
PLS methods carry out data processing in Horizon MB analysis softwares, choose 40 parts of samples as Prediction, use Calibration
Cross-validation is carried out, the RMSECV of DMAC is 0.268461, H2The RMSECV of O is 0.288993.When using forecast set sample
When evaluating the detectability of PLS models, the RMSEP of DMAC is 0.214264, H2The RMSEP of O is 0.187573.
Further is made to near-infrared spectroscopy of the present invention foundation and application process by way of example below
Illustrate, the embodiment should not be construed as limitation of the present invention.
Embodiment 1：
Near-infrared spectroscopy of the present invention is set up and application process such as accompanying drawing 1, specific as follows：
1st, the treatment of instrument condition and sample：
Instrument：Near infrared spectrum is gathered by ABB AB of Switzerland MB3600 Fourier Transform Near Infrared instruments, and the instrument is matched somebody with somebody
There are Horizon MB and QA analysis softwares, quartzy liquid cell and InGaAs detectors.The spectrogram of each sample is by through 64
Secondary scanning is averaged and obtains.Sweep limits is 12000~4000cm-1
Sample：Sample used is for a tower is fed, a tower is distillated in refined recovery system in spandex production process in experiment
The sample of collection.
2nd, sample near-infrared spectral measurement：
This experiment uses quartzy liquid absorption pond, and liquid absorption pond is poured into after sample is well mixed, and is preheated to 50
± 0.5 DEG C, detection cell is put into, carries out the spectra collection of sample, same sample is scanned 64 times, final light is obtained according to after average
Spectrogram, such as accompanying drawing 2.
3rd, predict：
Fig. 2 show the initial data of spectrum, after normalization, standardization, confirmation 5508-6534cm-1、7143-
7976cm-1、8092-9273cm-1、9751-11602cm-1Four spectral detection scopes are set up as modeling wave band using PLS methods
Quantitative calibration models.To avoid the occurrence of " over-fitting " phenomenon, using a cross-validation method reasonable selection main cause subnumber is stayed, intersection is tested
DMAC, H that card is obtained2Respectively as shown in Figure 3 and Figure 4, optimal main cause subnumber is 5 to the main cause subnumber of O content.
4th, analyze：
By 140 spandex performed polymer samples, wherein 100 samples are used as calibration set, 40 samples are used as forecast set.With most
The predicted value of the corresponding sample DMAC contents of good main cause subnumber with actual value matched curve as shown in figure 5, with optimal main cause subnumber
Corresponding sample H2The predicted value of O content is with actual value matched curve as shown in fig. 6, the phase relation of the predicted value and true value of DMAC
Number R2=0.99996, H2The predicted value of O and the coefficient R of true value2=0.99994, concrete numerical value is shown in Table 2, modeling result reason
Think, it is reliable.
The sample of 40 forecast sets is predicted using newly-built near infrared spectrum calibration model, DMAC, H2O predicted values
Correlation curve with true value is distinguished as shown in Figure 7, Figure 8.Relative coefficient R2=0.99996, predicted root mean square error RMSEP=
0.187573 (H2O), RMSEP=0.214264 (DMAC), it is basically identical with cross validation root-mean-square error (RMSECV), specifically
Numerical value is shown in Table 2.
Table 1
Claims (4)
1. it is a kind of for detecting the method that spandex produces solvent and moisture in solvent recovering system simultaneously, it is characterised in that the method
Comprise the following steps：
1) a series of various concentrations N, N '-dimethyl acetamide DMAC and water H are prepared2The standard liquid of O, selection is enough representative
The calibration set sample of property；
2) after sample spectra pretreatment, the near infrared spectrum spectrogram of calibration set sample, 12000~4000cm of sweep limits are determined-1
Wave band, and after carrying out Pretreated spectra, with DMAC in standard sample and H2O content is associated, and is distinguished using PLS
Set up calibration model；
3) determine testing sample near infrared spectrum spectrogram, using with step 2) in identical preprocess method treatment gained spectrum
Figure, the near infrared spectrum spectrogram of sample is divided using calibration model through ABB AB's Horizon MB analysis softwares after pretreatment
Analysis, obtains DMAC and H in testing sample2O content；
Wherein,
The preprocessing procedures are preheated to 50 DEG C to sample loading 8mm colorimetric cylinders after mixing sample；
Enough representational calibration set sample numbers are more than 100；
The H of the sample for infrared diaphanoscopy2O mass percents are 2.0%-100%, and DMAC mass percents are 0-
98%.
