CN102023140A - Method for measuring 1-2 propylene glycol content by using near infrared ray (NIR) technology - Google Patents

Method for measuring 1-2 propylene glycol content by using near infrared ray (NIR) technology Download PDF

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CN102023140A
CN102023140A CN 201110003063 CN201110003063A CN102023140A CN 102023140 A CN102023140 A CN 102023140A CN 201110003063 CN201110003063 CN 201110003063 CN 201110003063 A CN201110003063 A CN 201110003063A CN 102023140 A CN102023140 A CN 102023140A
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propylene glycol
sample
nir
content
forecast model
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CN102023140B (en
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胡立中
薛训明
张胜军
李长兴
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China Tobacco Anhui Industrial Co Ltd
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China Tobacco Anhui Industrial Co Ltd
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Abstract

The invention relates to a method for measuring 1-2 propylene glycol content by using a near infrared ray (NIR) technology, which is characterized in that the structural feature that a 1-2 propylene glycol molecule contains groups of a C-H key, an H-O key and an R-OH key which are relatively sensitive to the NIR is used to collect the spectral information of the 1-2 propylene glycol; the spectroscopic data of samples are analyzed by principal component analysis (PCA), and a partial least squares (PLS) method is used to establish a model and optimize, namely, the NIR prediction model of the 1-2 propylene glycol is established; the prediction model is used to measure the 1-2 propylene glycol content in the process of producing cigarettes. According to the method for measuring the 1-2 propylene glycol content by using the NIR technology, the samples are in no need of pretreatment and drugs are also not needed; and the method can be used for environmentally-friendly, safe, no-wear, rapid, accurate, mass and continuous detection.

