CN101806763A - Olfactory analog instrument and qualitative, quantitative and simultaneous analysis method of various gases - Google Patents
Olfactory analog instrument and qualitative, quantitative and simultaneous analysis method of various gases Download PDFInfo
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Abstract
The invention relates to an olfactory analog instrument and a qualitative, quantitative and simultaneous analysis method of various gases, and has the following characteristics that: firstly, the instrument comprises a test box, headspace gas generating devices, a computer and a clean air bottle; secondly, the constant temperatures of a gas sensor array workroom, a sample to be detected and a headspace volatile gas are 55+-0.1 DEG C, heating but no refrigerating is carried out in the process at constant temperature, and the volume of the headspace volatile gas is 180 milliliters; thirdly, gas headspace sampling is carried out automatically within five seconds by a micro-vacuum pump, a magnetic valve, a throttle valve, a sample injector, an automatic sample lifting device of the test box and the computer; fourthly, the hole of the sample injector is directly communicated with the air inlet hole of the gas sensor array workroom; fifthly, the qualitative, quantitative and simultaneous analysis method of various gases is realized by a structurized neural network module. The olfactory analog instrument is provided with six headspace gas generating devices capable of measuring six samples within one hour, thereby having the advantages of high automatic degree, simple and convenient operation and low test cost.
Description
Technical field
The present invention-a kind of olfactory analog instrument and multiple smell qualitative, quantitative be analytical approach simultaneously, relates to computing machine, precision measurement, control automatically, precision optical machinery, analytical chemistry, spices, field of food.The present invention mainly solves gas sensor array operating room and sample and head space Volatile Gas exact constant temperature, the generation of high capacity head space Volatile Gas, head space sampling automatically, multiple smell is discerned simultaneously and the concentration estimation problem.
Background technology
The olfactory analog instrument is mainly used in smell identification, odour intensity quantitative test and key component concentration thereof and estimates.
The gas sensor of a sensitivity is enough to finish to the qualitative of a kind of single smell even quantitative test task.Yet, non-existent during only to a kind of gas sensor of gas sensitization, there are thousands of kinds of smells in the real world, consider the ever-changing of ambient temperature and humidity again, make the qualitative and quantitative analysis of multiple smell become a difficult problem that needs to be resolved hurrily.The research of this respect has important significance for theories and practical value.Say in a sense, the gas sensor array technology of olfactory analog theory and implementation method, especially core, qualitative and quantitative analysis proposes when solving multiple smell.
Except that good selectivity, the olfactory analog instrument must have necessary sensitivity, long-term repeatability, long-term stability.Studies show that the sensitivity of gas sensor is a double-edged sword.Highly sensitive no doubt can the generation comparatively significantly the subtle change of smell reflected, but meanwhile, the noise of environmental change and the too high generation of sensitivity also can influence the credibility of gas sensor sensing results greatly.At present, single gas sensor maximum sensitivity has reached inferior ppb promptly 10
-8Level, this is much of that to routine measurement.
Along with the appearance of gas sensor array technology, adopt suitable mode identification method, the olfactory analog instrument can have good selectivity.But the olfactory analog experimental study is the analysis result to limited several smells (more being 2 kinds) and concentration thereof at present, with people's requirement and the very big gap of objective reality existence.
Long term repeatability and long-time stability are the life of instrument, are research focus and difficult point always.Say that in a sense we would rather sacrifice sensitivity to a certain degree, also will make instrument have good long term repeatability and long-time stability.If a kind of instrument does not have long term repeatability and long-time stability, so, so-called highly sensitive also be false.
The present invention adopts technology maturation, commercialized degree high, with SnO
2Metal-oxide semiconductor (MOS) (Metal oxidesemiconductor, MOS) type gas sensor composition gas sensor array for representative.MOS type gas sensor exists that own vol is big, self form these two major defects of thermal source, and this just means will put forth effort to solve the realization of high capacity gas head space sampling apparatus and the stable problem of gas sensor array self duty.
One of precondition that the olfactory analog instrument carries out the qualitative and quantitative analysis to multiple smell is, to certain liquid state, solid-state or paste aroma-producing substance, as long as its composition and concentration are constant, in any environment, the head space Volatile Gas constituent and the concentration of its generation also should remain unchanged.A kind of aroma-producing substance may not have smell at low temperatures, and with regard to scent of, this explanation temperature is very big to the influence of smell power when temperature is elevated to a certain degree.Therefore, liquid state, head space Volatile Gas composition and concentration solid-state or that the paste aroma-producing substance produces are in any environment remained unchanged, must carry out precision control head space gas generating unit internal temperature.
The olfactory analog instrument multiple smell is carried out the qualitative and quantitative analysis precondition two be no matter who no matter when and where, to taking multiple measurements with a kind of aroma-producing substance, should obtain same result.This is that requirement reduces operate miss as far as possible on the one hand, and another side is long-time stability and the error that requirement reduces the instrument internal except that the gas sensor self reason as far as possible.This solves the instrument internal especially stability problem and the automatic head space sampling problem of gas sensor array operating room internal work state with regard to needs.
Gas chromatograph is main at present by manual injection's sample introduction, and test result and operating personnel's skill level relation is very big.In order to reduce operate miss, gas chromatograph manufacturer is devoted to develop automatic sampling apparatus for many years always both at home and abroad.One of method of gas chromatography instrument analytical gas sample is to adopt the head space gas sampling assembly; Two of method is to adopt the preprocessing process of gaseous sample collection-enrichment-condensation-syringe sampling.Aim at the supporting commercial head space gas sampling assembly of gas chromatograph, as 7694E, HS40X1 etc., only 20 milliliters of its sample bottle max capies can not satisfy the requirement of olfactory analog instrument.The sample bottle volume is little, and the available gas amount that can be inhaled in the gas sensor operating room is just little, and consequently gas is diluted in the gas sensor operating room greatly, has been equivalent to reduce the detection lower limit and the sensitivity of gas sensor.Commercial head space sampling apparatus also exists price height, complex structure, big, the complex operation problem of volume, for example, and more than unit price 100,000 Renminbi of 7694E type head space sampling apparatus.From the requirement of olfactory analog instrument self, automatically the head space sampling apparatus should be an ingredient of instrument, and only in this way, the olfactory analog instrument could realize real time implementation, scene, to the less demanding original intention of test environment.
A gas sensor self is a thermal source, gas sensor array is that a plurality of gas sensors are worked simultaneously, that is to say, the heat that a plurality of work thermals source produce gets up accumulation, thereby cause the instability of machine olfaction Instrument working state, this is very disadvantageous to long term repeatability and the long-time stability that keep the machine olfaction instrument.Patent of invention " a kind of machine olfaction device and olfactory analog method of testing thereof " (referring to number of patent application: 02111046.8) and patent of invention " a kind of small automatic machine sense of smell instrument and smell analytical approach " (referring to number of patent application: 200710036260.4) lining, we point out, the advantage that adopts gas sensor array annular working chamber is to make spread heat when a plurality of gas sensors are worked simultaneously.But, directly can cause annular working chamber volume not effectively reduce in gas sensor array annular working chamber interior 7 core ceramic socket gluings, remove 7 core ceramic sockets and can have influence on the sensitivity of gas sensor self and the reliability of connection line again.Single gas sensor volume is bigger, the gas sensor array swept volume of a single chamber should be as far as possible little and thermal diffusivity as well as possible, how to solve these contradictions, be one of the present invention's major issue that will solve.
