CN104483288A - Perfluoro-isopropyl-hexanone fire extinguishing agent recognition and detection method - Google Patents

Abstract

The invention discloses a method for identifying and detecting a perfluoroisopropylhexanone fire extinguishing agent. The method is to collect near-infrared spectra of a standard sample and a sample to be tested, and then pass through the two near-infrared spectra with wavenumbers of 4065.2 cm ^-1 and 4670.8 cm ^-1 , 4790.3cm ^-1 and 5280.1cm ^-1 absorption peaks were compared to preliminarily determine whether the unknown sample is a perfluoroisopropylhexanone fire extinguishing agent; then select a specific wave number range to establish a perfluoroisopropylhexanone The test model of ketone fire extinguishing agent is used, so that the fire extinguishing agent sample to be tested can be accurately identified by using the established model. The invention realizes the purpose of accurately identifying whether an unknown sample is the perfluoroisopropylhexanone fire extinguishing agent through chemometric analysis and modeling, and the method is simple and convenient to operate, rapid in analysis and low in analysis cost.

Description

Identification and detection method of perfluoroisopropylhexanone fire extinguishing agent

technical field

The invention relates to the field of fire protection, in particular to a method for identifying and detecting a perfluoroisopropylhexanone fire extinguishing agent.

Background technique

A variety of fire extinguishing agents are restricted by the United Nations Treaty on the Protection of the Ozone Layer due to their serious damage to the environment. The development of environmentally friendly, efficient and safe fire extinguishing agents has become a problem faced by countries all over the world. Existing fire extinguishing agents such as heptafluoropropane and hexafluoropropane have certain corrosiveness and toxicity in the decomposition products at high temperature. Therefore, it is very necessary to develop and utilize new fire extinguishing agents.

Perfluoroisopropylhexanone is a new type of efficient, safe and environmentally friendly fire extinguishing medium. Its molecules contain bromine and unsaturated olefins, which can cut off the combustion chain reaction during the fire extinguishing process; and when it is released into the environment, the existing double bonds are easily destroyed by the combined action of light and hydrogen and oxygen radicals in the atmosphere. Decomposition, so it will not enter the ozone layer and cause damage to it, and has no greenhouse effect; the results of toxicity and corrosion tests show that the fire extinguishing agent is within its fire extinguishing concentration range, non-toxic to the human body, non-corrosive to electrical equipment, etc., and conforms to environmental protection requirements. However, there is currently no rapid detection and identification method for perfluoroisopropylhexanone fire extinguishing agent in my country.

Contents of the invention

The main purpose of the present invention is to provide a method for identifying and detecting perfluoroisopropylhexanone fire extinguishing agent, aiming to fill the gap in domestic methods for identifying and detecting perfluoroisopropylhexanone fire extinguishing agent.

In order to achieve the above object, a kind of perfluoroisopropylhexanone fire extinguishing agent identification and detection method provided by the invention comprises the following steps:

Step 1. Determining the absorption spectrum of the sample to be tested for near-infrared light with a wavenumber range of 4050cm ^-1 to 5323cm ^-1 , the wavenumber and absorbance of the absorption peak;

Step 2. Detect the sample to be tested at wavenumbers of 4065.2cm ^-1 (±5cm ^-1 ), 4670.8cm ^-1 (±5cm ^-1 ), 4790.3cm ^-1 (±5cm ^-1 ), 5280.1cm ^-1 (±5cm ^-1 ) whether there is an absorption peak, if not, then determine that the sample to be tested is a non-perfluoroisopropylhexanone fire extinguishing agent; if there is, then enter the next step to continue testing;

Step 3: After the second-order derivation pretreatment is performed on the absorption spectrum of the sample to be tested, the preprocessed spectrum of the sample to be tested is obtained, and according to the spectrum in the wavenumber bands are 4049.8cm ^-1 ~ 4998.6cm ^-1 and 5237.7cm ^-1 ~ The derivative value corresponding to 5322.6cm ^-1 establishes the Euclidean distance model, the similarity coefficient model or the consistency test model;

Step 4, comparing the calculated value of the Euclidean distance model, similarity coefficient model or consistency check model with the preset detection limit, when the value calculated by the Euclidean distance model and the similarity coefficient model is not less than If the preset detection limit is exceeded, it is determined whether the sample to be tested is a perfluoroisopropylhexanone fire extinguishing agent, otherwise it is determined that the sample to be tested is a non-perfluoroisopropylhexanone fire extinguishing agent;

When the value calculated by the consistency check model is less than the preset detection limit, it is determined that the sample to be tested is a perfluoroisopropylhexanone fire extinguishing agent, otherwise it is determined that the sample to be tested is a non-perfluoroisopropylhexanone fire extinguisher agent.

