CN102636588A - Method for discriminating white spirits by using quartz crystal oscillator electronic nose - Google Patents
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- CN102636588A CN102636588A CN2012101278602A CN201210127860A CN102636588A CN 102636588 A CN102636588 A CN 102636588A CN 2012101278602 A CN2012101278602 A CN 2012101278602A CN 201210127860 A CN201210127860 A CN 201210127860A CN 102636588 A CN102636588 A CN 102636588A
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Abstract
The invention discloses a method for discriminating white spirits by using quartz crystal oscillator electronic nose, comprising the steps of: detecting the smell of a standard white spirit sample by using the electronic nose, processing data by using electronic nose system software so as to generate a first-order derivative curve peak graph presenting volatility smell frequency functions of different white spirit samples so as to establish a discriminating standard 1 by using the first-order derivative curve peak graph, selecting characteristic variables according to area values of curve peaks, carrying out typical discriminance analysis by using statistic analysis software, classifying different white spirit standards, establishing a discriminating standard 2, and taking the discriminating standard 2 as the basis of white spirit discrimination. According to the invention, the quartz crystal oscillator electronic nose and a mathematic statistic method are firstly combined to discriminate white spirits, the detection speed is high and the discrimination correctness is high, data can be automatically generated and processed, the chemical compositions of different smells can be qualitatively and quantitively reflected, the steps are simple, the operation is convenient, large-scale popularization and application are convenient, and the types and maturity degrees of different white spirits, especially the white spirits with small year difference and similar varieties, can be rapidly and effectively discriminated.
Description
Technical field
The present invention relates to the liquor discrimination method, be specifically related to adopt the quartz oscillator Electronic Nose to differentiate the method for liquor.
Background technology
The discrimination method of liquor mainly comprises the Shi Jianding that samples wine, gc analysis etc. at present.Rely on specialty teacher of the sampling wine to differentiate liquor with mouthfeel and color and luster, influenced greatly by subjective factor, evaluation result is objective inadequately because of often, and odorousness also can't quantitative expression, is difficult to be applied to industrialization, automated production; Though vapor-phase chromatography accurately qualitative, quantitative ground is measured the multiple compositions such as acids, ester class, aldehydes and alcohols in the liquor; But analytic process is comparatively complicated; Institute's use checkout equipment cost is higher; Length consuming time, and the high-speed centrifugal seperator of gas chromatograph can be smashed the big molecule of liquor, the compound of destruction reflection liquor aging degree.
Electronic Nose is to develop a kind of faster artificial olfactory system in recent years.The maximum Electronic Nose of utilization is a sensor array formula Electronic Nose at present; Sensor array formula Electronic Nose is the combination of 10 ~ 30 sensors, and when odor adsorption was to sensor, its resistance changed; Different sensor is different to different odor responses; These signal combination are got up, analyze, establish the characteristic spectrum of different odor at last with mode identification technology.But this type of Electronic Nose is not suitable for detecting China white wine, because changes in resistance is more responsive to ethanol, has covered and has only accounted for fragrant composition of being of 1-2% ratio; And this type of sensor saturated reaction time is long, and speed is slow, and detecting data needs the artificial mathematical statistics method statistic of using; Can't realize robotization, final data is a pattern-recognition collection of illustrative plates also, and its data and chemical constitution disconnect fully; Particularly to the liquor that the time is more or less the same or kind is similar, resolution is not high, and recognition accuracy is low.
The quartz oscillator Electronic Nose can detect the chemical constitution of volatile matter in one minute.Quartz crystal sensor energising back is with high hunting of frequency, and its oscillation frequency changes when test compound drops on the sensor, and the variable quantity of frequency is relevant with quantity, the kind of compound.The frequency variation of sensor is detected by microprocessor, and finally being reflected in becomes a peak on the number axis, and peak area is with regard to the quantity (Peak Area – PA) of representation compound.Volatile matter was separated by the chromatographic column of a weak point earlier before arriving sensor, wherein different and unique (Retention Time-RT) of the hold-up time of different compounds in chromatographic column.Peak face amount PA and hold-up time RT combine; Different compound compositions in just can quantitative, qualitative reflection volatile matter; And this characteristic peak figure can be used as the characteristic spectrum of different liquor, is used for the Preliminary Identification of liquor, combines the mathematical statistics analytic approach on this basis; Can do further discriminating to liquor, therefore have very high resolution.The separating column of this Electronic Nose is short than gas chromatograph, and disengaging time is short, and speed is fast, and separation accuracy is not high, but can keep the big molecule of the aging degree of reaction in the liquor effectively, therefore is particularly suitable for the detection of China white wine.In addition, the used separating column of this Electronic Nose is only collected the C5-C20 molecule, has comprised human appreciable liquor aromatic odor molecule basically, does not but absorb ethanol molecule, thereby has avoided the influence of alcohol to testing result.