In sum, the key technical problem that the present invention will solve is how (1) promptly realizes the precision control of instrument internal working temperature as how " ten thousand changes " of " constant " reply external environment condition of instrument internal; (2) the accurate constant temperature of the realization of high capacity head space Volatile Gas generating means and sample and head space Volatile Gas; (3) the automatic head space sampling apparatus of development is to eliminate the manual operation error; (4) for cooperating the precision control of instrument internal working temperature, solve the problem of distributing of the heat of inner accumulation; (5) how to make gas flow duct short as far as possible, reduce the residual space of scent molecule; (6) how to realize that smell contacted with the moment of gas sensor sensitive membrane, gas sensor operating room and inner-walls of duct, so that the fast quick-recovery of gas sensor and the removal of residual scent molecule; (7) pattern recognition model and the Program Realizing Method analyzed simultaneously of multiple smell qualitative, quantitative.
Summary of the invention
200710036260.4) and " also a kind of-series model recognition methods and the application in machine olfaction thereof " (application number: on the basis 200710042607.6), for making the test of multiple liquid state, solid-state or paste aroma-producing substance and analysis result are had a kind of olfactory analog instrument that good selectivity, long term repeatability and long-time stability propose and multiple smell qualitative, quantitative analytical approach simultaneously the present invention is (referring to number of patent application: in existing patent of invention " a kind of small automatic machine sense of smell instrument and smell analytical approach ".Olfactory analog instrument of the present invention has that volume is little, head space Volatile Gas volume is big, constant temperature precision height, automaticity height, long term repeatability and long-time stability are good, analysis speed is fast, easy to use advantage.
To achieve these goals, the present invention-a kind of olfactory analog instrument is made up of test box, head space gas generating unit, computing machine, pure air bottle.
Test box is connected with umbilical cable by the signal transmission with computing machine; Test box is connected by gas pipeline with the pure air bottle; The variation of the gas sensor array perception smell in the test box obtains multichannel analog signals; Computing machine changes into the multi-path digital signal with gas sensor array to the multichannel analog signals that the smell perception produces, and in view of the above smell is carried out qualitative and quantitative analysis; Pure air takes multiple measurements gas sensor array on stable gaseous state basis.
The head space gas generating unit is connected with test box with signal-transmitting cable by power supply, is used for liquid, the solid-state or paste sample of heating with generation high capacity head space Volatile Gas; Under the control of computing machine and test box, the temperature constant of sample and head space Volatile Gas is at 55 ± 0.1 ℃.
Before the gas headspace sampling, operating personnel are fixed on the head space gas generating unit on the support disk of auto injection jacking gear in the test box; In gas headspace when sampling,, the head space gas generating unit rises under the promotion of auto injection jacking gear, is fixed in the test box sample introduction needle on the constant temperature oven thereby pierces through the silicone rubber seal sheet of head space gas generating unit and touch the head space Volatile Gas; After gas headspace sampling finished, operating personnel unclamped and remove the head space gas generating unit of the tested mistake of sample from support disk, and the head space gas generating unit of packing into new is prepared for measure next time.
Test box is by constant temperature oven, auto injection jacking gear, vacuum pump, two-position two-way solenoid valve 3, and two-position two-way solenoid valve 4, two-position two-way solenoid valve 5, flowmeter, four road D.C. regulated power supplies, driving and control circuit, throttling valve 7, throttling valve 8 are formed; Wherein, constant temperature oven is made up of gas sensor array, gas sensor array annular working chamber, sample introduction needle, sample introduction needle joint, outer-hexagonal nut, heat insulation disk, resistance heating wire, temperature sensor, fan, thermofin; Constant temperature oven is fixed on the test box casing.
Gas sensor array is overlapped each other by 16 performances and mutually different gas sensor is formed, and the variation of perception smell produces 16 tunnel analogue response voltage signal; Gas sensor array annular working chamber is fixed together by socket head cap screw by sensor holder and sender unit cap and forms, and forms the annular cavity that seals by 2 O RunddichtringOs, places 16 gas sensors; The annular cavity mean diameter is 140 millimeters, and cross dimensions is 20 millimeters * 16 millimeters; Sensor holder is that 140 millimeters annular cavity is evenly equipped with 18 through holes along mean diameter, and wherein 16 is the mounting hole of 7 core ceramic sockets, and 2 is air admission hole and venthole; Air admission hole and venthole are adjacent, and the centre is separated by dividing plate, thereby force tested gas to flow around gas sensor array annular working chamber; 7 commercial core ceramic sockets, and are connected with control circuit with driving with four road D.C. regulated power supplies of test box by lead on the mounting hole of sensor holder with tasteless bonding agent gluing; Gas sensor directly is inserted on the 7 core ceramic sockets.
The sample introduction needle joint directly is fixed on air admission hole below, gas sensor array annular working chamber; Sample introduction needle is that the aperture is 1.0 millimeters a clinical syringe needles, is fixed on the sample introduction needle joint by the outer-hexagonal nut, reaches the short as far as possible purpose of air inlet gas circuit; Fit together mutually by tapering between sample introduction needle and the sample introduction needle joint; The step of changing sample introduction needle is, 1. takes off the heat insulation disk that is fixed on the constant temperature oven, 2. backs out the fixedly outer-hexagonal nut of sample introduction needle, 3. takes off old sample introduction needle, 4. changes new sample introduction needle, and 6. the outer-hexagonal nut of 5. screwing on loads onto heat insulation disk.
The vent port of gas sensor array annular working chamber and two-position two- way solenoid valve 3 and 5, two-position two-way solenoid valve 5 and pure air bottle, two-position two-way solenoid valve 3 and vacuum pump, vacuum pump and throttling valve 7 and two-position two-way solenoid valve 4, throttling valve 7 and two-position two-way solenoid valve 4 and flowmeter, two-position two-way solenoid valve 5 and throttling valve 8, throttling valve 8 and pure air bottle all are connected by gas pipeline; Tested gas enters gas sensor array annular working chamber from sample introduction needle, and flows through two-position two-way solenoid valve 3, vacuum pump, throttling valve 7, flowmeter successively, and the outlet port by gas pipeline is discharged in the atmosphere at last.
It is in 55 ± 0.1 ℃ the constant temperature oven that gas sensor array annular working chamber, a part of sample introduction needle all are fixed on temperature; Constant temperature oven inside is heated by the resistance heating wire, and fan makes the temperature inside the box even, and thermofin prevents that heat from outwards distributing, the variation of temperature sensor detected temperatures; The thermostatic process of constant temperature oven only heats, and does not freeze.
The auto injection jacking gear is made up of stepper motor, gear 29, gear 30, nut, screw rod, support disk, guide pole, ball bearing, bearing seat, base, limit switch, inner spacing collar, outer separator, interior jump ring, outer jump ring, gear 29 is fixed on the step motor shaft, gear 30 is fixed together with nut, screw rod and support disk are fixed together, bearing seat is fixed on the base, and base and limit switch are fixed on the test box casing.
The gear 29 of auto injection jacking gear is No. 45 Fine Steel Casting iron materials, and gear 30 and screw rod are nonmetallic materials, and support disk and screw rod are aluminum alloy materials; Auto injection jacking gear apply oil not in the long-term work process does not produce noise.
