CN102095714B - Flashing point forecasting method for mixed solution of flammable liquid - Google Patents
Flashing point forecasting method for mixed solution of flammable liquid Download PDFInfo
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- CN102095714B CN102095714B CN201010537224A CN201010537224A CN102095714B CN 102095714 B CN102095714 B CN 102095714B CN 201010537224 A CN201010537224 A CN 201010537224A CN 201010537224 A CN201010537224 A CN 201010537224A CN 102095714 B CN102095714 B CN 102095714B
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Abstract
The invention discloses a flashing point forecasting method for a mixed solution of flammable liquid, which is combined with the laser Raman spectroscopy to obtain the relationship between the flashing point of the mixed solution and the intensity of a characteristic peak of the Raman spectrum, and forecasts the flashing point of the mixed solution by utilizing the relationship. The flashing point forecasting method is simple, dispenses with complex calculation, and can be applied to multiple fields of daily experimental study, online real-time detection in industrial production, and the like.
Description
Technical field
The present invention relates to a kind of method of testing, particularly a kind of Forecasting Methodology of flammable liquid mixed solution flash-point.
Background technology
Flash-point is the steam of volatile combustible surface formation and the minimum temperature that AIR MIXTURES is met fire burns, is the important physical parameter of weighing the inflammable degree of compound.Among the GB GB6944-2005 " classification and code of dangerous goods ", flammable liquid is defined as: emit the liquid or the liquid mixture of inflammable vapour in its flash temperature when not being higher than 65.6 ℃ (closed cup test flash-point be not higher than 60.5 ℃ or its open cup test flash-point).At present, flash-point has become lubricating oil, the important performance characteristic of products such as liquid fuel and gasoline.
Mainly adopt experimental technique and mathematical computations Forecasting Methodology to the flash(ing) test of chemical substance at present, and the flash-point of chemical substance is predicted inaccurate at present and unified method.Most studies person adopts D-M (Determiner-Measure) construction-property correlation (QSPR) method that organic flash-point is carried out forecasting research in recent years; In conjunction with statistics software and specific mathematic calculation; According to molecular structure; The substituting group kind, quantity, information such as relative molecular weight are set up the Forecasting Methodology of flash-point.But,, adopt test method directly to measure flash-point and can produce chemical pollutant by disengaged vapor so at present main application experiment method is analyzed and researched to the Changing Pattern of mixed solution flash-point because this method is confined to the research of pure material.
Raman spectrum is a kind of scattering spectrum, and nineteen twenty-eight found by India physicist C .V.Raman, is widely used as a kind of analytical test means of the structure of matter.Be widely used in fields such as material, chemical industry, oil, macromolecule, biology, environmental protection, geology at present, become an important branch in the molecular spectroscopy.
The Raman spectrum analysis technology is a comprehensive analysis technology that learns a skill in spectral measurement methods, stoichiometry, grows up on the basis of computer technology and application testing technology, and in numerous spectrum, Raman spectrum has special advantages.
One. sensing range is wide, comprises common inorganics and organism, can realize detecting to biomacromolecule, natural and synthetic material (like CNT, photonic crystal etc.), ore, live body animal vegetable tissue, water contaminated samples, chemical reaction catalyst or the like.
Two. Raman spectrum does not destroy sample, does not need specimen preparation.
Three. be applicable to the measurement of water solution system.
Four. can be used for low concentration sample and detect.The detection sensitivity of Raman optical spectrum method is very high, especially to organic principle and biomacromolecule etc. in the water environment, very low detectability is arranged, and generally can reach mg/l or mmol/l.
Five. the intensity of Raman scattering concentration common and scatterer is linear relation, and this provides theoretical foundation for the quantitative test of sample.
Six. frequency multiplication that comprises in the Raman spectrum and group spectral band are than lacking in the infrared spectrum, so fundamental frequency band often only appears in Raman spectrum, bands of a spectrum are clear, analyze simply, are beneficial to identification.
Seven. can be in real time, detect on the spot.Spectrometer can adopt CCD as spectral detector, utilizes CCD can realize all band spectral scan characteristic at a high speed, can the spectral scan time be foreshortened to several seconds even shorter.
This patent has been invented a kind of test method that combines Raman spectrum prediction flammable liquid mixed solution flash-point, utilizes the Raman spectrum non-destructive determination, need not advantage such as specimen preparation and realizes the accurate prediction to flammable liquid mixed solution flash-point.This test method can be avoided complicated computing method, and the chemical pollutant of generation is few, and method is simple.
Summary of the invention
The object of the invention for a kind of Forecasting Methodology of flammable liquid mixed solution flash-point is provided, utilizes the Raman spectrum non-destructive determination exactly, need not advantage such as specimen preparation and realizes the accurate prediction to flammable liquid mixed solution flash-point.