Preferably, the Euclidean distance model is:

$\mathrm{<span\; class="notranslate">\; D.</span>}<span\; class="notranslate">\; =</span>\sqrt{\underset{\mathrm{<span\; class="notranslate">\; i</span>}<span\; class="notranslate">\; =</span>\mathrm{<span\; class="notranslate">\; 1</span>}}{\overset{\mathrm{<span\; class="notranslate">\; no</span>}}{\mathrm{<span\; class="notranslate">\; \&Sigma;</span>}}}{<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; x</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>{\mathrm{<span\; class="notranslate">\; the\; s</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; )</span>}^{\mathrm{<span\; class="notranslate">\; 2</span>}}}$

Wherein, i is a natural number in [1,+∞), x _i is the derivative value corresponding to the i-th wavenumber in the wavenumber section in step three, and _si is the wavenumber of perfluoroisopropylhexanone in step three The derivative value corresponding to the i-th wavenumber in the segment;

When defining _xi = 0, the corresponding Euclidean distance value takes the maximum value D _max ; when defining _xi = s _i , the corresponding Euclidean distance value takes the minimum value D _min ; linearly transform D _max and D _min into 0-100 The matching value between, if the calculated matching value is not less than the detection limit of 95, it is determined that the sample to be tested is a perfluoroisopropyl hexanone fire extinguishing agent, otherwise it is determined to be a non-perfluoroisopropyl hexanone fire extinguishing agent.

Preferably, the similarity coefficient model is:

$\mathrm{<span\; class="notranslate">\; R</span>}<span\; class="notranslate">\; =</span>\mathrm{<span\; class="notranslate">\; R</span>}<span\; class="notranslate">\; =</span>\frac{\mathrm{<span\; class="notranslate">\; cov</span>}<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; x</span>}<span\; class="notranslate">\; ,</span>\mathrm{<span\; class="notranslate">\; the\; s</span>}<span\; class="notranslate">\; )</span>}{{\mathrm{<span\; class="notranslate">\; \&delta;</span>}}_{\mathrm{<span\; class="notranslate">\; x</span>}}{\mathrm{<span\; class="notranslate">\; \&delta;</span>}}_{\mathrm{<span\; class="notranslate">\; the\; s</span>}}}<span\; class="notranslate">\; =</span>\frac{{\mathrm{<span\; class="notranslate">\; \&Sigma;</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}<span\; class="notranslate">\; =</span>\mathrm{<span\; class="notranslate">\; 1</span>}}^{\mathrm{<span\; class="notranslate">\; no</span>}}<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; x</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>\stackrel{<span\; class="notranslate">\; \&OverBar;</span>}{\mathrm{<span\; class="notranslate">\; x</span>}}<span\; class="notranslate">\; )</span><span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; the\; s</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>\stackrel{<span\; class="notranslate">\; \&OverBar;</span>}{\mathrm{<span\; class="notranslate">\; the\; s</span>}}<span\; class="notranslate">\; )</span>}{\sqrt{{\mathrm{<span\; class="notranslate">\; \&Sigma;</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}<span\; class="notranslate">\; =</span>\mathrm{<span\; class="notranslate">\; 1</span>}}^{\mathrm{<span\; class="notranslate">\; no</span>}}{<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; x</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>\stackrel{<span\; class="notranslate">\; \&OverBar;</span>}{\mathrm{<span\; class="notranslate">\; x</span>}}<span\; class="notranslate">\; )</span>}^{\mathrm{<span\; class="notranslate">\; 2</span>}}}<span\; class="notranslate">\; \&Center\; Dot;</span>\sqrt{{\mathrm{<span\; class="notranslate">\; \&Sigma;</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}<span\; class="notranslate">\; =</span>\mathrm{<span\; class="notranslate">\; 1</span>}}^{\mathrm{<span\; class="notranslate">\; no</span>}}{<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; the\; s</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>\stackrel{<span\; class="notranslate">\; \&OverBar;</span>}{\mathrm{<span\; class="notranslate">\; the\; s</span>}}<span\; class="notranslate">\; )</span>}^{\mathrm{<span\; class="notranslate">\; 2</span>}}}}$