Summary of the invention
To weak point of the prior art; The present invention combines the smell first order derivative curve peak figure that quartz oscillator Electronic Nose fast detecting generates with the mathematical statistics analytic approach, provide a kind of fast, accurate, liquor discrimination method that high resolution is arranged.
Technical scheme of the present invention is following:
A kind of method that adopts the quartz oscillator Electronic Nose to differentiate liquor comprises that concrete steps are following:
(1) adopt the head space method to collect Chinese sprits standard sample volatile matter sample;
(2) with the quartz oscillator Electronic Nose liquor standard model smell is detected; Generate the first order derivative curve peak figure of the frequency function of corresponding different liquor sample volatile flavors by electric nasus system software, set up discrimination standard 1 with this characteristic spectrum as different liquor;
(3) utilize statistical analysis software to carry out typical diagnostic method analysis; From first order derivative curve peak figure, choose all and set up linear discriminant function as characteristic variable greater than 200 peak area value; With this discriminant function the liquor sample is differentiated classification; And choose preceding two the canonical variable values of this function, thereby set up discrimination standard 2 as the horizontal ordinate typical discriminatory analysis scatter diagram that draws;
(4) according to the said same method of operating of setting up discrimination standard in step (1)～(3); Detect liquor sample to be checked; Gained first order derivative curve peak figure and typical discriminatory analysis scatter diagram are compared judgement with the discrimination standard 2 that the discrimination standard 1 and the step (3) of step (2) foundation are set up respectively, can learn the kind and the aging degree of liquor to be checked.
The said head space method of step (1) is: the liquor sample of device in airtight vial accounts for 25～75% of vial volume, and at room temperature places 30～120 minutes.
The said quartz oscillator Electronic Nose of step (2) to the step that liquor standard model smell detects is: the initial temperature of each parts of Electronic Nose is set, wherein 40～80 ℃ of sensors, 20～60 ℃ of chromatographic columns, 140～180 ℃ of rotary valves, 180～220 ℃ of injection ports, 200～300 ℃ of adsorbers; Carrier gas flow velocity 2～4cm is set
3/ min; From the airtight vial of said apparatus liquor, drew the liquor volatile matter 5～20 seconds through the sampling syringe needle; Chromatographic column at the uniform velocity is heated to 150～250 ℃ from above-mentioned initial temperature with the speed of 10 ℃ of per seconds, carries out data acquisition then, data acquiring frequency 0.01～1 second/inferior, 10～30 seconds duration.
Said carrier gas is helium.
Beneficial technical effects of the present invention is:
The smell first order derivative curve peak figure that the present invention generates quartz oscillator Electronic Nose fast detecting first combines with the mathematical statistics analytic approach and is used for the discriminating of liquor; The combination of above-mentioned two kinds of methods; Can effectively improve the discriminating accuracy of liquor; Thereby it is not high to the liquor resolution to solve prior art, the problem that recognition accuracy is low.Detection speed of the present invention is fast, can reflect the chemical constitution of different odor qualitative, quantitatively, and step is simple; Easy to operate; Be convenient to large-scale promotion application, can identify the kind of different liquor and the liquor that aging degree, particularly time are more or less the same or kind is similar quickly and efficiently.
Description of drawings
Fig. 1 is the first order derivative curve peak figure of six kinds of different Fenyang wine in the embodiment of the invention (50 years states hide Fenyang wine, 10 old Bai Fen, a year Fenyang wine, glass Fen, string and steam wine, the Xinghua Village) and n-alkane n-Alkanes standard solution volatile flavor frequency function.
Fig. 2 is a typical discriminatory analysis scatter diagram in the embodiment of the invention.
Embodiment
Do further description below in conjunction with the embodiment specific embodiments of the invention, following examples are convenient to understand better the present invention, but do not limit the present invention.
50 years states among the following embodiment hide Fenyang wine, 10 old Bai Fen, 1 year Fenyang wine, glass Fen, the Xinghua Village, string and steam wine and provide by Chinese Fenyang wine group.