Description

NIR technical measurement 1-2 content of propylene glycol method
Technical field
The present invention relates to a kind of NIR technical measurement 1-2 content of propylene glycol method, particularly in tobacco, add known 1-2 propylene glycol degree, adopt NIR to capture the sample sets spectral information, through PCA technical Analysis sample spectra information data, utilize PLS to set up forecast model, detect 1-2 propylene glycol degree in the unknown sample by forecast model, change the method for the 1-2 of detection content of propylene glycol commonly used.
Background technology
Present stage, State Tobacco Monopoly Bureau's issue " the inhomogeneity mensuration of cigarette charging " (soliciting original text), solicit the method that adopts in the original text and be and in the production of cigarettes process, add the 1-2-propylene glycol thing that serves as a mark, by the reinforced uniformity ratio reinforced the analysis of label content detection.Detection method is to adopt traditional vapor-phase chromatography, and the problem that this method exists has: to the sample pre-treatments more complicated, the mensuration cycle is long, detects to lag behind weak points such as unsuitable continuous batch detection.
Summary of the invention
The present invention is the new assay method of 1-2-propylene glycol, this method is avoided gas chromatography and the existing weak point of high-efficient liquid phase chromatogram technology, a kind of quick, accurate, continuous and a large amount of detection mode is provided, can be applicable in the reinforced process of cigarette producing process, assessment cigarette charging homogeneity realizes the quick consistance that effectively instructs cigarette charging.Method of the present invention can also realize Long-distance Control and on-site supervision analysis.
Technical solution problem of the present invention adopts following technical scheme.
NIR technical measurement 1-2 content of propylene glycol method, carry out as follows:
A, utilization uniform Design method are foundation with the content of 1-2 propylene glycol, establish the quantity of sample sets;
B, will behind the mixing tobacco leaf, choose a sample in per 60 seconds greater than the tobacco leaf of the thin material of at least 25 different brackets in 10 areas from tobacco export, independent sealed preservation, quantity is formed sample by the requirement of a step;
The sample of c, oven dry b step is guaranteed moisture content in leaves less than 5%, weighing 20 gram samples; Smoking sample is to make moisture and ethanol volatilization, gets rid of the two interference to 1-2 propylene glycol spectral information.
D, the 1-2 propylene glycol after will diluting with atomization sprayer evenly are sprayed onto in the sample of the c step after the weighing;
E, with the sample oven dry that contains the 1-2 propylene glycol of d step, preserve to the room temperature sealing, it is to be measured to form sample sets;
F, the sample sets spectral information of using near infrared (NIR) to capture, utilization PCA technical finesse spectral information data; Set up 1-2 content of propylene glycol forecast model; The homogeneity of the forecast model assessment cigarette charging that utilization is set up.
The characteristics of the inventive method also are:
Described 1-2 propylene glycol value is by the determined value of a step method uniform Design, takes by weighing described 1-2 propylene glycol amount by mass percentage, with the number percent of sample quality be 0.3%～2%.
Among the described step f, forecast model after PLS optimizes, coefficient of determination R 2＞95.00%, mean square deviation RMSECV＜0.500.
The detection method of 1-2 content of propylene glycol of the present invention is compared with vapor-phase chromatography, high performance liquid chromatograph method that present China uses always, and beneficial effect is embodied in:
1. need not the sample that need detect is carried out pre-treatment.
2. testing process need not medicine, realizes environmental protection.
3. quick, pollution-free, nothing consume, continuous and accurate.
4. model can be converted into on-line monitoring, realizes remote on-line analytic.
5. expand and to apply to other outer reinforced link of cigarette process, as technological processs such as flavoring and casing, leaves moistings.
This method can detect and monitor the additive in the process according to the production technology actual demand.By measuring the homogeneity of 1-2 content of propylene glycol, assess the homogeneity of whole reinforced process, thereby effectively ensure the consistance of producing the product interior quality.
Description of drawings
Fig. 1 is the distribution situation figure of pure content; Fig. 2 is sheet cigarette 1-2 propylene glycol near infrared forecast model figure.
Embodiment
The present invention is described in further detail below in conjunction with embodiment
Embodiment:
1, sample is selected and is made
1.1, by specification technical scheme a step design sample quantity.By the consumption of actual production of cigarettes processing technology 1-2 propylene glycol, uniform Design is provided with 1-2 propylene glycol percentage composition (%), resolution (cm -1) and offal quality (g) 3 factors, 2 horizontal indexs, each factor 37 number of levels, 37 test numbers.Total inventory is 20g, and 3 factors are carried out control line setting up and down: 1-2 propylene glycol percentage composition (%) 0.3%～2%, resolution (cm -1) 4cm -1～8cm -1, offal quality (g) 10g～20g, by the interval of Automatic Program setting level value, adopting factor determines minimum number of run, at U 37(37 12) the design table in, the table that 3 factors of choosing are formed, design deviation is 0.0913, forms U 37(37 3) the Uniform Design form, again resolution in the uniform Design form and offal quality are solidified, be respectively 8cm -1And 20g, calculate 1-2 propylene glycol percentage composition with 20 grams again, obtain 37 groups of sample sets, 1-2 propylene glycol percentage composition be multiply by the offal quality, obtain 1-2 propylene glycol quality; 2 conversion 1-2 propylene glycol percentage compositions, resolution and offal quality again, same disposal route obtains 37 * 2 forms.Have the sample sets of 37 * 3 quantity.The distribution situation of alcohol content as shown in Figure 1.
1.2, by specification technical scheme b step makes 1.1 sample.
Get the pure tobacco leaf of the many grades in a plurality of areas (〉=10) (〉=25), place in the reinforced drum apparatus, close the feed liquid feeding device, after treating the tobacco leaf mixing, chose a sample in per 60 seconds, each sample 30 gram from tobacco export, independent sealed preservation, quantity are 37 * 3 requirement, form sample.Sample is being put into 45 ℃ of baking ovens, drying by the fire 6 hours, guaranteeing that moisture content in leaves is less than 5% (detecting with Oven Method).Through 60 order whirlwind bevellers, the sample after the baking is ground, take by weighing quantitative values and be the sample after the grindings of 20 grams.
