CN1367381A - Olfactory simulator and its olfactory simulation testing method - Google Patents
Olfactory simulator and its olfactory simulation testing method Download PDFInfo
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- CN1367381A CN1367381A CN 02111046 CN02111046A CN1367381A CN 1367381 A CN1367381 A CN 1367381A CN 02111046 CN02111046 CN 02111046 CN 02111046 A CN02111046 A CN 02111046A CN 1367381 A CN1367381 A CN 1367381A
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Abstract
The present invention relates to an olfactory simulation device and its olfactory simulation testing method. Said device is formed from main machine box, computer processing portion, display portion and power supply circuit, and said method includes the following steps: a). the odor to be tested can be sucked into ring testing box by means of miniature diaphragm pump, said gas can be quickly passed through sensing membrane surface of every sensor, then discharged from outlet; b). every response produced by every gas sensor when the gas is passed through every sensor can be collected into data collecting card, passed through A/D converter to obtain a multidimensional response signal; and c). said signal is processed by computer so as to can obtain the type of odor to be tested, integral intensity and its simple component composition, and can be displayed.
Description
Technical field
The present invention relates to a kind of olfactory analog device and olfactory analog method of testing thereof.
Background technology
Smell is to estimate to be one of leading indicator of fragrant goods inherent quality and ambient air quality quality.Up to now, the evaluation of article aroma qualities such as spices and essence, cigarette, wine, tea, soy sauce, vinegar, cosmetics and style is mainly still relied on people's sense of smell.Owing to be subjected to the influence of physiologic factors such as subjective and objective factor such as experience, mood, environment and fatigue, adaptation, custom, say in a sense, the sense organ method is difficult to the science of accomplishing and objective, than physics, the more difficult grasp of chemical analysis method, and, lean on people's sense organ to carry out quality monitoring not only arduous but also loaded down with trivial details work especially to being perfumery product production run.
For a long time, people long for by measuring chemical composition always and determine the quality of smell, component analyzing method such as gas chromatography, mass spectrum thereby obtained application comparatively widely.But the chemical composition of smell is various, and what influence sense organ impression belongs to trace, trace and even ultratrace level mostly; Some composition instability, instant promptly become in the smell, are difficult to extract effectively, concentrate and separate; Some compound structure is similar and the smell quality is widely different, promptly so-called " chirality " phenomenon; Scent of during some composition individualism, odorlessness again when existing jointly with other compositions; Odorlessness during some composition individualism, scent of again when existing jointly with other compositions; Smell was not strong when some composition concentrated, and watered down obviously grow of back; As if smell was very strong when some composition concentrated, obviously weaken after watering down, or the like.All this kind phenomenon explanation, although sensitivity day by day along with analytical instrument, people have found more and more many chemical constitutions from smell, but from qualitative angle, those factors that smell is produced special influence are also seldom understood by people and are grasped, therefore, the effect of component analyzing method is very limited.The problem that the spices worker often runs in practice is: two bottles of spices A, B of same kind different batches, and the gas chromatographic analysis result is that the purity of A is more much higher than B, but the subjective appreciation result thinks that the fragrance of B is better than A.With the exception of this, attempt determines that by measuring all chemical constitutions the idea of article aroma quality is unpractical under many circumstances in process of production.For example, the chemical constitution of cigarette smoke has kind more than 4,000, and these data are that American scholar obtains through making great efforts for many years, impossible often measurement.People expect analytical instrument resulting be not only chemical composition and concentration, but the result who conforms to the impression of people's sense organ.Just in this case, olfactory analog technology paid more and more attention.