In order to achieve the above object, the present invention has adopted following technical scheme: a kind of Forecasting Methodology of flammable liquid mixed solution flash-point may further comprise the steps:
(1) be solute with a kind of flammable liquid; Another kind of flammable liquid is a solvent; Prepare the standard mixed solution of one group of flammable liquid mixed solution to be measured, make its concentration of volume percent be respectively 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% and 100%;
(2) flash-point of each standard mixed solution in the employing GB/T disclosed method difference determination step of 21615-2008 (1);
(3) adopt the laser Raman spectroscopy of each standard mixed solution in the laser Raman spectrometer determination step (1), choose suitable Raman spectrum characteristic peak, calculate the peak by force than;
(4) peak to each standard mixed solution is strong than carrying out fitting of a polynomial with the relation of flash-point, obtains the graph of relation of the strong ratio in flash-point one peak;
(5) measure the Raman spectrum of flammable liquid mixed solution to be measured, read the Raman spectrum characteristic peak intensity level, calculate the peak by force than, the graph of relation of the strong ratio in flash-point-peak that obtains according to step (4) reads the flash-point value of flammable liquid mixed solution to be measured;
Described suitable Raman spectrum characteristic peak is the Raman spectrum characteristic peak of solute in the mixed solution, and the foundation of choosing of the Raman spectrum characteristic peak of this solute is:
1) Raman spectrum of the solvent in the mixed solution does not produce interference to the Raman spectrum characteristic peak of this solute;
2) the Raman spectrum characteristic peak peak of selected solute is relatively stable by force.
Described Raman spectrum characteristic peak peak is strong to be that benchmark calculates than the characteristic peak intensity with pure component.
Described solute is selected from a kind of in ethanol and the acetonitrile, and described solvent is selected from a kind of in formamide and the cyclohexanone.
The present invention has following advantage and characteristics owing to adopted above technical scheme:
(1) sample size that needs is few, need not sample pretreatment, and process of the test does not produce chemical pollutant;
(2) can be used for the flash-point value of the inflammable mixed solution of fast measuring, can be applicable to real-time online and detect.
(3) can adopt this test method to measure the strong curve of flash-point-Raman spectrum characteristic peak that is fit to the different solutions system respectively to different solution systems.
(4) can avoid complicated computing method, method is simple.
Description of drawings
Fig. 1 is the Raman spectrum that adopts the ethanol of laser Raman spectrometer mensuration;
Fig. 2 is the Raman spectrum that adopts the acetonitrile of laser Raman spectrometer mensuration;
Fig. 3 is the Raman spectrum that adopts the formamide of laser Raman spectrometer mensuration;
Fig. 4 is the Raman spectrum that adopts the cyclohexanone of laser Raman spectrometer mensuration;
Fig. 5 be the Raman spectrum characteristic peak peak intensity of ethanol in formamide and cyclohexanone solution than
with the graph of relation of flash-point.
Fig. 6 be the Raman spectrum characteristic peak peak of acetonitrile in formamide and cyclohexanone solution by force than
with the graph of relation of flash-point.
Embodiment
The i-Raman type portable laser Raman spectrometer that following embodiment adopts U.S. Bi Da Imtech to produce, this Raman spectrometer selects for use the 785nm laser instrument as excitation source, and the spectral scan scope of this spectrometer is 175cm
-1～3200cm
-1Excitation wavelength is 785nm; Resolution is 5cm
-1Exciting power>=300mW.
Embodiment 1:
(1) with formamide and cyclohexanone as solvent, as solute, the dose volume percent concentration is four kinds of standard mixed solutions of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% and 100% respectively with ethanol and acetonitrile;
(2) adopt the flash point tester flash-point of each mixed solution of determination step (1) preparation respectively;
(3) Raman spectrogram of each mixed solution of employing laser Raman spectrometer determination step (1) preparation, continuous sweep three times, the equal spectrum of making even.The Raman spectrum that obtains ethanol is as shown in Figure 1, and the Raman spectrum of acetonitrile is as shown in Figure 2, and the Raman spectrum of formamide is as shown in Figure 3, and the Raman spectrum of cyclohexanone is as shown in Figure 4.
(4) choose raman characteristic peak according to the Raman spectrum of the pure component (solute) of research object, the main foundation of choosing raman characteristic peak is:
1) the Raman bands of a spectrum of the characteristic peak of solute and solvent do not disturb mutually;
2) the characteristic peak-to-peak is relatively stable by force;
According to above principle, choosing the ethanol peak shift is 883cm
-1Stretching vibration peak is characteristic peak (peak 2 among Fig. 1) in the C-C-O face at place, and choosing the acetonitrile peak shift is 2253cm
-1The flexible peak of the C ≡ N at place is characteristic peak (peak 3 among Fig. 2).
Characteristic peak intensity with pure component is that benchmark carries out normalization calculating to the Raman spectrum characteristic peak intensity of each mixed solution, the ratio that the characteristic peak-to-peak of the ethanol when obtaining variable concentrations according to following formula, acetonitrile is strong with the characteristic peak-to-peak of pure component by force:
R
n＝In
，mix/I
n，pure
In the formula: R
nThe expression peak shift be the n place the peak by force than; I
N, mixPeak shift is the intensity of the Raman peaks at n place in the expression mixed solution; I
N, pureThe expression pure material is the intensity of the Raman peaks at n place at peak shift.