Among them, R∈[-1,1], i∈[1,+∞) is a natural number, x _i is the derivative value corresponding to the i-th wavenumber position in the wavenumber segment in step 3, and s _i is perfluoroisopropyl The original spectrum of base hexanone carries out the derivative value corresponding to the i-th wavenumber in the wavenumber segment of the spectrum after the second-order derivation pretreatment, is the average value of the derivative value of the sample to be tested in the wavenumber segment; The average value of the derivative value of the spectrum in the wave number segment after the second-order derivation pretreatment is carried out for the original spectrum of perfluoroisopropylhexanone;

When R∈[-1,0], it means that the near-infrared spectrum similarity between the sample to be tested and perfluoroisopropylhexanone is 0%, and when R∈(0,1], it means that the sample to be tested is similar to perfluoroisopropyl The near-infrared spectrum similarity of isopropylhexanone is the corresponding percentage between R ₀ ∈ (0% ~ 100%], when R ₀ is not less than 95% of the detection limit, it is determined that the sample to be tested is perfluoroisopropyl Hexanone fire extinguishing agent, otherwise it is judged as non-perfluoroisopropylhexanone fire extinguishing agent.

Preferably, the consistency check model is:

${\mathrm{<span\; class="notranslate">\; CI</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; =</span><span\; class="notranslate">\; |</span>\frac{{\mathrm{<span\; class="notranslate">\; x</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>{\stackrel{<span\; class="notranslate">\; \&OverBar;</span>}{\mathrm{<span\; class="notranslate">\; the\; s</span>}}}_{\mathrm{<span\; class="notranslate">\; i</span>}}}{\mathrm{<span\; class="notranslate">\; \&sigma;</span>}}<span\; class="notranslate">\; |</span>$

Wherein, a natural number in i∈[1,+∞), x _i is the derivative value corresponding to the i-th wavenumber position in the wavenumber section in step 3, and the perfluoroisopropylhexanone in the wavenumber section The average value of the derivative value measured multiple times at the i-th wavenumber position is The standard deviation is σ;

When the CI _i is less than the detection limit 3, it is determined that the sample to be tested is a perfluoroisopropyl hexanone fire extinguishing agent, otherwise it is determined as a non-perfluoroisopropyl hexanone fire extinguishing agent.

Preferably, the method further includes step 4 before step 1: measuring the absorption spectrum and wavenumber of the absorption peak of the standard sample of perfluoroisopropylhexanone to near-infrared light with a wavenumber range of 4050cm ^-1 to 5323cm ^-1 ;

Preferably, the purity of the standard sample of perfluoroisopropylhexanone is greater than 99%.

Preferably, performing second-order derivation preprocessing on the absorption spectrum of the sample to be measured includes: performing standard normal variable transformation and second-order derivation of five-point smoothing and five-point differential width on the original spectrum of the sample to be measured.

Preferably, the collection of the standard sample of perfluoroisopropylhexanone or the near-infrared spectrum of the sample to be tested is to store the sample to be tested in a quartz glass tube in a liquid state under constant temperature conditions, and place the quartz glass tube in a near-infrared The spectrum is collected on the transmission accessory of the equipment.

Preferably, the collection of the near-infrared spectrum of the same standard sample of perfluoroisopropylhexanone or the same sample to be tested is repeated at least three times, and five spectra are continuously collected each time, wherein perfluoroisopropylhexanone All spectra of the standard sample are averaged and converted into a spectrum, which represents the spectrum of the standard sample of perfluoroisopropylhexanone; all spectra of the sample to be tested are converted into a spectrum after averaging, and the spectrum represents the spectrum to be Measure the spectrum of the sample.

The invention achieves the purpose of accurately identifying whether an unknown sample is the perfluoroisopropylhexanone fire extinguishing agent through chemometrics analysis modeling and setting the detection limit.

Description of drawings

Figure 1 is the near-infrared original spectrum of perfluoroisopropylhexanone.

Fig. 2 is the near-infrared pretreatment spectrogram of perfluoroisopropylhexanone;

Figure 3 is the near-infrared original spectrum of unknown sample X3;

Fig. 4 is the near-infrared pretreatment spectrogram of unknown sample X3;

Figure 5 is the near-infrared original spectrum of unknown sample X6;

Figure 6 is the near-infrared pretreatment spectrum of unknown sample X6.