The Electronic Nose device is a kind of instrument with ability of the simple and complicated smell of identification, and gas sensor that it is overlapped each other by a plurality of performances and suitable data analysis and disposal route are formed.Its strong point is and can carries out qualitative analysis to smell apace.To aroma-producing substances such as spices and essence, food, cosmetics, it can determine its classification, quality grade, freshness, the place of production with smell as the people, and even distinguishes that it is true and false.It is unique especially advantage in the mensuration of head perfume (or spice), body note and basic note, even can judge whether the content of objectionable constituent such as formaldehyde, ammonia in the air surpasses specified standard, or the like.Utilize the Electronic Nose device, public security traffic department can judge whether someone carries dangerous material with smell, and medical department can judge whether patient suffers from certain disease (as ephritis etc.) with the smell of breathing out, body gas or urine flavor; In addition, Electronic Nose also can be used for aspects such as chemical industry, war gas detection.Its test speed is fast, and application prospect is very wide.Report that western developed countries such as Japan have been classified the olfactory analog technology as one of important directions of new and high technology development outline in nearly mid-term " Economic Daily " 2000.1.14 day.
Begin the research of Electronic Nose Technology at the beginning of the eighties abroad, the mid-90 begins to occur commercial means, and is several as the intelligent nose (FOX series) of France, the smell scanner (Aromascan) of Britain etc.At present, Electronic Nose Technology is mainly used in the classification and the concentration of simple gases such as prediction CO, ethanol, CH4 and composition thereof, the classification of wine, milk, coffee, olive oil and the place of production, the freshness of meat products and aquatic products, the maturity of fruit etc.Report that the U.S. will consider to search for according to smell terrorist's hiding-place with Electronic Nose " Liberation Daily " 2001.1.10 day.But existing bibliographical information nearly all is that the following classification of 10 classes is judged, each class is only gathered ten several and even several samples and analyzed, and greatly differs from each other with application request.Do not stop after the intelligent nose of the smell scanner of Britain in 1998 and France in 1999 enters Chinese market, trace it to its cause, have the following subject matter to be solved that has:
1, the test box volume is excessive.Consider factors such as heat radiation, stirring, people often adopt big volume test box (common 1～5 liter).So, if will be diluted greatly after using carrier gas, gas to enter test box, equal significantly to have reduced the sensitivity and the perception lower limit of sensor; Moreover, if sensor directly places the head space of liquid and solid,, make the time of sensor contact gas increase corresponding prolongation of recovery time because the Volatile Gas equilibration time is very long.This runs in the opposite direction with the requirement that monitor in real time at the scene, the proving installation volume is little.
2, feature extraction mode is too single.Nearly all method is all only utilized the steady-state response of gas sensor.Because some compound is promptly to become in unsettled, instant in the smell, the intensity of smell also is time to time change; Because the influence of factors such as ambient temperature and humidity and sensor drift, absolute stable state does not exist.Therefore, the method for getting steady-state value is unfavorable for improving and improving sensitivity, the repeatability of sensor.For example, two its integrated values of bar response curve that " stable state " value is identical may differ greatly.
3, smell head space sampling mode is too complicated, the sampling poor repeatability.For example, the BH114 type Electronic Nose device of Britain attempts to make smell to be measured and atmospheric environment to isolate fully, and both the mode with people's perception smell was different fully, and range of application is very limited again.
4, data analysis and disposal route far can not satisfy the selectivity and the repeated requirement of Electronic Nose.For the subtle change of perception odour intensity, the high sensitivity of pursuing single gas sensitive device merely is far from being enough, to a great extent, also depends on the degree of accuracy and the antijamming capability of test circuit, the precision of data analysing method, fault-tolerance and popularization ability.In addition, data processing method also should have the compensation ability to sensor drift.Meanwhile, how extracting and to analyze the small useful signal of multidimensional down in very strong background " noise " is that the olfactory analog device moves towards practical necessary condition.