Under the control of computing machine, the stepper motor of auto injection jacking gear makes gear 30 rotation by gear 29, the nut thereby the rotation that are fixed together with gear 30, thus make screw rod and support disk to do the rise and fall campaign together; The pitch of screw rod and nut is 3 millimeters, and support disk rose 20 millimeters in 3 seconds, descends 20 millimeters in 3 seconds.
The head space gas generating unit is made up of glass sample bottle, resistance heating wire, heat-conducting layer, thermofin, 2 temperature sensors, bowl cover, silicone rubber seal sheet, cup overcoat, cup end disk, claw, 6 core cables; Heat-conducting layer is fixed together by aluminium alloy heat conduction cover and aluminium alloy heat conduction disk and forms, the resistance heating wire is wrapped in aluminium alloy heat conduction disk bottom and aluminium alloy heat conduction puts, a temperature sensor is fixed on aluminium alloy heat conduction disk bottom aluminium alloy heat conduction cover outside surface top respectively, and the glass sample bottle is positioned on the aluminium alloy heat conduction disk of heat-conducting layer inside; The heat that the resistance heating wire produces heats the sample in the glass sample bottle by aluminium alloy heat conduction disk and aluminium alloy heat conduction cover, and thermofin and bowl cover prevent that jointly heat from distributing, and the silicone rubber seal sheet prevents that the head space Volatile Gas in the glass sample bottle from leaking.
Sample and head space Volatile Gas thermostat temperature are 55 ± 0.1 ℃ in the head space gas generating unit, and 2 temperature sensors that are fixed in aluminium alloy heat conduction disk bottom and aluminium alloy heat conduction cover outside surface top detect the interior temperature variation of glass sample bottle; If the temperature survey mean value of 2 temperature sensors is higher than 55 ℃, then computing machine cuts off the power supply the resistance heating wire by the signal transmission with umbilical cable; If this temperature survey mean value is lower than 55 ℃, then computing machine switches on the resistance heating wire by the signal transmission with umbilical cable; Therefore, even environment temperature reaches 45 ℃, this head space gas generating unit still only heats, and does not freeze.
Capacity is that 180 milliliters glass sample bottle and silicone rubber seal sheet all buied from the market, and each glass sample bottle and silicone rubber seal sheet only use once, do not produce cross-infection.
The cup end disk bottom of head space gas generating unit is agreed with along diametric 2 draw-in grooves in the rim, support garden of diametric 2 claws and auto injection jacking gear; Before the gas headspace sampling, operating personnel aim at 2 draw-in grooves with 2 claws earlier, rotate 5 ° of head space gas generating units then, and cup end disk just is fixed together with support disk, and both vertical centres overlap; Otherwise operating personnel can take the head space gas generating unit away from support disk fast; Head space gas generating unit and support disk fixing or take process away and all can in 10 seconds, finish.
During the gas headspace sampling, under the control of computing machine, support disk is done the rise and fall campaign with the head space gas generating unit, and the maximum perpendicular displacement is 20 millimeters; When the head space gas generating unit rises, be fixed on the sample introduction needle of air admission hole below, gas sensor array annular working chamber thereby pierce through silicone rubber seal sheet on the glass sample bottle, thereby touch the head space Volatile Gas.
The voltage of four road D.C. regulated power supplies is respectively 5V, 10V, 12V and 36V; Wherein, 5V is the heating voltage of 16 gas sensors, and 10V is the operating voltage of gas sensor, and 12V is the operating voltage of 3 two-position two-way solenoid valves, vacuum pump, fan and stepper motors, and 36V is the heating voltage of test box and head space gas generating unit; 5V and 10V are linear power supply, and 12V and 36V are Switching Power Supply.
Vacuum pump is worked in a continuous manner, computing machine is by the energising and the outage of data collecting card and signal transmission and umbilical cable control two-position two- way solenoid valve 3,4 and 5, to control the through and off of gas sensor array annular working chamber and head space Volatile Gas, pure air and surrounding air respectively.
Head space Volatile Gas sampling volume is 50 milliliters, by flowmeter and computing machine accurate measurement; During the gas headspace sampling, under the effect of computing machine, two-position two- way solenoid valve 3,4 and 5, the pure air passage is disconnected, head space Volatile Gas in the glass sample bottle is aspirated by vacuum pump, via sample introduction needle, with the flow of the 600 ml/min gas sensor array annular working chamber of flowing through, be discharged into the atmosphere from outlet port then.
Under the control of computing machine, by two-position two- way solenoid valve 3,4 and 5 and the conversion and the control of throttling valve 7 and 8, make that the interior head space Volatile Gas sampling flow of glass sample bottle is 600 ml/min, the pure air flow is 600 ml/min, and ambient air is respectively 600 ml/min and 6000 ml/min; Flow is the surrounding air flushing of 6000 ml/min, the one, make the preliminary fast recovery of gas sensor; The 2nd, the heat that accumulation produces when taking away indoor 16 gas sensors of gas sensor array annular working and working simultaneously; The 3rd, wash away the scent molecule that is adsorbed on gas sensor array annular working chamber and the gas inner-walls of duct.
Pure air is with 600 ml/min, oppositely be blown into gas sensor array annular working chamber by gas pipeline, throttling valve 8 and two-position two-way solenoid valve 5 from venthole, and finally be discharged to the atmosphere, thereby make 16 gas sensors when repeatedly sampling, all be in the steady state (SS) of repetition from sample introduction needle.
The data collecting card that is inserted on the computer motherboard is 16 way word signals with 16 A/D conversions with gas sensor array 16 tunnel analog signal conversion that perception obtains to smell; This 16 way word signal is kept on the hard disc of computer as a data file, is the olfactory analog instrument carries out qualitative and quantitative analysis to smell foundation; The time span that is recorded data is 60 seconds.
Computing machine carries out qualitative and quantitative analysis with structurized neural network module software simultaneously to multiple smell; The digitalized signature that sample is a smell sample is represented, is the response of gas sensor array; The structure of a neural network module is the single hidden layer of single output; A pair of neural network module is represented a kind of smell, wherein, previous neural network module is responsible for discerning a sample whether from the smell of representative, and under the prerequisite of confirming "Yes", the neural network module of a back correspondence is responsible for estimating the intensity and the concentration of this sample; The logarithm of neural network module equals the classification number of smell, and is corresponding one by one; During decision-making, be responsible in all neural network modules of identification, the neural network module of output valve maximum is determining the classification of the smell sample of a sample and correspondence thereof.