1.3, the sample with 1.2, make the sample sets contain label 1-2 propylene glycol by the c step, to be measured.
Take by weighing 1-2 propylene glycol quality after step 1.1 converts in the 10ml volumetric flask, add 5-10 times of amount of alcohol dilution.1-2 propylene glycol after the dilution evenly is sprayed onto in the offal with atomizer, and the offal that will spray again behind the 1-2 propylene glycol is put into 45 ℃ of baking ovens, smokes 4-6 hour, and the process of smoking will be stirred 2-3 time, guarantees ethanol volatilization (detection of usefulness GC method).Preserve to the room temperature sealing, it is to be measured to form sample sets.
2, set up forecast model: set up forecast model by the d step.
The testing sample collection places 9cm quartz specimen cup, is positioned over the near infrared spectrum of gathering each sample in the near infrared spectrometer.The s main working parameters of FT-NIR spectrometer is set to: spectral scan scope 12000cm -1～4000cm -1, scanning times 64 times, resolution 8cm -1, the mug rotation sweep.Capture the sample sets spectral information, by PCA methods analyst sample spectra information, carry out the number percent true value (Actual) that predicted value (Calculated) and 1-2 propylene glycol take by weighing related, choose corresponding wave band (seeing Table 1), through the PLS of OPUS/QUANT-2 quantitative analysis software (partial least square method) sample spectral data is handled, carried out validation-cross (Crossvalidation) again and set up forecast model.
Table 1 chosen spectrum frequency-range table
Sequence number Starting point (cm -1) Terminal point (cm -1) Corresponding group
1 7097.1 6749.9 CH、CH 2、CH 3Two frequencys multiplication
2 6071.1 5430.8 CH、CH 2、CH 3Fundamental frequency
3 4883.1 4736.5 ROH
4 4451.1 4165.7 CH、CH 2、CH 3Mixing
3, modelling verification: in 0.3%-2%1-2 propylene glycol percentage composition scope, take by weighing 20 groups of samples at random, make sample, predict, will predict the outcome and actual value is compared by 2 steps by 1.2 and 1.3 steps.Determine the accuracy and the stability of forecast model.The results are shown in following table 2:
Table 2 checking result
Sequence number Actual concentrations (%) Prediction concentrations (%) Relative error Sequence number Actual concentrations (%) Prediction concentrations (%) Relative error
1 0.7528 0.7415 1.50％ 11 1.4098 1.4324 1.60％
2 0.3306 0.3291 0.45％ 12 1.2033 1.2213 1.50％
3 0.2727 0.2653 2.71％ 13 0.2469 0.2365 4.21％
4 1.3013 1.3114 0.78％ 14 0.31144 0.3258 4.61％
5 1.3977 1.3509 3.35％ 15 1.2692 1.2458 1.84％
6 0.347 0.3538 1.96％ 16 1.3403 1.3675 2.03％
7 1.5554 1.5789 1.51％ 17 0.4720 0.4487 4.94％
8 0.3663 0.3716 1.45％ 18 0.36107 0.36428 0.89％
9 1.8853 1.9699 4.49％ 19 0.9715 1.0197 4.96％
10 2.0179 2.113 4.71％ 20 0.9018 0.8940 0.86％
By table 2 comparison data as can be seen, relative error is less than 5%, illustrates that the forecast model of setting up by above-mentioned 1,2,3 steps predicts the outcome and has certain accuracy and stability.For the foundation of near infrared forecast model and the online application of sheet cigarette are laid a good foundation.
4, set up sheet cigarette 1-2 propylene glycol near-infrared model: (do not close the charging valve door, sample is not smoked, ground) step is got tobacco sample collection quantity according to 1.1 and 1.2, sampling amount is 50g/ time, be divided into 2 parts, a part is carried out spectral information and is captured (setting the spectrum running parameter by 2 steps), and another part utilizes gas Chromatographic Determination 1-2 content of propylene glycol (as actual value).Actual value and predicted value are carried out related, set up sheet cigarette 1-2 propylene glycol near infrared forecast model (shown in Figure 2).
From the model chart as can be seen: coefficient of determination R 2＞95.00%, mean square deviation RMSECV＜0.500.Therefore, institute's established model meets the demand that near infrared is set up forecast model, satisfies the forecast model condition of using as detecting.
5, sheet cigarette-12 propylene glycol near infrared forecast model checking: randomly draw reinforced certain board name cigarette, the forecast model that utilizes step 4 to set up the sheet cigarette is verified, the results are shown in following table 3.
Table 3 a cigarette forecast model checking result
Figure BDA0000043044930000041
As can be seen from Table 3: in the scope that the near infrared forecast model is contained, the relative error of prediction sample is basically less than 5%, and prediction effect is comparatively desirable.
6, utilization and evenly reinforced the evaluation: in the cigarette charging process exit of ZGF, XZW, three cigarette boards of HW name, 60s sampling at interval, the 30g that at every turn takes a sample, each serial sampling 50 times, wherein per 10 times is one group.Utilize the sheet cigarette 1-2 propylene glycol near infrared forecast model of having set up, dope the 1-2 content of propylene glycol (%) (the results are shown in following table 4, table 5, table 6) of sample.Calculate reinforced uniformity ratio (the results are shown in Table 7) with following formula (1),, the results are shown in Table result of calculation and be accurate to 0.1% by the reinforced homogeneity of reinforced uniformity ratio evaluation.
CU = ( 1 - 1 n - 1 Σ i = 1 n ( x i - x ‾ ) 2 x ‾ ) × 100 % . . . . . . ( 1 )
In the formula: the CU-uniformity ratio (%) that feeds in raw material;
x iThe content of propylene glycol an of-Di i sample, unit is massfraction (%);
Figure BDA0000043044930000043
The mean value of the content of propylene glycol of-i sample, unit are massfraction (%).
By estimating explanation:
1, three cigarette board name feeding homogeneities are comparatively desirable.
2, NIR technical measurement 1-2 content of propylene glycol new method have green, rapidly, continuously, pollution-free, do not have consume, an advantage continuously and accurately.
3, can realize on-line monitoring, realize remote on-line analytic.Satisfy high rate of industrialization production demand
4, can be extended to the on-line monitoring of other production (as medicine, food etc.) according to principle, realize the unanimity of product quality.
The table 7 uniformity coefficient measurement result (%) that feeds in raw material
Sequence number Board name 1ZGF Board name 2XZW Board name 3HW
1 87.2 88.7 90.9
2 86.2 87.8 89.0
3 85.4 86.6 91.3
4 89.7 91.4 92.2
5 90.8 91.1 91.1
Mean value 87.9 89.1 90.9
Standard deviation 2.06 1.86 1.05
The coefficient of variation 2.35 2.09 1.15
Table 4ZGFW board name 1-2 content of propylene glycol NIR predicts the outcome and gathers
Figure BDA0000043044930000051
Table 5XZW board name 1-2 content of propylene glycol NIR predicts the outcome and gathers
Unit: (%)
Figure BDA0000043044930000052
Table 6HW board name 1-2 content of propylene glycol NIR predicts the outcome and gathers
Unit: (%)