5, owing to the existence of phenomenons such as spatial isomerism, chirality, polarity, functional group, the composition of structural similarity has diverse smell, and vice versa.That is to say that the sample that measurement space is adjacent may belong to diverse classification, the sample of measurement space wide apart might belong to same classification again.The complicated mode classification and the mapping problems of these higher dimensional spaces have proposed challenge to statistical analysis technique.Easily be absorbed in local minimum in the general feedforward neural network learning process commonly used, learning time is long, and structure is determined by rule of thumb, can not be provided gratifying result equally to this type of challenge.Classification is many more, and dimension is high more, and the defective of data processing method is just obvious more in the olfactory analog system.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming of existing olfactory analog system, and a kind of novel olfactory analog device that annular gas sensor array carries out gas test and the method for olfactory analog test thereof of adopting that proposes, the present invention has that device volume is little, perfect heat-dissipating, the concentration that does not reduce smell to be measured, easy, the advantage of high precision of test.
In order to realize purpose of the present invention, the technical scheme that the present invention takes is: a kind of olfactory analog device, be characterized in, and form by mainframe box, Computer Processing part, display part and power circuit;
Be provided with annular test box in the described mainframe box, this annular test box one side is provided with dividing plate, and the dividing plate both sides are respectively equipped with air intake opening and gas outlet, provide admission line and outlet pipe on this air intake opening and the gas outlet respectively; Be sequentially with second solenoid valve of control gas break-make to be measured and first solenoid valve that control recovers gas one oxygen break-make on the admission line, its first solenoid valve is communicated with oxygen or pure air by pipeline, and second solenoid valve is communicated with testing sample by pipeline; Be sequentially with the 3rd solenoid valve, flow control valve, flowmeter, the membrane pump of control toxic emission on the outlet pipe; Be spaced in the described annular test box and be provided with a plurality of gas sensors, form gas sensor array;
Described Computer Processing partly comprises the high-accuracy data collection card that is connected with the output of each gas sensor in the annular test box, and with the two-way computer data processing section that is connected of this high-accuracy data collection card;
Described display part comprises display driver circuit that is connected with the computing machine output signal and the display that is connected with this display driver circuit;
Described power circuit comprises the galvanic stabilized voltage supply of exportable three tunnel high precision.
Above-mentioned olfactory analog device, wherein, described data collecting card by the storer of A/D converter, gas multidimensional response signal to be measured and in advance the memory all gases memory of data; Described A/D converter is connected with the output terminal of each gas sensor, and the storer of gas multidimensional response signal to be measured is connected with the input end of computer data processing section respectively with all gases memory of data of memory in advance.
Above-mentioned olfactory analog device, wherein, described power circuit comprises that one can export three tunnel high precision D.C. regulated power supplies of 12V, 5V and 10V respectively; Wherein: 5V and the work of 10V power supply air feed dependent sensor; The 12V power supply is for other components and parts work.
Above-mentioned olfactory analog device, wherein, described testing sample is located in the sample bottle, and this sample bottle is located in the thermostatted water.
Method according to above-mentioned olfactory analog device carries out the olfactory analog test wherein, may further comprise the steps:
A, the liquid or solid of gas to be measured is contained in the sample bottle, places the inflow point of induction pipe;
B, miniature diaphragm pump suck annular test box with the smell to be measured in the liquid or solid, and this gas skips over the sensitive membrane surface of each sensor rapidly, discharges from exhausr port then;
C, in the gas flow process, smell to be measured goes on record by gas data storer to be measured after A/D converter is changed to data collecting card through the response that gas sensor one by one produces, and obtains a multidimensional response signal therefrom;
D, this multidimensional response signal can obtain the concentration estimated value of classification, bulk strength or the gas componant of smell to be measured after machine data is handled as calculated, and show the epicycle end of test (EOT) by display;
E, last time after the end of test (EOT), before a step of beginning new round test, feed surrounding air earlier in annular test box, make each gas sensor tentatively be returned to original state, aerating oxygen or pure air make each gas sensor accurately be returned to original state in annular test box then;
F, repetition a～e step are repeatedly tested.
Above-mentioned olfactory analog device, wherein, described testing sample is located in the sample bottle, and this sample bottle is located in the thermostatted water.
Because the present invention has adopted above technical scheme, therefore have following effect:
1, in the annular test box of volume less than 200ml annular gas sensor array is set.The advantage of this structure is that volume is little, and thermal diffusivity is good, and the concentration of smell to be measured is not had to reduce substantially.