The olfactory analog instrument carries out qualitative, quantitative to multiple smell to be analyzed simultaneously, may further comprise the steps:
(1), start, instrument preheating 30 minutes, two-position two- way solenoid valve 3 and 4 is connected, two-position two-way solenoid valve 5 disconnects, under the swabbing action of vacuum pump, surrounding air flows through gas sensor array annular working chamber by sample introduction needle with the flow of 6000 ml/min; Computing machine with the 30th minute when last gas sensor array the response of surrounding air is designated as original state;
(2), earlier 10 milliliters of liquid state, solid-state or paste sample to be put into volume be 180 milliliters glass sample bottle to operating personnel, then this glass sample bottle put into the heat conduction cover of head space gas generating unit, covers the silicone rubber seal sheet, tightens bowl cover then; Press the acknowledgement key on the computer keyboard, sample begins to be heated, and constant temperature picks up counting; Sample is under the effect of the heat that the resistance heating wire distributes by aluminium alloy heat conduction disk and aluminium alloy heat conduction cover, and accurately constant temperature is 30 minutes; In period, operating personnel are fixed on the head space gas generating unit on the support disk of auto injection jacking gear at this section;
(3), at sample constant temperature after 30 minutes, two-position two-way solenoid valve 5 is connected, and two-position two- way solenoid valve 3 and 4 disconnects, and pure air blows back into gas sensor array annular working chamber with the flow of 600 ml/min from vent port, be discharged to the atmosphere from sample introduction needle then, last 40 seconds; In this process, gas sensor array is able to accurately demarcate with pure air;
(4), two-position two- way solenoid valve 3,4 and 5 all disconnects the balance period that gas sensor array entered for 5 seconds; During this period, the indoor gas of gas sensor array annular working remains static, the auto injection jacking gear of test box makes the head space gas generating unit rise 20 millimeters in 3 seconds, therefore the sample introduction needle that is fixed on below, gas sensor array annular working chamber passes the silicone rubber seal sheet, touches the head space Volatile Gas in the glass sample bottle;
(5), two-position two-way solenoid valve 3 is connected, two-position two- way solenoid valve 4 and 5 all disconnects, vacuum pump sucks gas sensor array annular working chamber with the flow of 600 ml/min via sample introduction needle with the head space Volatile Gas, make it to skim over rapidly gas sensor sensitive membrane surface, be discharged into the atmosphere from outlet port through throttling valve 7 then; When head space Volatile Gas sampling accumulation reached 50 milliliters, the gas headspace sampling process finished; This process lasted for 5 seconds;
(6), in the head space Volatile Gas is flowed through the process of gas sensor array annular working chamber, each gas sensor produces responsive response to tested smell, these responsive responses are sent to computing machine by the signal transmission with umbilical cable; Computing machine obtains one 16 dimension response vector by 16 data collecting card, after structurized neural network module software analysis is handled, can obtain tested smell sample classification, intensity or key component concentration estimated value within 10 seconds, and show by the display of computing machine;
(7), after the gas headspace sampling process finishes, gas sensor array enters head space Volatile Gas flow and reduces transitional period of increasing gradually with ambient air gradually, lasts 5 seconds; The head space gas generating unit is descending 20 millimeters within 3 seconds under the effect of auto injection jacking gear, and sample introduction needle finally withdraws from the glass sample bottle fully; Two-position two-way solenoid valve 3 is still connected, and two-position two- way solenoid valve 4 and 5 still all disconnects, and vacuum pump sucks gas sensor array annular working chamber with gas from sample introduction needle; Gas carries out the transition to the surrounding air of final 600 ml/min gradually from the head space Volatile Gas of initial 600 ml/min;
(8), after the transitional period end that the head space Volatile Gas reduces to increase gradually with surrounding air gradually, two-position two- way solenoid valve 3 and 4 is connected, two-position two-way solenoid valve 5 disconnects, vacuum pump sucks gas sensor array annular working chamber with surrounding air from sample introduction needle with the flow of 6000 ml/min, lasts 240 seconds; During this period, operating personnel take the head space gas generating unit of the tested mistake of sample away, change sample and glass sample bottle, place new head space gas generating unit;
(9), repeat (2)～(8), repeatedly sample, a complete sampling process continues 295 seconds;
Except that step (2) and (8), whole process is finished automatically by the olfactory analog instrument under the control of computing machine.
6 head space gas generating units of a kind of olfactory analog instrument configuration were measured 6 samples in 1 hour.
(referring to number of patent application: 200710036260.4) compare, analytical approach has that structure is succinct more, gas circuit is shorter simultaneously, solenoid valve is reduced to from 4 that 3, sample introduction pin hole directly communicate with gas sensor array annular working chamber air admission hole, the surrounding air flush time of 6000 ml/min is longer, gas headspace is sampled the higher characteristics of automaticity for olfactory analog instrument of the present invention and multiple smell qualitative, quantitative with invention " a kind of small automatic machine sense of smell instrument and smell analytical approach ".
Description of drawings
Fig. 1 is a present invention-a kind of olfactory analog instrument and multiple smell qualitative, quantitative analytical approach-when not sampling simultaneously, olfactory analog instrument component units synoptic diagram.
Fig. 2 is the present invention-a kind of olfactory analog instrument and multiple smell qualitative, quantitative simultaneously during analytical approach-sampling, olfactory analog instrument component units synoptic diagram.
Fig. 3 is the present invention-a kind of olfactory analog instrument and multiple smell qualitative, quantitative while analytical approach-olfactory analog instrument fundamental diagram.
Fig. 4 is the present invention-a kind of olfactory analog instrument-test box structure principle chart.
Fig. 5 is a present invention-a kind of olfactory analog instrument and multiple smell qualitative, quantitative analytical approach-in a work period simultaneously, gas flow and gas sensor response change situation map.
Fig. 6 is the present invention-a kind of olfactory analog instrument-auto injection lifting device structure figure.
Fig. 7 is the present invention-a kind of olfactory analog instrument-head space gas generating unit structural representation.
Fig. 8 is the present invention-a kind of olfactory analog instrument-head space gas generating unit element mutual alignment synoptic diagram.
Fig. 9 is that the gas sensor of the present invention-a kind of olfactory analog instrument-gas sensor array annular working chamber 2 is installed sectional view.
Figure 10 is the present invention-a kind of olfactory analog instrument-gas sensor array annular working chamber, sample introduction needle, auto injection jacking gear shown in Figure 6, the position and the annexation figure of head space gas generating unit when gas headspace is sampled shown in Figure 7.
Figure 11 is the present invention-a kind of olfactory analog instrument-sample introduction needle replacing method synoptic diagram.
Figure 12 is the present invention-a kind of olfactory analog instrument and multiple smell qualitative, quantitative while analytical approach-structurized neural network module implementation method synoptic diagram.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing.
The component units of the present invention-when a kind of olfactory analog instrument is not sampled is characterized in that as shown in Figure 14 big component units of this instrument are test box I, head space gas generating unit II, Computer I II, pure air bottle IV; Be connected by 6 core cables between test box I and the head space gas generating unit II, wherein 2 is power lead, and 4 is signal transmssion line; Be connected by 37 core flat cables between test box I and the Computer I II, be used to transmit the response signal of gas sensor array and the control signal that Computer I II sends by data collecting card; Be connected by gas pipeline between test box I and the pure air bottle IV.
Component units during the sampling of the present invention-a kind of olfactory analog instrument as shown in Figure 2, at this moment, a head space gas generating unit II is fixed on the support disk of the jacking gear of sampling automatically in the test box I, and other head space gas generating unit II is in the thermostatic process of sample and head space Volatile Gas.