The realization of the purpose of the present invention, functional characteristics and advantages will be further described in conjunction with the embodiments and with reference to the accompanying drawings.

Detailed ways

It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

The invention provides a method for identifying and detecting perfluoroisopropylhexanone fire extinguishing agent, which is characterized in that it comprises the following steps:

Step 1. Determining the absorption spectrum and wavenumber of the absorption peak of the sample to be tested for near-infrared light with a wavenumber range of 4050cm ^-1 to 5323cm ^-1 ;

Step 2. Detect the sample to be tested at wavenumbers of 4065.2cm ^-1 (±5cm ^-1 ), 4670.8cm ^-1 (±5cm ^-1 ), 4790.3cm ^-1 (±5cm ^-1 ), 5280.1cm ^-1 (±5cm ^-1 ) whether there are obvious absorption peaks, if not, then determine that the sample to be tested is a non-perfluoroisopropylhexanone fire extinguishing agent; if there is, then enter the next step to continue testing;

Step 3: After the second-order derivation pretreatment is performed on the absorption spectrum of the sample to be tested, the preprocessed spectrum of the sample to be tested is obtained, and the corresponding derivative value of the spectrum in the wavenumber range of 4061.3cm ^-1 to 4636.1cm ^-1 is used to establish the Euclidean The distance model, similarity coefficient model or consistency test model;

Step 4, comparing the calculated value of the Euclidean distance model, similarity coefficient model or consistency test model with the preset detection limit, so as to judge whether the sample to be tested is perfluoroisopropylhexanone fire extinguishing agent.

Specifically, since the spectrograms of the sample to be tested and the standard sample of perfluoroisopropylhexanone will be compared, it is also necessary to measure the standard sample of perfluoroisopropylhexanone in the wavenumber range of 4050cm ^-1 before step one. ~5323cm ^-1 near-infrared light absorption spectrum and the wavenumber of the absorption peak; of course, the spectrogram of the standard sample for determination of perfluoroisopropylhexanone can be determined on the spot, or it can be measured and recorded before.

The near-infrared spectrum collection of the standard sample is under the condition of constant temperature and humidity, through the near-infrared special quartz glass tube, the perfluoroisopropyl hexanone fire extinguishing agent with a purity greater than 99.0% is collected, and the quartz glass tube is placed in the transmission of the near-infrared equipment. The spectrum is collected on the accessory, and the spectrum collection is repeated at least three times for the same standard sample, and five spectra are continuously collected each time, and the spectra are averaged and converted into one spectrum to represent the standard sample;

The near-infrared spectrum collection of the sample to be tested is also under constant temperature and humidity conditions. The sample to be tested is stored in a quartz glass tube in a liquid state, and the quartz glass tube is placed on the transmission accessory of the near-infrared device for spectrum collection. For the same A sample to be tested is repeated at least three times for spectrum collection, and five spectra are continuously collected each time, and the spectra are averaged and converted into one spectrum to represent an unknown sample;

In addition, in order to obtain better spectrograms and spectral data, the perfluoroisopropylhexanone fire extinguishing agent identification and detection method also includes performing spectral preprocessing on the original spectrum, and the spectral preprocessing includes one of the following processing methods or Combinations: mean centering, standardized normalization, moving average smoothing, convolution smoothing, first derivative, second derivative, convolution derivation, standard normal variable transformation, multivariate scatter correction, Fourier transform, and wavelet transform.

In the second-order derivation preprocessing of the absorption spectrum of the sample to be measured, it is preferable to perform standard normal variable transformation and second-order derivation of five-point smoothing and five-point differential width on the original spectrum of the sample to be measured.

The method will be further described in detail through three examples below.