2. according to claim 1 for detecting the method that spandex produces solvent and moisture in solvent recovering system simultaneously,
Characterized in that, the assay method of described atlas of near infrared spectra is to use ABB AB MB3600 Fourier transformation near infrared lights
Spectrometer, using transmission mode, liquid cell dedicated test passage, each Sample Scan is averaged for 64 times and obtains.
3. according to claim 1 for detecting the method that spandex produces solvent and moisture in solvent recovering system simultaneously,
Characterized in that, the method for the pretreatment of described near infrared spectrum spectrogram is：Normalization, standardization.
4. according to claim 1 or 3 for simultaneously detect spandex production solvent recovering system in solvent and moisture side
Method, it is characterised in that the optimal wave band for being used to set up calibration model of the near infrared spectrum spectrogram of sample after described pretreatment
Confirm as 5508-6534cm-1、7143-7976cm-1、8092-9273cm-1、9751-11602cm-1Four spectral detection scopes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510109451.3A CN104730029B (en) | 2015-03-12 | 2015-03-12 | Method for detecting solvent and moisture in spandex production solvent recovering system simultaneously |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510109451.3A CN104730029B (en) | 2015-03-12 | 2015-03-12 | Method for detecting solvent and moisture in spandex production solvent recovering system simultaneously |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104730029A CN104730029A (en) | 2015-06-24 |
| CN104730029B true CN104730029B (en) | 2017-06-20 |
Family
ID=53454125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510109451.3A Active CN104730029B (en) | 2015-03-12 | 2015-03-12 | Method for detecting solvent and moisture in spandex production solvent recovering system simultaneously |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104730029B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111855605B (en) * | 2020-07-06 | 2022-03-25 | 中船(邯郸)派瑞特种气体股份有限公司 | Method and device for measuring water content in hydrogen fluoride by utilizing Fourier transform infrared spectroscopy |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001061320A1 (en) * | 2000-02-15 | 2001-08-23 | Kowalski Craig R | Plural component coating analysis |
| CN101403689A (en) * | 2008-11-20 | 2009-04-08 | 北京航空航天大学 | Nondestructive detection method for physiological index of plant leaf |
| CN102814888A (en) * | 2012-08-29 | 2012-12-12 | 广州华工百川科技股份有限公司 | Metal composite delivery pipe with polyurethane elastomer lining and manufacturing method and application of metal composite delivery pipe |
| CN102967579A (en) * | 2012-11-19 | 2013-03-13 | 深圳大学 | Method for representing polyurethane curing reaction by in-situ diffuse reflection infrared spectrum |
| CN104266998A (en) * | 2014-10-28 | 2015-01-07 | 浙江华峰氨纶股份有限公司 | Near-infrared spectrum detection method for isocyanate group content in spandex prepolymer |
-
2015
- 2015-03-12 CN CN201510109451.3A patent/CN104730029B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001061320A1 (en) * | 2000-02-15 | 2001-08-23 | Kowalski Craig R | Plural component coating analysis |
| CN101403689A (en) * | 2008-11-20 | 2009-04-08 | 北京航空航天大学 | Nondestructive detection method for physiological index of plant leaf |
| CN102814888A (en) * | 2012-08-29 | 2012-12-12 | 广州华工百川科技股份有限公司 | Metal composite delivery pipe with polyurethane elastomer lining and manufacturing method and application of metal composite delivery pipe |
| CN102967579A (en) * | 2012-11-19 | 2013-03-13 | 深圳大学 | Method for representing polyurethane curing reaction by in-situ diffuse reflection infrared spectrum |
| CN104266998A (en) * | 2014-10-28 | 2015-01-07 | 浙江华峰氨纶股份有限公司 | Near-infrared spectrum detection method for isocyanate group content in spandex prepolymer |
Non-Patent Citations (1)
| Title |
|---|