The present invention-a kind of olfactory analog instrument and multiple smell qualitative, quantitative simultaneously analytical approach-olfactory analog instrument fundamental diagram as shown in Figure 3, the concrete component units of instrument is gas sensor array 1, gas sensor array annular working chamber 2, two-position two-way solenoid valve 3, two-position two-way solenoid valve 4, two-position two-way solenoid valve 5, sample introduction needle 6, throttling valve 7, throttling valve 8, flowmeter 9, vacuum pump 10, dividing plate 11, the resistance heating wire 12, temperature sensor 13, fan 14, thermofin 15, high precision four road D.C. regulated power supplies 16 drive and control circuit 17, auto injection jacking gear 18, head space gas generating unit 19, casing 20; Main frame 21, be inserted in data collecting card 22, display 23, pure air bottle 24, gas pipeline 25 on the computer motherboard, be used for 6 core cables 26 of power supply and signal transmission, the 37 core flat cables 27 that are used for signal transmission and control are the commercial standard (CS) parts.Gas sensor array annular working chamber is evenly equipped with 18 through holes, and wherein 16 is the mounting hole of 7 core ceramic sockets, and 2 is air admission hole and venthole; Air admission hole and venthole are adjacent, and the centre is separated by dividing plate, thereby force tested gas to flow around gas sensor array annular working chamber; Gas sensor directly is inserted on the 7 core ceramic sockets;
The structure principle chart explanation of olfactory analog instrument-test box that accompanying drawing 4 provides, constant temperature oven is parts of test box, by gas sensor array 1, gas sensor array annular working chamber 2, dividing plate 11, resistance heating wire 12, temperature sensor 13, fan 14, thermofin 15 is formed, and the part of resistance heating wire 12, temperature sensor 13, fan 14 and sample introduction needle 6 is positioned at the constant temperature oven that is formed by thermofin.
Considering does not need refrigeration and solenoid valve and the bonding agent working temperature should not too high these two factors when environment temperature is the highest, the inner thermostat temperature of constant temperature oven is set at 55 ℃.The measurement range of temperature sensor 13 and sensitivity thereof are 0-100 ± 0.1 ℃.When the constant temperature oven internal temperature surpasses 55 ℃, according to the instruction that computing machine 21 sends by data collecting card 22 and 37 core flat cables 27, resistance heating wire's 12 outages, constant temperature oven internal temperature thereby decline; Otherwise, resistance heating wire's 12 energisings, constant temperature oven internal temperature thereby rising.Therefore, no matter how external environment condition changes, constant temperature oven internal work temperature is constant all the time to be 55 ± 0.1 ℃.The effect of fan 14 is to make that constant temperature the temperature inside the box is even, prevents to produce thermograde.
Accompanying drawing 5 explanations, the present invention-a kind of olfactory analog instrument and multiple smell qualitative, quantitative be analytical approach simultaneously, and in a work period, gas flow and sensor response change situation are as follows:
1. surrounding air stage of tentatively recovering-at flow is under the washing action of surrounding air of 6000 ml/min, last 192 seconds, gas sensor tentatively returns to normal condition, operating personnel during this period of time inject sample to the glass sample bottle, cover the silicone rubber seal sheet, tighten bowl cover, remove old and fixing new head space gas generating unit;
2. pure air calibration phase-flow is the flushing that the pure air of 600 ml/min lasts 40 seconds, makes gas sensor accurately return to normal condition;
3. equilibrium stage-gas sensor array annular working indoor gas does not flow, and lasts for 5 seconds, and the head space gas generating unit rises 20 millimeters, and sample introduction needle touches the head space Volatile Gas;
4. gas headspace sample phase-head space Volatile Gas is skimmed over gas sensor sensitive membrane surface with the flow of 600 ml/min, and therefore gas sensor produces responsive response, lasts for 5 seconds;
5. transition period-head space gas generating unit descends, and sample introduction needle withdraws from and breaks away from gradually and the contacting of head space Volatile Gas, and meanwhile, surrounding air enters the flow of gas sensor annular working chamber from zero 600 ml/min that are increased to gradually from sample introduction needle;
6. surrounding air rinse stage-break away from fully with after the head space Volatile Gas contacts in sample introduction needle, the flow of surrounding air is increased to 6000 ml/min from 600 ml/min, residual scent molecule is flushed away on gas pipeline and the gas sensor annular working chamber interior walls, the heat that the gas sensor array accumulation is distributed is pulled away, and gas sensor tentatively recovers; Meanwhile, computing machine provides the analysis result of tested smell kind, intensity and critical ingredient content, and operating personnel prepare for measure next time.
Accompanying drawing 6 has provided the component units of auto injection jacking gear 18, comprise stepper motor 28, gear 29, gear 30, screw rod 31, nut 32, support disk 33, guide pole 34, ball bearing 35, bearing seat 36, base 37, limit switch 38, inner spacing collar 39, outer separator 40, interior jump ring 41, outer jump ring 42 are formed, gear 29 is fixed on the axle of stepper motor 29, gear 30 is same part with nut 32, screw rod 31 is same part with support disk 33, and bearing seat 36 is fixed on the base 37, and base 37 and limit switch 38 are fixed on the test box casing 20; Guide pole 34 makes 33 of support disk do the rise and fall campaign, and inner spacing collar 39, outer separator 40, interior jump ring 41 and outer jump ring 42 make 2 ball bearings rotate in the fixed position, and bearing seat 36 is fixed together by base 37 and test box casing 20; Stepper motor 29 also is fixed on the base 37, and two center pits of base 37 have determined that the centre distance of gear 29 and gear 30 is 45 millimeters; Screw rod 31 is 20 millimeters with the maximum perpendicular displacement of support disk 33.
See also accompanying drawing 7, the component units of the present invention-a kind of olfactory analog instrument-head space gas generating unit 19 is that volume is 180 milliliters and is the glass sample bottle 43 of wide-mouth, sample 44, silicone rubber seal sheet 45, the resistance heating wire 46, aluminium alloy heat conduction chassis 47, aluminium alloy heat conduction cover 48, thermofin 49, bowl cover 50, temperature sensor 51, cup overcoat 52, claw 53, cup end disk 54,6 core cables and plug 26; Tested liquid state, solid-state or paste sample 44 produce the head space Volatile Gas in glass sample bottle 43; Cup end disk 54 is fixed on the inboard of glass overcoat 52, at the bottom of 2 claws 53 are welded on glass along diametric(al) on the disk 54, diametric 2 draw-in grooves in rim, support garden of 2 claws and auto injection jacking gear agree with, be used to make head space gas generating unit 19 and auto injection jacking gear 18 support disk 33 fixing fast with throw off; Before the gas headspace sampling, operating personnel aim at 2 draw-in grooves with 2 claws earlier, rotate 5 ° of head space gas generating units then, and cup end disk just is fixed together with support disk, and both vertical centres overlap; Otherwise 5 ° of operating personnel's reverse rotation head space gas generating units can unclamp fast on the support disk and take it away; Head space gas generating unit and support disk fixing or take process away and all can in 10 seconds, finish;
Head space gas generating unit 19 is connected with test box by 6 core cables 26, and the electric energy that the 36V direct supply of test box produces is converted to heat energy by resistance heating wire 46; These heat energy pass to glass sample bottle 43 and sample 44 by aluminium alloy heat conduction chassis 47 and aluminium alloy heat conduction cover 48, the temperature of two temperature sensor 51 perception samples, driving and control circuit 17,37 core flat cables 27 and the data collecting card 22 of the real-time change of temperature by 6 core cables 26, test box is delivered to computing machine 21, and computing machine 21 is implemented accurate control to the temperature of glass sample bottle 43 and sample 44 and head space Volatile Gas in view of the above.