Embodiment one

The Euclidean distance model is established according to the derivative values corresponding to the preprocessed spectra with wavenumber bands ranging from 4049.8cm ^-1 to 4998.6cm ^-1 and 5237.7cm ^-1 to 5322.6cm ^-1 :

$\mathrm{<span\; class="notranslate">\; D.</span>}<span\; class="notranslate">\; =</span>\sqrt{\underset{\mathrm{<span\; class="notranslate">\; i</span>}<span\; class="notranslate">\; =</span>\mathrm{<span\; class="notranslate">\; 1</span>}}{\overset{\mathrm{<span\; class="notranslate">\; no</span>}}{\mathrm{<span\; class="notranslate">\; \&Sigma;</span>}}}{<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; x</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>{\mathrm{<span\; class="notranslate">\; the\; s</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; )</span>}^{\mathrm{<span\; class="notranslate">\; 2</span>}}}$

Wherein, i is a natural number in [1,+∞), x _i is the derivative value corresponding to the i-th wavenumber in the wavenumber segment in step 3, and _si is 2-bromo-3,3,3-trifluoro The derivative value corresponding to the i-th wavenumber in the wavenumber segment of the spectrum after the second-order derivation preprocessing of the original spectrum of propylene.

When defining _xi = 0, the corresponding Euclidean distance value takes the maximum value D _max , indicating that the two spectra do not match completely; when defining _xi = _si , the corresponding Euclidean distance value takes the minimum value D _min , indicating that the two spectra are completely matched ;Convert D _max and D _min to a matching value between 0 and 100, if the calculated matching value is not less than the detection limit of 95, it is determined that the sample to be tested is a perfluoroisopropylhexanone fire extinguishing agent , otherwise it is judged as non-perfluoroisopropylhexanone fire extinguishing agent.

Referring to Fig. 1 and Fig. 2, through calculation, it is obtained that D _max = 0.6223 and D _min = 0 in the range of wave number ranges of 4049.8cm ^-1 to 4998.6cm ^-1 and 5237.7cm ^-1 to 5322.6cm ^-1 of the spectrum;

${\mathrm{<span\; class="notranslate">\; D.</span>}}_{\mathrm{<span\; class="notranslate">\; max</span>}}<span\; class="notranslate">\; =</span>\sqrt{{\mathrm{<span\; class="notranslate">\; the\; s</span>}}_{\mathrm{<span\; class="notranslate">\; 1</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; the\; s</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; the\; s</span>}}_{\mathrm{<span\; class="notranslate">\; 3</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; +</span><span\; class="notranslate">\; \&Center\; Dot;</span><span\; class="notranslate">\; \&Center\; Dot;</span><span\; class="notranslate">\; \&Center\; Dot;</span><span\; class="notranslate">\; +</span>{\mathrm{<span\; class="notranslate">\; the\; s</span>}}_{\mathrm{<span\; class="notranslate">\; no</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}}$

Linearly transform D _max and D _min into matching values between 0 and 100, that is, 0.6223 corresponds to 0 (matching value), and 0 (D _min ) corresponds to 100 (matching value); through the above two sets of data calculation Conversion formula: y=-160.694x+100.

Using the same method as the standard sample to carry out spectral pretreatment on 7 unknown samples, the Euclidean distance values between the unknown sample and the standard sample can be calculated by the established Euclidean distance discriminant model as D ₁ , D ₂ , D ₃ , D _4. D ₅ , D ₆ , D ₇ , and convert D into a matching value through the conversion formula y=-160.694x+100 according to D _max and D _min (wherein, a negative value indicates that the sample to be tested has an inverted peak), see Shown in table 1, only have the matching value of test sample _X1 to be greater than 95, therefore judge _X1 is perfluoroisopropyl hexanone fire extinguishing agent (1230) (for convenience of expression, following to perfluoroisopropyl hexanone fire extinguishing agent Agents are referred to as 1230 fire extinguishing agent), and the remaining 6 samples are not perfluoroisopropylhexanone fire extinguishing agent.

Table 1 Prediction results of Euclidean distance model for perfluoroisopropylhexanone (1230) fire extinguishing agent

Table 2 Derivative value of original absorbance of standard sample of 1230 fire extinguishing agent after pretreatment

Table 3 The original absorbance value and pretreatment derivative value of unknown sample X3

Table 4 The original absorbance and derivative value after pretreatment of unknown sample X6

Among them, the data in Table 2 comes from Figure 1 and Figure 2; the data in Table 3 comes from Figure 3 and Figure 4; the data in Table 4 comes from Figure 5 and Figure 6.