| 近红外光谱测定聚四氢呋喃混合液;高俊 等;《应用化学》;20081231;第25卷(第12期);第1435-1438页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104730029A (en) | 2015-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104062257B (en) | A kind of based on the method for general flavone content near infrared ray solution | |
| CN104062256B (en) | A kind of flexible measurement method based near infrared spectrum | |
| CN102879340A (en) | Method for quickly detecting nutritional quality of root/stem crops on basis of near-infrared spectrum | |
| CN101221125A (en) | Method for measuring eutrophication water body characteristic parameter by spectrum technology | |
| CN102539566B (en) | Method for fast detecting content of dioscin in dioscorea zingiberensis by utilizing near infrared spectrum technology | |
| CN104062259B (en) | A kind of use the method for total saponin content near infrared spectrum quick test complex prescription glue mucilage | |
| CN111488926B (en) | Soil organic matter determination method based on optimization model | |
| CN108267414A (en) | The near-infrared spectral analytical method of textile fiber content | |
| CN103091274B (en) | The method of near-infrared diffuse-reflectance spectroscopic assay Radix Salviae Miltiorrhizae for injection Polyphenol Acids moisture | |
| CN103969212B (en) | The method utilizing Terahertz frequency range FTIR technology detection by quantitative Pesticide Residues In Grain | |
| CN104266998A (en) | Near-infrared spectrum detection method for isocyanate group content in spandex prepolymer | |
| CN103592255A (en) | Soft method for measuring total protein content of donkey-hide gelatin skin solution on basis of near infrared spectrum technology | |
| CN102608057A (en) | Method for measuring contents of lamivudine and zidovudine in mixture | |
| CN104849232A (en) | Method for rapid detection of contents of water and protein in royal jelly | |
| CN105372200A (en) | Rapid detection method for SBS modified asphalt modifier contents | |
| CN101791331B (en) | Method for rapid determination of tannin content in Slvia Miltiorrhiza Bunge extracting solution | |
| CN105758819A (en) | Method for detecting organic components of soil by utilizing near infrared spectrum | |
| CN105784628A (en) | Method for detecting chemical composition of soil organic matter with mid-infrared spectra | |
| CN105784672A (en) | Drug detector standardization method based on dual-tree complex wavelet algorithm | |
| CN105486662A (en) | Cottonseed gossypol content non-destructive measurement method based on near-infrared spectrum technology | |
| CN103175805A (en) | Method for determining indexes of COD and BOD5 in sewage through near infrared spectrometry | |
| CN107064057A (en) | A kind of method for rapidly testing of low-water-content oil field sludge oil content | |
| CN106053384A (en) | Rapid quantitative detection method for sweet wormwood and honeysuckle alcohol precipitation concentration process | |
| CN105486663B (en) | A method of detecting the stable carbon isotope ratio of soil using near infrared spectrum | |
| CN101339150A (en) | Method for determining octane number based on dielectric spectra technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190826 Address after: 325206 Ruian Economic Development Zone, Dongshan Road, Zhejiang, No. 1788, No. Co-patentee after: Chongqing Huafeng spandex Co., Ltd. Patentee after: Zhejiang Huafeng Spandex Co., Ltd. Address before: 325206 Ruian Economic Development Zone, Dongshan Road, Zhejiang, No. 1788, No. Patentee before: Zhejiang Huafeng Spandex Co., Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: No. 1788, Dongshan Economic Development Zone, Ruian, Wenzhou, Zhejiang Patentee after: Huafeng Chemical Co.,Ltd. Patentee after: HUAFON CHONGQING SPANDEX Co.,Ltd. Address before: No. 1788, Dongshan Economic Development Zone, Ruian, Wenzhou, Zhejiang Patentee before: ZHEJIANG HUAFENG SPANDEX Co.,Ltd. Patentee before: HUAFON CHONGQING SPANDEX Co.,Ltd. |