The present invention adopts commercial 180 milliliters glass sample bottle and silicone rubber seal sheet, and disposable use avoids reusing the cross pollution of generation.Consider this precondition of need not freezing when environment temperature is the highest, the sample thermostat temperature is set at 55 ± 0.1 ℃.The head space Volatile Gas that produces in sample 44 thermostatic processes is prevented to leak by silicone rubber seal sheet 45; In gas headspace when sampling,, glass sample bottle 43 is promoted to rise by auto injection jacking gear 18, is fixed on the sample introduction needle 6 of air admission hole below, gas sensor array annular working chamber thereby wears silicone rubber seal sheet 45 to touch head space Volatile Gas in the glass sample bottle 43; The constant temperature time of sample 44 is implemented accurate control by computing machine 21 equally.
Accompanying drawing 8 has shown the present invention-a kind of olfactory analog instrument-head space gas generating unit 19 element mutual alignment synoptic diagram; Before the test, operating personnel move into 10 milliliters of samples 44 the glass sample bottle 43 of wide-mouth earlier, and glass sample bottle 43 is put on the aluminium alloy heat conduction chassis 47 is within the aluminium alloy heat conduction cover 48, cover silicone rubber seal sheet 45 again, tighten bowl cover 50 then, energized, constant temperature 30 minutes is fixed on whole head space gas generating unit 19 on the support disk 33 of auto injection jacking gear 18 by 2 claws 53 at last.
See also accompanying drawing 9, the gas sensor of the present invention-a kind of olfactory analog instrument-gas sensor array annular working chamber 2 is installed sectional view, its component units is a sensor holder 55, sender unit cap 56,7 core ceramic sockets 57, socket head cap screw 58, O RunddichtringO 59, O RunddichtringO 60, tasteless bonding agent 61.Gas sensor array operating room 2 is an annular, and the inner chamber mean diameter is 140 millimeters of φ, and the inner chamber cross dimensions is 20 millimeters * 16 millimeters; It is on the stainless sensor holder 55 that 7 core ceramic sockets 57 are bonded in material by tasteless bonding agent 61; Socket head cap screw 58 with sensor holder 55, material be similarly stainless sender unit cap 56, O- ring seals 59 and 60 links together, add tasteless bonding agent 61 leads ends of 7 core ceramic sockets 57 is all shut, thereby form the gas sensor array annular working chamber that seals.
Although the gas sensor of 16 TGS800 series that the gas sensor array do as one likes can overlap each other is formed, concrete model is TGS800,816,821,823,825,826,830,831,832,883T, 812,813,822,824,842,880; But from geometric configuration, this serial gas sensor has only 2 kinds of sizes; The left profile of accompanying drawing 9 last figure is that the gas sensor of the heat resistant type of metal shell is installed section, and TGS800 is installed, 816,821,823,825,826,830,831,832, and 883T; The right section of accompanying drawing 9 last figure is that the plain edition gas sensor of plastic casing is installed section, TGS812 is installed, 813,822,824,842,880; 7 core ceramic sockets 57 of accompanying drawing 9 last figure left profiles are that the step with 7 core ceramic sockets 57 of right section commercialization grinds off the back and obtains, accompanying drawing 9 figure below have provided 7 core ceramic sockets 57 and have transformed preceding and improved structure, so, the diameter of 16 ceramic socket mounting holes on the sensor holder 55 is 16 millimeters of φ, sees also accompanying drawing 3.Gas sensor array annular working chamber interior walls polishing, the possibility of adhering to effective minimizing scent molecule.
Figure 10 has provided gas sensor array annular working chamber 2, sample introduction needle 6, auto injection jacking gear 18 shown in Figure 6 and the position and the annexation figure of head space gas generating unit 19 when gas headspace is sampled shown in Figure 7; Sample introduction needle 6 is fixed on the sample introduction needle joint 63 that welds together with sensor holder 55 by outer-hexagonal nut 62, fit together mutually by tapering between sample introduction needle 6 and the sample introduction needle joint 63, thereby realized the sample mode of proposition of the present invention " the motionless bottle of pin is moving "; This sample mode not only makes the structure of automatic sampling apparatus simplify greatly, and the gas circuit length from sample introduction needle pin mouth to gas sensor array annular working chamber is effectively shortened, and has realized the robotization of sampling process; For making things convenient for the replacing of sample introduction needle 6, the heat insulation disk 64 that the present invention increases in the bottom of constant temperature oven thermofin 15.
See also accompanying drawing 3, accompanying drawing 6, accompanying drawing 7 and accompanying drawing 10, auto injection jacking gear 18 makes head space gas generating unit 19 rise overally 20 millimeters, and the sample introduction needle 6 that is fixed on 2 air admission holes below, gas sensor array annular working chamber pierces through the silicone rubber seal sheet 45 on the glass sample bottle 43 and touches the head space Volatile Gas; Under the swabbing action of vacuum pump 10, the head space Volatile Gas gas sensor array annular working chamber 2 of flowing through; Gas sensor array 1 thereby produce 16 tunnel simulating signals, the A/D conversion of 16 of high precision on machine 21 mainboards and 16 tunnel data collecting card 22 as calculated, computing machine 21 obtains representing 16 way word signals of odor characteristics; The structuring neural network module software of computing machine 21 is made the decision-making of smell kind, intensity or key component concentration in view of the above, and shows by display 23.
For avoiding repeatedly Push And Release to cause flow rate fluctuation and influence the life-span, vacuum pump 10 employing continuously-running duties.Two-position three way magnetic valve 3,4 and 5 is controlled opening with disconnected of head space Volatile Gas, pure air, surrounding air respectively, thus the size of pilot-gas flow.When gas headspace was sampled, pure air inlet disconnected by two-position two-way solenoid valve 5, and two-position two-way solenoid valve 4 also is in off-state, and two-position two-way solenoid valve 3 is connected, thereby forced the head space Volatile Gas throttling valve 7 of flowing through; At this moment, under the effect of vacuum pump 10, the head space Volatile Gas is with the flow of 600 ml/min flow through sample introduction needle 6, air admission hole, gas sensor array annular working chamber 2, gas sensor array 1, venthole, two-position two-way solenoid valve 3, throttling valve 7, flowmeter 9, and the outlet port from gas pipeline 25 enters atmosphere at last.
After the gas headspace sampling process finishes, whole instrument enters transition state, see also accompanying drawing 3, accompanying drawing 5 and accompanying drawing 10, three two-position two-way solenoid valves remain unchanged, head space gas generating unit 19 is descending 20 millimeters within 3 seconds under the effect of auto injection jacking gear 18, withdraw from the glass sample bottle fully until sample introduction needle, disengaging contacts with the head space Volatile Gas; In this process, gas flow still is 600 ml/min, but the head space Volatile Gas that vacuum pump 10 extracts is fewer and feweri, and surrounding air is more and more, until being entirely surrounding air; This transfer process is achieved, and is owing to implemented the computing machine accurate control technique fully.
See also accompanying drawing 3 and accompanying drawing 5, because tested head space Volatile Gas is that transient flow is crossed sample introduction needle 6, gas sensor array annular working chamber 2 and gas pipeline 25, after lasting the gas headspace sampling process and transient process end that is 5 seconds, two-position two-way solenoid valve 4 is also connected, at this moment, surrounding air still flows through gas sensor array annular working chamber from the sample introduction needle mouth with the flow of 6000 ml/min, two-position two-way solenoid valve 3, two-position two-way solenoid valve 4, flowmeter 7, outlet port by gas pipeline 25 is drained into again in the atmosphere at last, and this process continues 240 seconds.The purpose of doing like this one is the fast quick-recovery of gas sensor, the 2nd, and the flushing of sample introduction needle 6, gas pipeline 25 and the residual scent molecule of gas sensor array annular working chamber 2 inwalls, the 3rd, gas sensor is accumulated taking away of heat.Operating personnel should during this period of time remove the sample of tested mistake, remove old head space gas generating unit 19 exactly, and change newly, carry out the measurement of fresh sample.