Embodiment two

The similarity coefficient model is established according to the derivative values corresponding to the preprocessed spectra with wavenumber bands ranging from 4049.8cm ^-1 to 4998.6cm ^-1 and 5237.7cm ^-1 to 5322.6cm ^-1 :

$\mathrm{<span\; class="notranslate">\; R</span>}<span\; class="notranslate">\; =</span>\frac{\mathrm{<span\; class="notranslate">\; cov</span>}<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; x</span>}<span\; class="notranslate">\; ,</span>\mathrm{<span\; class="notranslate">\; the\; s</span>}<span\; class="notranslate">\; )</span>}{{\mathrm{<span\; class="notranslate">\; \&delta;</span>}}_{\mathrm{<span\; class="notranslate">\; x</span>}}{\mathrm{<span\; class="notranslate">\; \&delta;</span>}}_{\mathrm{<span\; class="notranslate">\; the\; s</span>}}}<span\; class="notranslate">\; =</span>\frac{{\mathrm{<span\; class="notranslate">\; \&Sigma;</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}<span\; class="notranslate">\; =</span>\mathrm{<span\; class="notranslate">\; 1</span>}}^{\mathrm{<span\; class="notranslate">\; no</span>}}<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; x</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>\stackrel{<span\; class="notranslate">\; \&OverBar;</span>}{\mathrm{<span\; class="notranslate">\; x</span>}}<span\; class="notranslate">\; )</span><span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; the\; s</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>\stackrel{<span\; class="notranslate">\; \&OverBar;</span>}{\mathrm{<span\; class="notranslate">\; the\; s</span>}}<span\; class="notranslate">\; )</span>}{\sqrt{{\mathrm{<span\; class="notranslate">\; \&Sigma;</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}<span\; class="notranslate">\; =</span>\mathrm{<span\; class="notranslate">\; 1</span>}}^{\mathrm{<span\; class="notranslate">\; no</span>}}{<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; x</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>\stackrel{<span\; class="notranslate">\; \&OverBar;</span>}{\mathrm{<span\; class="notranslate">\; x</span>}}<span\; class="notranslate">\; )</span>}^{\mathrm{<span\; class="notranslate">\; 2</span>}}}<span\; class="notranslate">\; \&Center\; Dot;</span>\sqrt{{\mathrm{<span\; class="notranslate">\; \&Sigma;</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}<span\; class="notranslate">\; =</span>\mathrm{<span\; class="notranslate">\; 1</span>}}^{\mathrm{<span\; class="notranslate">\; no</span>}}{<span\; class="notranslate">\; (</span>{\mathrm{<span\; class="notranslate">\; the\; s</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>\stackrel{<span\; class="notranslate">\; \&OverBar;</span>}{\mathrm{<span\; class="notranslate">\; the\; s</span>}}<span\; class="notranslate">\; )</span>}^{\mathrm{<span\; class="notranslate">\; 2</span>}}}}$

Among them, R∈[-1,1], i∈[1,+∞) is a natural number, x _i is the derivative value corresponding to the i-th wavenumber position in the wavenumber segment in step 3, and s _i is the The original spectrum of propylhexanone carries out the derivative value corresponding to the i-th wavenumber in the wavenumber segment of the spectrum after the second-order derivation pretreatment, is the average value of the derivative value of the sample to be tested in the wavenumber segment, and is the first value of the sample to be tested in the wavenumber segment The original spectrum of perfluoroisopropylhexanone is the average value of the derivative value of the spectrum after second-order derivation pretreatment in the wave number segment; cov (x, s) is closer to the value of δ _x δ _s , Indicates that the sample to be tested is more similar to 1230, that is, when the R value is closer to 1, the sample to be tested is more similar to 1230.

When R∈[-1,0], it means that the near-infrared spectrum similarity between the sample to be tested and perfluoroisopropylhexanone is 0%, and when R∈(0,1], it means that the sample to be tested is similar to perfluoroisopropyl The near-infrared spectrum similarity of isopropylhexanone is the corresponding percentage between R ₀ ∈ (0% ~ 100%], when R ₀ is not less than 95% of the detection limit, it is determined that the sample to be tested is perfluoroisopropyl Hexanone fire extinguishing agent, otherwise it is judged as non-perfluoroisopropylhexanone fire extinguishing agent.

The spectral pretreatment of 7 unknown samples was carried out by the same method as the standard sample, and the correlation coefficient between the unknown sample and the standard sample could be calculated through the established correlation coefficient model. Referring to Table 5, Table 5 is the prediction result of the similarity coefficient model of 1203 fire extinguishing agents, wherein only the correlation coefficient numbered _X1 is above 95%.