Claims (4)

1.NIR technical measurement 1-2 content of propylene glycol method is characterized in that carrying out as follows:
A, utilization uniform Design method are foundation with the content of 1-2 propylene glycol, establish the quantity of sample sets;
B, will behind the mixing tobacco leaf, choose a sample in per 60 seconds greater than the tobacco leaf of the thin material of at least 25 different brackets in 10 areas from tobacco export, independent sealed preservation, quantity is formed sample by the requirement of a step;
The sample of c, oven dry b step is guaranteed moisture content in leaves less than 5%, the weighing sample quality;
D, the 1-2 propylene glycol after will diluting with atomization sprayer evenly are sprayed onto in the sample of the c step after the weighing;
E, with the sample oven dry that contains the 1-2 propylene glycol of d step, preserve to the room temperature sealing, it is to be measured to form sample sets;
F, the sample sets spectral information of using near infrared (NIR) to capture, utilization PCA technical finesse spectral information data; Set up 1-2 content of propylene glycol forecast model; The homogeneity of the forecast model assessment cigarette charging that utilization is set up.
2. NIR technical measurement 1-2 content of propylene glycol method according to claim 1, it is characterized in that described 1-2 propylene glycol value is by the determined value of a step method uniform Design, take by weighing described 1-2 propylene glycol amount by mass percentage, with the number percent of sample quality be 0.3%～2%.
3. NIR technical measurement 1-2 content of propylene glycol method according to claim 1, the quantitative values that it is characterized in that sample among the described step c are 20 grams.
4. NIR technical measurement 1-2 content of propylene glycol method according to claim 1 is characterized in that in described step f, forecast model after PLS optimizes, coefficient of determination R 2＞95.00%, mean square deviation RMSECV＜0.500.
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CN103886224A (en) * 2014-04-15 2014-06-25 江西理工大学 Method for predicting melting temperature of metallurgical slag
CN114384039A (en) * 2020-10-20 2022-04-22 贵州中烟工业有限责任公司 Cigarette charging uniformity detection method based on spectral projection residual error

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CN1482455A (en) * 2003-04-30 2004-03-17 中国科学院山西煤炭化学研究所 Analytical method for chloramphenicol and 1,2-dihydroxypropane in medicine or skin care products

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Publication number Priority date Publication date Assignee Title
CN103886224A (en) * 2014-04-15 2014-06-25 江西理工大学 Method for predicting melting temperature of metallurgical slag
CN114384039A (en) * 2020-10-20 2022-04-22 贵州中烟工业有限责任公司 Cigarette charging uniformity detection method based on spectral projection residual error
CN114384039B (en) * 2020-10-20 2024-03-01 贵州中烟工业有限责任公司 Cigarette feeding uniformity detection method based on spectrum projection residual error

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