Accompanying drawing 11 has provided the present invention-a kind of olfactory analog instrument sample introduction needle replacing method synoptic diagram.After work a period of time, or because smell is residual too much or because the wearing and tearing of pin mouth are sharp inadequately, sample introduction needle needs regularly to change.At this moment, operating personnel can take off heat insulation disk 64, outer-hexagonal nut 62 and old sample introduction needle 6 successively, and change new sample introduction needle, and then tighten hexagonal nut 62, fix heat insulation disk 64 and get final product.The replacing process of sample introduction needle is convenient and swift just as the syringe needle that the doctor changes syringe.
See also Figure 12, a kind of olfactory analog instrument and multiple smell qualitative, quantitative analytical approach-structurized neural network module simultaneously are made up of two neural networks of itemizing the single hidden layer of output, are used for multiple smell is carried out qualitative and quantitative analysis; From horizontal direction, a pair of neural network module is represented a kind of smell, and wherein, previous neural network module the number of hidden nodes is s
1, be responsible for sample of identification whether from the smell of representative, under the prerequisite of confirming "Yes", a back neural network module the number of hidden nodes s
2, responsible intensity and the concentration of estimating this sample; The logarithm of neural network module equals the classification number of smell, and is corresponding one by one; The basic studies algorithm of neural network module is an error back propagation algorithm; Be responsible for the smell qualitative analysis neural network module the learning sample subclass by " a pair of all " of localization (One-against-all, OAA) decomposition method produces, and has only near the training sample the decision boundary to participate in study; Be responsible for the study subclass of the neural network module of smell quantitative test and only participate in study by the training sample of representative; The study factor is the inverse of sample number, the number of hidden nodes s
1And s
2Between 5～8, select; From vertical direction, the structuring neural network module is made up of a plurality of neural network module row-the first row and a plurality of neural network module row-secondary series that are used for the odorousness quantification that are used for smell identification; In order to determine the classification and the concentration of a smell sample undetermined, a plurality of all neural network modules that are used for smell identification of first row must be participated in decision-making, wherein the maximum neural network module of output has determined the classification of sample, yet, need only be listed as concentration and the intensity that neural network module of exporting in the corresponding secondary series of maximum neural network module quantizes the smell sample with first.
See also accompanying drawing 5, a complete sampling process of the present invention comprises the steps:
(1), start, instrument preheating 30 minutes, two-position two- way solenoid valve 3 and 4 is connected, and two-position two-way solenoid valve 5 disconnects, under the swabbing action of vacuum pump 10, surrounding air flows through gas sensor array annular working chamber 2 by sample introduction needle 6 with the flow of 6000 ml/min; Computing machine 21 is designated as original state with the response of the 30th minute this 1 pair of surrounding air of gas sensor array constantly of end;
(2), operating personnel earlier 10 milliliters of liquid state, solid-state or paste sample 44 to be put into volume be 180 milliliters glass sample bottle 43, then this glass sample bottle is put into the heat conduction cover 48 of head space gas generating unit 19, cover silicone rubber seal sheet 45, tighten bowl cover 50 then; Press the acknowledgement key on computing machine 21 keyboards, sample 44 begins to be heated, and computing machine 21 begins to calculate constant temperature time; Sample 44 is under the effect of resistance heating wire 46 by aluminium alloy heat conduction disk 47 and aluminium alloy heat conduction cover 48 heats that distribute, and accurately constant temperature is 30 minutes; In period, operating personnel are fixed on head space gas generating unit 19 on the support disk 33 of auto injection jacking gear 18 at this section;
(3), at sample constant temperature after 30 minutes, two-position two-way solenoid valve 5 is connected, and two-position two- way solenoid valve 3 and 4 disconnects, and pure air blows back into gas sensor array annular working chamber 2 with the flow of 600 ml/min from vent port, be discharged to the atmosphere from sample introduction needle 6 then, last 40 seconds; In this process, gas sensor array 1 is able to accurately demarcate with pure air;
(4), in the balance period in 5 seconds, two-position two- way solenoid valve 3,4 and 5 all disconnects, gas in the gas sensor array annular working chamber 2 remains static, the auto injection jacking gear 18 of test box makes head space gas generating unit 19 rise 20 millimeters in 3 seconds, therefore the sample introduction needle 6 that is fixed on gas sensor array annular working chamber 2 air admission holes below passes the silicone rubber seal sheet 45 on the glass sample bottle 43, touches the head space Volatile Gas in the glass sample bottle 43;
(5), two-position two-way solenoid valve 3 is connected, two-position two- way solenoid valve 4 and 5 all disconnects, vacuum pump 10 sucks gas sensor array annular working chambers 2 with the flow of 600 ml/min via sample introduction needle 6 with the head space Volatile Gas, make it to skim over rapidly the sensitive membrane surface of gas sensor array 1, pass through two-position two-way solenoid valve 3, throttling valve 7, flowmeter 9 then, be discharged to the atmosphere from the outlet port of gas pipeline 25; When head space Volatile Gas accumulated samples reached 50 milliliters, the gas headspace sampling process finished; This process lasted for 5 seconds;
(6), in the head space Volatile Gas is flowed through the process of gas sensor array annular working chamber 2, each gas sensor of forming gas sensor array 1 produces responsive the response to tested smell, and these responsive responses are delivered to computing machine 21 by being used for the signal transmission with the 37 core flat cables of controlling 27; Computing machine 21 obtains the response vector of one 16 dimension by 16 bit data capture cards 22, after structurized neural network module software analysis is handled, can obtain tested smell sample classification, intensity or key component concentration estimated value within 10 seconds, and show by the display 23 of computing machine;
(7), after the gas headspace sampling process finishes, gas sensor array 1 enters the transitional period that the head space Volatile Gas of lasting 5 seconds and surrounding air replace; Head space gas generating unit 19 is descending 20 millimeters within 3 seconds under the effect of auto injection jacking gear 18, and therefore sampling needle 6 withdraws from glass sample bottle 43 gradually; Two-position two-way solenoid valve 3 is still connected, and two-position two- way solenoid valve 4 and 5 still all disconnects, and vacuum pump 10 sucks gas sensor array annular working chamber 2 with head space Volatile Gas and surrounding air from sample introduction needle with the flow of 600 ml/min; This process is the process that the head space Volatile Gas reduces gradually, surrounding air increases gradually, and gas carries out the transition to the surrounding air of final 600 ml/min gradually from the head space Volatile Gas of initial 600 ml/min;
(8), after the transitional period end that the head space Volatile Gas reduces to increase gradually with surrounding air gradually, two-position two- way solenoid valve 3 and 4 is connected, two-position two-way solenoid valve keeps 5 to disconnect, vacuum pump 10 sucks gas sensor array annular working chamber 2 with surrounding air from sample introduction needle 6 with the flow of 6000 ml/min, lasts 240 seconds; During this period, operating personnel take the head space gas generating unit 19 of tested mistake away, change sample 44 and glass sample bottle 43, place new head space gas generating unit 19;
(9), repeat (2)～(8), repeatedly sample, a complete sampling process continues 295 seconds;
Except that step (2) and (8), whole process is finished automatically by the olfactory analog instrument under computer control.