Table 5 Prediction results of the similarity coefficient model for perfluoroisopropylhexanone (1230) fire extinguishing agent

Embodiment Three

Select the derivative values corresponding to the pretreatment spectra from 4049.8cm ^-1 to 4998.6cm ^-1 and 5237.7cm ^-1 to 5322.6cm ^-1 to establish a consistency test model:

${\mathrm{<span\; class="notranslate">\; CI</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; =</span><span\; class="notranslate">\; |</span>\frac{{\mathrm{<span\; class="notranslate">\; x</span>}}_{\mathrm{<span\; class="notranslate">\; i</span>}}<span\; class="notranslate">\; -</span>{\stackrel{<span\; class="notranslate">\; \&OverBar;</span>}{\mathrm{<span\; class="notranslate">\; the\; s</span>}}}_{\mathrm{<span\; class="notranslate">\; i</span>}}}{\mathrm{<span\; class="notranslate">\; \&sigma;</span>}}<span\; class="notranslate">\; |</span>$

Wherein, a natural number in i∈[1,+∞), x _i is the derivative value corresponding to the i-th wavenumber position in the wavenumber section in step 3, and the perfluoroisopropylhexanone in the wavenumber section The average value of the derivative value measured multiple times at the i-th wavenumber position is The standard deviation is σ; the mean value of the position derivative value for each wave number Add or subtract 3 times the standard deviation (σ), then the consistency limit value CI _limit = 3, take 3 as the detection limit, when CI _i is less than the detection limit 3, it is determined that the sample to be tested is perfluoroisopropyl Hexanone fire extinguishing agent, otherwise it is judged as non-perfluoroisopropylhexanone fire extinguishing agent.

Table 6 Derivative value, average value and standard deviation of 1230 fire extinguishing agent standard samples after multiple pretreatments

Table 7 shows the calculation results of the consistency index CI _i value for the derivative values corresponding to the wave number bands of 3303 fire extinguishing agent from 4049.8cm ^-1 to 4998.6cm ^-1 and 5237.7cm ^-1 to 5322.6cm ^-1 .

Table 7 Prediction results of consistency model of perfluoroisopropylhexanone (1230) fire extinguishing agent

The above are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process conversion made by using the description of the present invention and the contents of the accompanying drawings, or directly or indirectly used in other related technical fields , are all included in the scope of patent protection of the present invention in the same way.

Claims (9)

1. a perfluoroisopropyl hexanone fire extinguishing agent recognition detection method, is characterized in that, comprise the following steps:

Step one, mensuration testing sample are 4050cm to wave-number range ^-1~ 5323cm ^-1the absorption spectrum of near infrared light, the wave number of absorption peak and absorbance;

Step 2, detection testing sample are 4065.2cm in wave number ^-1(± 5cm ^-1), 4670.8cm ^-1(± 5cm ^-1), 4790.3cm ^-1(± 5cm ^-1), 5280.1cm ^-1(± 5cm ^-1) whether place all have absorption peak, if do not had, then judge to treat that test sample is as non-perfluorinated isopropyl hexanone fire extinguishing agent; If had, then enter next step and continue to detect;

Step 3, second order differentiate pre-service is carried out to the absorption spectrum of testing sample after, obtain the pre-processed spectrum of testing sample, and be 4049.8cm according to this spectrum in wave number section ^-1~ 4998.6cm ^-1and 5237.7cm ^-1~ 5322.6cm ^-1corresponding derivative value sets up Euclidean distance model, similarity coefficient model or consistency check model;

Step 4, by the calculated value of described Euclidean distance model, similarity coefficient model or consistency check model with preset detection limit contrast, the value calculated when described Euclidean distance model and described similarity coefficient model is not less than default detection limit, then judge testing sample whether perfluoroisopropyl hexanone fire extinguishing agent, otherwise judge that testing sample is as non-perfluorinated isopropyl hexanone fire extinguishing agent;

When the value that described consistency check model calculates is less than default detection limit, then judge that testing sample is as perfluoroisopropyl hexanone fire extinguishing agent, otherwise judge that testing sample is as non-perfluorinated isopropyl hexanone fire extinguishing agent.