(5) peak that obtains in the step (4) is by force carried out fitting of a polynomial than the flash-point value that obtains with step (1) with ORIGIN software; The polynomial fitting that adopts is:
y＝a+bx+cx
2+dx
3
Fig. 5 be the peak of ethanol in formamide and cyclohexanone solution by force than
with the relation curve of flash-point; Fig. 6 be the peak of acetonitrile in formamide and cyclohexanone solution by force than
with the relation curve of flash-point.Adopt following formula to carry out match, the result shows that the precision of match is higher, coefficient R
2＞0.98, explain that fitting result is better.Can know that from matched curve acetonitrile, ethanol reduce along with the increase of the strong ratio of its raman signatures peak-to-peak with the flash-point of formamide, cyclohexanone mixed solution, and reduction trend slows down gradually.
In the time of can finding out the solvent that in low flashpoint liquid, adds high-flash on the curve from Fig. 5 and Fig. 6, flash-point is to changing between the two.But for different solution systems, because the character of solution itself, the intermolecular force between solute and the solvent is different, can cause the polynomial coefficient of match different.And for the flash-point Changing Pattern of solute of the same race in different solvents, because intermolecular acting force is different, the polynomial expression after the match does not possess identical fitting coefficient yet.So the flash-point-peak that need adopt this test method to measure respectively to be fit to the different solutions system to different solution systems is by force than curve.
Utilize the present invention can analyze the Changing Pattern of the flash-point of flammable liquid mixed solution,, can analyse in depth flash-point from the molecular structure aspect with the strong Changing Pattern of raman characteristic peak through measuring the Raman spectrum of mixed solution.Can predict simultaneously that this method can be applicable in the actual productions such as day-to-day test research and on-line real time monitoring to the flash-point of unknown flammable liquid mixed solution.
Claims (3)
1. the Forecasting Methodology of a flammable liquid mixed solution flash-point is characterized in that, may further comprise the steps:
(1) be solute with a kind of flammable liquid; Another kind of flammable liquid is a solvent; Prepare the standard mixed solution of one group of flammable liquid mixed solution to be measured, make its concentration of volume percent be respectively 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% and 100%;
(2) flash-point of each standard mixed solution in the employing GB/T disclosed method difference determination step of 21615-2008 (1);
(3) adopt the laser Raman spectroscopy of each standard mixed solution in the laser Raman spectrometer determination step (1), choose suitable Raman spectrum characteristic peak, calculate the peak by force than;
(4) peak to each standard mixed solution is strong than carrying out fitting of a polynomial with the relation of flash-point, obtains the graph of relation of the strong ratio in flash-point-peak;
(5) measure the Raman spectrum of flammable liquid mixed solution to be measured, read the Raman spectrum characteristic peak intensity level, calculate the peak by force than, the graph of relation of the strong ratio in flash-point-peak that obtains according to step (4) reads the flash-point value of flammable liquid mixed solution to be measured;
Described suitable Raman spectrum characteristic peak is the Raman spectrum characteristic peak of solute in the mixed solution, and the foundation of choosing of the Raman spectrum characteristic peak of this solute is:
1) Raman spectrum of the solvent in the mixed solution does not produce interference to the Raman spectrum characteristic peak of this solute;
2) the Raman spectrum characteristic peak peak of selected solute is relatively stable by force.
2. the Forecasting Methodology of flammable liquid mixed solution flash-point as claimed in claim 1 is characterized in that: described Raman spectrum characteristic peak peak is strong to be that benchmark calculates than the characteristic peak intensity with pure component.
3. the Forecasting Methodology of flammable liquid mixed solution flash-point as claimed in claim 1 is characterized in that: described solute is selected from a kind of in ethanol and the acetonitrile, and described solvent is selected from a kind of in formamide and the cyclohexanone.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101806729A (en) * | 2010-03-31 | 2010-08-18 | 中国人民解放军总后勤部油料研究所 | In-use lubricating oil quality rapid testing method |
| CN101839877A (en) * | 2010-04-22 | 2010-09-22 | 上海化工研究院 | Combined type refrigerant low-temperature flash point testing system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101806729A (en) * | 2010-03-31 | 2010-08-18 | 中国人民解放军总后勤部油料研究所 | In-use lubricating oil quality rapid testing method |
| CN101839877A (en) * | 2010-04-22 | 2010-09-22 | 上海化工研究院 | Combined type refrigerant low-temperature flash point testing system |
Non-Patent Citations (1)
| Title |
|---|
| 王艳斌等.人工神经网络用于近红外光谱测定柴油闪点.《分析化学研究报告》.2000,第28卷(第9期),第1070-1073页. * |
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