2, gas sampling is done carrier gas without inert gas, because the carrier gas meeting reduces the concentration of smell to be measured.
3, the time of single gas sensor contact measured smell very short, generally have only the several seconds.Like this, can shorten the release time of sensor greatly, reduce the chance of its " poisoning ", thereby improve the test speed of olfactory analog device effectively.
4, utilize cheap oxygen as recovering gas, interference gas is to the influence of test result, with the benchmark unanimity that guarantees repeatedly to measure in eliminating environment temperature, humidity and the surrounding air.
5, use thermostatic water-circulator bath as critical component, place the outside of olfactory analog device, steady temperature is 25 ± 0.1 ℃.Testing liquid or solid were placed in the water bath with thermostatic control about 30 minutes, guaranteeing the concentration unanimity of smell to be measured, thereby make test error≤3%RSD (relative standard deviation).
6, maximal value, the sensor of getting sensor response simultaneously reaches average gradient before the maximal value, the integrated value feature (input component) as input pattern, to improve the sensitivity and the selectivity of test macro.
Description of drawings
Specific structural features of the present invention is further provided by following embodiment and accompanying drawing thereof.
Fig. 1 is the structural representation of olfactory analog device of the present invention.
Fig. 2 is a single-sensor circuit working schematic diagram of the present invention.
Fig. 3 is the principle schematic of olfactory analog method of testing of the present invention.
Fig. 4 is the schematic flow sheet of three (air recoveries) of gaseous mass analysis state of the present invention.
Fig. 5 is the schematic flow sheet of two (oxygen reductions) of gaseous mass analysis state of the present invention.
Fig. 6 is the schematic flow sheet of one of gaseous mass analysis state of the present invention (sample introduction, sensor produce response).
Embodiment
See also Fig. 1.A kind of olfactory analog device of olfactory analog device of the present invention is characterized in, is made up of mainframe box 1, Computer Processing part 2, display part 3 and power circuit 4.
Be provided with annular test box 11 in the mainframe box 1, this annular test box one side is provided with dividing plate 12, and the effect of dividing plate is that air intake opening and gas outlet are separated, and forces gas around belt one week of test box.The dividing plate both sides are respectively equipped with air intake opening and gas outlet, provide admission line 13 and outlet pipe 14 on this air intake opening and the gas outlet respectively.Admission line is provided with second solenoid valve 16 of control test gas break-make and first solenoid valve 15 that control recovers the gas break-make, and its first solenoid valve is communicated with oxygen by pipeline or pure air 5, the second solenoid valves are communicated with testing sample 6 by pipeline; Be sequentially with the 3rd solenoid valve 17, flowmeter 18, the membrane pump 19 of control toxic emission on the outlet pipe; For making things convenient for gas collecting and toxic emission.The membrane pump that this device adopts is special-purpose minitype gas sampling pump, and weight is about 0.1kg, and the per minute sampling quantity is 1.5L, and pump places the gas circuit rear end, both can be used for gas to be measured is sucked in the test box, can be used for again waste gas in the case is discharged.Be spaced in the annular test box and be provided with a plurality of gas sensors 7, form gas sensor array.Test box adopts stainless steel material to make.Do not make the odorousness excess dilution, be equivalent to the detection lower limit that improves gas sensor, therefore, make the test box volume as far as possible little in the design, actual volume is about 200ml.Another principal feature of test box is, smell to be measured enters test box from air intake opening, skips over the sensor sensing film surface with the speed of 25ml/s, discharges from exhausr port then.In the gas flow process, the response of gas sensor generation goes on record by the precision measurement circuit one by one.This test box have volume ratio less, be convenient to gas circulation and circulation, be convenient to sensor heat radiation, advantages such as weight is light, good seal performance.