2. perfluoroisopropyl hexanone fire extinguishing agent recognition detection method as claimed in claim 1, it is characterized in that, described Euclidean distance model is:

Wherein, i be [1 ,+∞) in natural number, x _ifor the derivative value that i-th wave number in the wave number section in step 3 is corresponding, s _ifor the derivative value that i-th wave number is corresponding in described wave number section of perfluoroisopropyl hexanone in step 3;

Definition x _ieuclidean distance value corresponding when=0 gets maximal value D _max; Definition x _i=s _itime, corresponding Euclidean distance value gets minimum value D _min; By D _maxand D _mingeometric ratio is linearly converted into the matching value between 0 ~ 100, if when the matching value calculated is not less than detection limit 95, then judges that testing sample is as perfluoroisopropyl hexanone fire extinguishing agent, otherwise is judged to be non-perfluorinated isopropyl hexanone fire extinguishing agent.

3. perfluoroisopropyl hexanone fire extinguishing agent recognition detection method as claimed in claim 1, it is characterized in that, described similarity coefficient model is:

Wherein, R ∈ [-1,1], i ∈ [1 ,+∞) in natural number, x _ifor the derivative value that i-th beam location in the wave number section in step 3 is corresponding, s _ioriginal spectrum for perfluoroisopropyl hexanone carries out the pretreated spectrum of the second order differentiate derivative value that i-th wave number is corresponding in described wave number section, for the mean value of the derivative value of testing sample in described wave number section; original spectrum for perfluoroisopropyl hexanone carries out the mean value of the derivative value of the pretreated spectrum of second order differentiate in described wave number section;

When R ∈ [-1,0], represent that the near infrared spectrum similarity of testing sample and perfluoroisopropyl hexanone is 0%, when R ∈ (0,1] time, the near infrared spectrum similarity of expression testing sample and perfluoroisopropyl hexanone is R ₀∈ (0% ~ 100%] between corresponding number percent, work as R ₀when being not less than detection limit 95%, then judging that testing sample is as perfluoroisopropyl hexanone fire extinguishing agent, otherwise be judged to be non-perfluorinated isopropyl hexanone fire extinguishing agent.

4. perfluoroisopropyl hexanone fire extinguishing agent recognition detection method as claimed in claim 1, it is characterized in that, described consistency check model is:

Wherein, i ∈ [1 ,+∞) in natural number, x _ifor the derivative value that i-th beam location in the described wave number section in step 3 is corresponding, the derivative value mean value that i-th beam location of perfluoroisopropyl hexanone in described wave number section repeatedly measures is standard deviation is σ;

Work as CI _iwhen being less than detection limit 3, then judging that testing sample is as perfluoroisopropyl hexanone fire extinguishing agent, otherwise be judged to be non-perfluorinated isopropyl hexanone fire extinguishing agent.

5. as right wants the perfluoroisopropyl hexanone fire extinguishing agent recognition detection method as described in 1, it is characterized in that, the method also comprised step 4 before step one: the standard model measuring perfluoroisopropyl hexanone is 4050cm to wave-number range ^-1~ 5323cm ^-1the absorption spectrum of near infrared light and the wave number of absorption peak.

6. perfluoroisopropyl hexanone fire extinguishing agent recognition detection method as claimed in claim 5, it is characterized in that, the standard model purity of described perfluoroisopropyl hexanone is greater than 99%.

7. perfluoroisopropyl hexanone fire extinguishing agent recognition detection method as claimed in claim 1, it is characterized in that, comprise carrying out second order differentiate pre-service to the absorption spectrum of testing sample: standard normal variable conversion is carried out to the original spectrum of testing sample and the second order differentiate of 5 level and smooth, five points difference width.

8. the perfluoroisopropyl hexanone fire extinguishing agent recognition detection method as described in any one of claim 1 to 7, it is characterized in that, be under constant temperature, testing sample is stored in quartz glass tube with liquid state to the collection of the standard model of perfluoroisopropyl hexanone or the near infrared spectrum of testing sample, transmission annex quartz glass tube being positioned near infrared gear carry out spectra collection.

9. the perfluoroisopropyl hexanone fire extinguishing agent recognition detection method as described in any one of claim 1 to 7, it is characterized in that, to the collection of the standard model of same perfluoroisopropyl hexanone or the near infrared spectrum of same testing sample at least in triplicate, and each continuous acquisition five spectrum, wherein, all spectrum of the standard model of perfluoroisopropyl hexanone change into a spectrum after equalization, and this spectrum represents the spectrum of the standard model of perfluoroisopropyl hexanone; All spectrum of testing sample change into a spectrum after equalization, and this spectrum represents the spectrum of sample to be tested.