The foundation of 1: the six kind of aging degree Fenyang wine of difference of embodiment detection model and the detection of sample
State's Tibetan Fenyang wine, 10 old Bai Fen, 1 year Fenyang wine, glass Fen, the Xinghua Village, string steamed six kinds of Fenyang wine of wine and respectively get 14 samples as standard liquor sample in (1) 50 year.
(2) adopt the head space method to collect Chinese sprits standard sample volatile matter sample, be about to 20 milliliters of liquor samples and put into 40 milliliters of airtight vials, at room temperature placed 10 minutes.
(3) use Electronic Nose zNose
TMLiquor standard model smell is detected, and testing process is: initial temperature is set, 60 ℃ of sensors, 40 ℃ of chromatographic columns, 165 ℃ of rotary valves, 200 ℃ of injection ports, 250 ℃ of adsorbers; Helium flow velocity 3cm is set
3/ min; From the airtight vial of said apparatus liquor, drew the liquor volatile matter 10 seconds through the sampling syringe needle; Chromatographic column at the uniform velocity is heated to 180 ℃ from 40 ℃ of speed with 10 ℃ of per seconds; Carry out data acquisition then, data acquiring frequency 0.02 second/inferior, 20 seconds duration, each test sample duplicate detection six times; Data Detection finishes, and bakes sensor 30 seconds in 150 ℃, all according to above-mentioned flow process with Electronic Nose idle running once, to remove the remaining smell in the Electronic Nose, reduces the subsequent detection error after each liquor sample detection finishes.In said process, use n-alkane n-Alkanes standard solution per hour instrument to be proofreaied and correct simultaneously, its purpose or effect are to provide for the liquor smell first order derivative curve peak figure that detection by electronic nose generates the reference standard curve of a carbon atom distribution.
(4) generate the first order derivative curve peak figure of the frequency function of corresponding liquor samples and n-alkane n-Alkanes solution different odor by electric nasus system software MicroSense 4.0; Set up discrimination standard 1 with this curve as the characteristic spectrum of different liquor, the result sees Fig. 1.As shown in Figure 1, can be qualitative by the first order derivative curve peak figure that MicroSense 4.0 software processes generate, reflect the difference of quantity and chemical constitution between six kinds of Fenyang wine volatile flavors (C5-C20) quantitatively.Wherein, n-Alkanes numbering 6-14 representes the C6-C14 scent molecule, and 50 years states hide Fenyang wine numbering 1-9 and represent 1-peak, peak 9, represent its 9 types of different escaping gases.Comparatively speaking, its detected high carbon compound gas (C10-C14) of Fenyang wine of a specified duration more is many more the time.
(5) utilize SAS software to carry out typical diagnostic method analysis; From first order derivative curve peak figure, choose all and set up linear discriminant function as characteristic variable greater than 200 peak area value; With this discriminant function the liquor sample is differentiated classification; And choose preceding two the canonical variable values of this function as the horizontal ordinate typical discriminatory analysis scatter diagram that draws, thus setting up discrimination standard 2, the result sees Fig. 2.
(6) each 3 sample of liquor (state's Tibetan Fenyang wine, 10 old Bai Fen, 1 year Fenyang wine, glass Fen, the Xinghua Village, string steamed wine in 50 years) of getting 6 kinds of prior known kinds again are as sample to be checked; But suppose that when detecting its kind is unknown; Detect according to the said same method of operating of setting up discrimination standard in step (2)～(5); And the discrimination standard 2 that the discrimination standard of setting up with step (4) 1 and step (5) are set up compares judgement; Decision method is: the peak figure that the first order derivative curve peak figure of visual inspection and liquor to be checked coincide basically, and the liquor that this peak figure is corresponding is the kind of liquor to be checked; In typical discriminatory analysis scatter diagram, the calibration value zone that visual inspection liquor test value to be checked is fallen, the corresponding liquor in this zone is the kind of liquor to be checked.The result sees Fig. 2.As shown in Figure 2, through confirming that liquor sample survey value to be checked has nearly all dropped in the calibration value interval of its corresponding liquor kind.Wherein, CV1 is a canonical variable 1, and CV2 is a canonical variable 2, and C1-6 is a calibration value, and V1-6 is a test value.
Above-mentioned Electronic Nose zNose
TMBe a kind of typical quartz oscillator Electronic Nose, available from U.S. Electronic Sensor Technology company, 7100 models.The software that above-mentioned MicroSense 4.0 softwares carry for this Electronic Nose.