See also Fig. 2, this is the electrical connection synoptic diagram of the single gas sensor 7 of the present invention.The 5V power supply is connected with the resistance wire two ends of this single gas sensor, the 10V power supply is connected with the test loop two ends of this single gas sensor, output terminal connects a divider resistance (being referred to as pull-up resistor), and the response signal of its output (magnitude of voltage) is connected with the input end of data collecting card.
The principle of work of this single gas sensor is: 1, reduction phase: when the speed with certain of air or oxygen skips over the sensor sensing film surface, the negatron and the oxygen molecule that are in free state in the sensitive membrane combine by electron affinity, form a potential barrier, cause the increase of sensor resistance; 2, working stage: under the prerequisite that operating voltage remains unchanged, behind the sensor contact measured gas, the resistance at sensitive membrane two ends sends and changes, and the voltage at the resistance two ends of connecting with sensor just correspondingly changes, and this is the response of gas sensor to smell.
The type of gas sensor has many kinds such as metal-oxide semiconductor (MOS), organic polymer, surface acoustic wave, quartz crystal oscillator, present embodiment select TGS-8 series gas sensor that Japanese Figaro company produces totally 16 form gas sensor array, concrete model is TGS800,812,813,816,821,822,823,824,825,826,830,831,832,842,880,883T.
See also Fig. 3.The method that the present invention carries out the olfactory analog test is: the miniature diaphragm pump sucks annular test box with smell to be measured (gas or liquid and solid Volatile Gas), and at this moment gas skips over the sensor sensing film surface with the speed of 25ml/s, discharges from exhausr port then.In the gas flow process, the response of gas sensor generation goes on record by gas reservoir to be measured after the A/D converter conversion to data collecting card one by one, obtains a multidimensional response signal therefrom;
Because the array that this device is made up of 16 gas sensors, therefore, the dimension of response signal is 16.This 16 dimension voltage responsive signal is after machine data is handled as calculated, and classification, bulk strength or the gas composition concentration estimated value etc. that can obtain smell to be measured are experienced corresponding to result with people's sense organ, and show by display.
The present invention utilizes oxygen to eliminate the influence of environment to measuring accuracy, carrying out oxygen reduction handles, this oxygen reduction is treated to: last time after the end of test (EOT), before a step of beginning new round test, feed surrounding air earlier in annular test box, make each gas sensor tentatively be returned to original state, aerating oxygen or pure air make each gas sensor accurately be returned to original state in annular test box then; Carry out the next round test then.Can accelerate the resume speed of gas sensor like this, make repeatedly to measure on same foundation and carry out.
The present invention has three working stages, and its principle is shown in Fig. 4～6.
1, air recovers the stage.As shown in Figure 4, first solenoid valve 15 cuts out, and second solenoid valve 16 is opened.Under the effect of membrane pump, surrounding air flow through stainless steel pipes, second solenoid valve 16, air intake opening, annular test box 11, gas outlet, the 3rd solenoid valve 17, flow control valve 20, flowmeter 18 enter atmosphere at last.Because the temperature of the surrounding air in different time and place, humidity, composition can not be just the same, this process needs 240s approximately, and fundamental purpose is the state that makes before sensor roughly returns to contact gas.
2, oxygen recovers the stage.As shown in Figure 5, first solenoid valve 15 is opened, and second solenoid valve 16 cuts out, and membrane pump shuts down.Oxygen enters atmosphere at last through first solenoid valve 15, second solenoid valve 16, air intake opening, annular test box, gas outlet, the 3rd solenoid valve 17, flow control valve, flowmeter.This process is about 40s, and fundamental purpose is to make when repeatedly measuring, and the original state of sensor is identical, eliminates Effect of Environmental.