Above-mentioned experiment shows, method provided by the invention can be found out the difference of scent molecule quantity and chemical constitution between aged liquor and the low time liquor quickly and accurately on the basis of a cover discrimination standard of being set up, thereby identifies the liquor of different aging degree.The method is used to screen fake wine, the high imitative liquor that wine, particularly time are more or less the same or kind is similar, too fast effectively.
Claims (4)
1. method that adopts the quartz oscillator Electronic Nose to differentiate liquor is characterized in that concrete steps are following:
(1) adopt the head space method to collect Chinese sprits standard sample volatile matter sample;
(2) with the quartz oscillator Electronic Nose liquor standard model smell is detected; Generate the first order derivative curve peak figure of the frequency function of corresponding different liquor sample volatile flavors by electric nasus system software, set up discrimination standard 1 with this characteristic spectrum as different liquor;
(3) utilize statistical analysis software to carry out typical diagnostic method analysis; From first order derivative curve peak figure, choose all and set up linear discriminant function as characteristic variable greater than 200 peak area value; With this discriminant function the liquor sample is differentiated classification; And choose preceding two the canonical variable values of this function, thereby set up discrimination standard 2 as the horizontal ordinate typical discriminatory analysis scatter diagram that draws;
(4) according to the said same method of operating of setting up discrimination standard in step (1)～(3); Detect liquor sample to be checked; Gained first order derivative curve peak figure and typical discriminatory analysis scatter diagram are compared judgement with the discrimination standard 2 that the discrimination standard 1 and the step (3) of step (2) foundation are set up respectively, can learn the kind and the aging degree of liquor to be checked.
2. according to the said a kind of method that adopts the quartz oscillator Electronic Nose to differentiate liquor of claim 1; It is characterized in that the said head space method of step (1) is: the liquor sample of device in airtight vial accounts for 25～75% of vial volume, and at room temperature places 30～120 minutes.
3. according to the said a kind of method that adopts the quartz oscillator Electronic Nose to differentiate liquor of claim 1; It is characterized in that the said quartz oscillator Electronic Nose of step (2) to the step that liquor standard model smell detects is: the initial temperature of each parts of Electronic Nose is set, wherein 40～80 ℃ of sensors, 20～60 ℃ of chromatographic columns, 140～180 ℃ of rotary valves, 180～220 ℃ of injection ports, 200～300 ℃ of adsorbers; Carrier gas flow velocity 2～4cm is set
3/ min; From the airtight vial of said apparatus liquor, drew the liquor volatile matter 5～20 seconds through the sampling syringe needle; Chromatographic column at the uniform velocity is heated to 150～250 ℃ from above-mentioned initial temperature with the speed of 10 ℃ of per seconds, carries out data acquisition then, data acquiring frequency 0.01～1 second/inferior, 10～30 seconds duration.
4. according to the said a kind of method that adopts the quartz oscillator Electronic Nose to differentiate liquor of claim 3, it is characterized in that said carrier gas is helium.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102980948A (en) * | 2012-10-31 | 2013-03-20 | 湖南天之衡酒业有限公司 | Detection method for liquor grade |
| CN103235057A (en) * | 2013-04-27 | 2013-08-07 | 江南大学 | Method for identifying white spirit origin place by using gas phase chromatography-mass spectrometry without analyzing compounds |
| CN103278416A (en) * | 2013-05-24 | 2013-09-04 | 北京交通大学 | Preparation method of gas sensor array for detecting Luzhou-flavor liquor |
| CN104267134A (en) * | 2014-09-03 | 2015-01-07 | 上海应用技术学院 | Method for identifying brand of Chinese liquor by rapid gas phase electronic nose |
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| WO2006125848A1 (en) * | 2005-05-23 | 2006-11-30 | Consejo Superior De Investigaciones Científicas | Automatic system for the continuous analysis of the evolution of wine |
| CN101487824A (en) * | 2009-03-03 | 2009-07-22 | 中国农业大学 | Method for recognizing beer flavor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102980948A (en) * | 2012-10-31 | 2013-03-20 | 湖南天之衡酒业有限公司 | Detection method for liquor grade |
| CN103235057A (en) * | 2013-04-27 | 2013-08-07 | 江南大学 | Method for identifying white spirit origin place by using gas phase chromatography-mass spectrometry without analyzing compounds |
| CN103278416A (en) * | 2013-05-24 | 2013-09-04 | 北京交通大学 | Preparation method of gas sensor array for detecting Luzhou-flavor liquor |
| CN104267134A (en) * | 2014-09-03 | 2015-01-07 | 上海应用技术学院 | Method for identifying brand of Chinese liquor by rapid gas phase electronic nose |
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