3, sample introduction, data acquisition and the processing stage.As shown in Figure 6, first solenoid valve 15 cuts out, and second solenoid valve 16 is opened.Under the effect of membrane pump, the liquid or solid Volatile Gas of Erlenmeyer flask head space flow through stainless steel pipes, second solenoid valve, air intake opening, annular test box, gas outlet, the 3rd solenoid valve, flow control valve, flowmeter are discharged into atmosphere at last.When smell skipped over sensor sensing film with the speed of 25ml/s, the response of sensor (analog quantity) was converted into digital signal through the high accuracy data card, and is admitted to Computer Storage or processing.Computing machine at 10s with results such as the concentration of the interior classification that will provide smell to be measured, some composition or aroma strengths.This process needs 10s approximately.After the Volatile Gas 5s that extracts with static head space method in the Erlenmeyer flask, second solenoid valve is closed again.Treat that operating personnel take out after the Erlenmeyer flask, instrument changes air immediately over to and recovers the stage.
The present invention can make the gas sampling data repeatability reach more than 95% on the basis that environment temperature is controlled a little.
Claims (6)
1, a kind of olfactory analog device is characterized in that, is made up of mainframe box, Computer Processing part, display part and power circuit;
Be provided with annular test box in the described mainframe box, this annular test box one side is provided with dividing plate, and the dividing plate both sides are respectively equipped with air intake opening and gas outlet, provide admission line and outlet pipe on this air intake opening and the gas outlet respectively; Second solenoid valve and the control that are sequentially with control gas break-make to be measured on the admission line recover gas---first solenoid valve of oxygen or pure air break-make, its first solenoid valve is communicated with oxygen or pure air by pipeline, and second solenoid valve is communicated with testing sample by pipeline; Be sequentially with the 3rd solenoid valve, flow control valve, flowmeter, the membrane pump of control toxic emission on the outlet pipe; Be spaced in the described annular test box and be provided with a plurality of gas sensors, form gas sensor array;
Described Computer Processing partly comprises the high-accuracy data collection card that is connected with the output of each gas sensor in the annular test box, and with the two-way computer data processing section that is connected of this high-accuracy data collection card;
Described display part comprises display driver circuit that is connected with the computing machine output signal and the display that is connected with this display driver circuit;
Described power circuit comprises the galvanic stabilized voltage supply of exportable three tunnel high precision.
2, olfactory analog device according to claim 1 is characterized in that, described data collecting card by the storer of A/D converter, gas multidimensional response signal to be measured and in advance the memory all gases memory of data; Described A/D converter is connected with the output terminal of each gas sensor, and the storer of gas multidimensional response signal to be measured is connected with the input end of computer data processing section respectively with all gases memory of data of memory in advance.
3, olfactory analog device according to claim 1 is characterized in that, described power circuit comprises that an output voltage is respectively three tunnel high precision D.C. regulated power supplies of 12V, 5V and 10V; Wherein: 5V and the work of 10V power supply air feed dependent sensor; The 12V power supply is for other components and parts work.
4, olfactory analog device according to claim 1 is characterized in that, described testing sample is located in the sample bottle, and this sample bottle is located in the thermostatted water.
5, adopt the device of claim 1 to carry out the method that olfactory analog is tested, it is characterized in that, may further comprise the steps:
A, the liquid or solid of gas to be measured is contained in the sample bottle, places the inflow point of induction pipe;
B, miniature diaphragm pump suck annular test box with the smell to be measured in the liquid or solid, and this gas skips over the sensitive membrane surface of each sensor rapidly, discharges from exhausr port then;
C, in the gas flow process, smell to be measured goes on record by gas data storer to be measured after A/D converter is changed to data collecting card through the response that gas sensor one by one produces, and obtains a multidimensional response signal therefrom;
D, this multidimensional response signal can obtain the concentration estimated value of classification, bulk strength or the gas componant of smell to be measured after machine data is handled as calculated, and show the epicycle end of test (EOT) by display;
E, last time after the end of test (EOT), before a step of beginning new round test, feed surrounding air earlier in annular test box, make each gas sensor tentatively be returned to original state, aerating oxygen or pure air make each gas sensor accurately be returned to original state in annular test box then;
F, repetition a～e step are repeatedly tested.
6, olfactory analog method of testing according to claim 5 is characterized in that, described testing sample is located in the sample bottle, and this sample bottle is located in the thermostatted water.
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