6 head space gas generating units 19 of a kind of olfactory analog instrument configuration can be measured 6 samples in 1 hour.
Claims (26)
1. an olfactory analog instrument is characterized in that, is made up of test box, head space gas generating unit, computing machine, pure air bottle;
Described test box is connected with umbilical cable by the signal transmission with computing machine; Test box is connected by gas pipeline with the pure air bottle; The variation of the gas sensor array perception smell in the test box obtains multichannel analog signals; Computing machine changes into the multi-path digital signal with gas sensor array to the multichannel analog signals that the smell perception produces, and in view of the above smell is carried out qualitative and quantitative analysis; Pure air takes multiple measurements gas sensor array on stable gaseous state basis;
Described head space gas generating unit is connected with test box with signal-transmitting cable by power supply, is used for liquid, the solid-state or paste sample of heating with generation high capacity head space Volatile Gas; Under the control of computing machine and test box, the temperature constant of sample and head space Volatile Gas is at 55 ± 0.1 ℃;
Before the gas headspace sampling, operating personnel are fixed on the head space gas generating unit on the support disk of auto injection jacking gear in the test box; In gas headspace when sampling,, the head space gas generating unit rises under the promotion of auto injection jacking gear, is fixed in the test box sample introduction needle on the constant temperature oven thereby pierces through the silicone rubber seal sheet of head space gas generating unit and touch the head space Volatile Gas; After gas headspace sampling finished, operating personnel unclamped and remove the head space gas generating unit of the tested mistake of sample from support disk, and the head space gas generating unit of packing into new is prepared for measure next time.
2. test box according to claim 1, it is characterized in that, by constant temperature oven, auto injection jacking gear, vacuum pump, two-position two-way solenoid valve 3, two-position two-way solenoid valve 4, two-position two-way solenoid valve 5, flowmeter, four road D.C. regulated power supplies, driving and control circuit, throttling valve 7, throttling valve 8 are formed.
3. constant temperature oven according to claim 2, it is characterized in that, formed by gas sensor array, gas sensor array annular working chamber, sample introduction needle, sample introduction needle joint, outer-hexagonal nut, heat insulation disk, resistance heating wire, temperature sensor, fan, thermofin; Constant temperature oven is fixed on the test box casing.
4. constant temperature oven according to claim 3 is characterized in that, gas sensor array is overlapped each other by 16 performances and mutually different gas sensor is formed, and the variation of perception smell produces 16 tunnel analogue response voltage signal.
5. gas sensor array annular working according to claim 3 chamber, it is characterized in that, being fixed together by socket head cap screw by sensor holder and sender unit cap forms, and forms the annular cavity of sealing by 2 O RunddichtringOs, places 16 gas sensors; The annular cavity mean diameter is 140 millimeters, and cross dimensions is 20 millimeters * 16 millimeters; Sensor holder is that 140 millimeters annular cavity is evenly equipped with 18 through holes along mean diameter, and wherein 16 is the mounting hole of 7 core ceramic sockets, and 2 is air admission hole and venthole; Air admission hole and venthole are adjacent, and the centre is separated by dividing plate, thereby force tested gas to flow around gas sensor array annular working chamber; Commercial 7 a core ceramic sockets part is through transforming, and, and is connected with control circuit with driving with four road D.C. regulated power supplies of test box by lead on the mounting hole of sensor holder with tasteless bonding agent gluing; Gas sensor directly is inserted on the 7 core ceramic sockets.
6. constant temperature oven according to claim 3 is characterized in that, the sample introduction needle joint directly is fixed on air admission hole below, gas sensor array annular working chamber; Sample introduction needle is that the aperture is 1.0 millimeters a clinical syringe needles, is fixed on the sample introduction needle joint by the outer-hexagonal nut, reaches the short as far as possible purpose of air inlet gas circuit; Fit together mutually by tapering between sample introduction needle and the sample introduction needle joint; The step of changing sample introduction needle is, 1. takes off the heat insulation disk that is fixed on the constant temperature oven, 2. backs out the fixedly outer-hexagonal nut of sample introduction needle, 3. takes off old sample introduction needle, 4. changes new sample introduction needle, and 6. the outer-hexagonal nut of 5. screwing on loads onto heat insulation disk.
7. test box according to claim 2, it is characterized in that, the vent port of gas sensor array annular working chamber and two-position two-way solenoid valve 3 and 5, two-position two-way solenoid valve 5 and pure air bottle, two-position two-way solenoid valve 3 and vacuum pump, vacuum pump and throttling valve 7 and two-position two-way solenoid valve 4, throttling valve 7 and two-position two-way solenoid valve 4 and flowmeter, two-position two-way solenoid valve 5 and throttling valve 8, throttling valve 8 and pure air bottle all are connected by gas pipeline; Tested gas enters gas sensor array annular working chamber from sample introduction needle, and flows through two-position two-way solenoid valve 3, vacuum pump, throttling valve 7, flowmeter successively, and the outlet port by gas pipeline is discharged in the atmosphere at last.
8. constant temperature oven according to claim 3 is characterized in that, it is in 55 ± 0.1 ℃ the constant temperature oven that gas sensor array annular working chamber, a part of sample introduction needle all are fixed on temperature; Constant temperature oven inside is heated by the resistance heating wire, and fan makes the temperature inside the box even, and thermofin prevents that heat from outwards distributing, the variation of temperature sensor detected temperatures; The thermostatic process of constant temperature oven only heats, and does not freeze.
9. auto injection jacking gear according to claim 2, it is characterized in that, formed by stepper motor, gear 29, gear 30, nut, screw rod, support disk, guide pole, ball bearing, bearing seat, base, limit switch, inner spacing collar, outer separator, interior jump ring, outer jump ring, gear 29 is fixed on the step motor shaft, gear 30 is fixed together with nut, screw rod and support disk are fixed together, bearing seat is fixed on the base, and base and limit switch are fixed on the test box casing.
10. auto injection jacking gear according to claim 2 is characterized in that, gear 29 is No. 45 Fine Steel Casting iron materials, and gear 30 and screw rod are nonmetallic materials, and support disk and screw rod are aluminum alloy materials; Auto injection jacking gear apply oil not in the long-term work process does not produce noise.
11. auto injection jacking gear according to claim 2, it is characterized in that under the control of computing machine, stepper motor makes gear 30 rotations by gear 29, the nut thereby the rotation that are fixed together with gear 30, thus screw rod and support disk to do the rise and fall campaign together made; The pitch of screw rod and nut is 3 millimeters, and support disk rose 20 millimeters in 3 seconds, descends 20 millimeters in 3 seconds.
12. head space gas generating unit according to claim 1, it is characterized in that, formed by glass sample bottle, resistance heating wire, heat-conducting layer, thermofin, 2 temperature sensors, bowl cover, silicone rubber seal sheet, cup overcoat, cup end disk, claw, 6 core cables; Heat-conducting layer is fixed together by aluminium alloy heat conduction cover and aluminium alloy heat conduction disk and forms, the resistance heating wire is wrapped in aluminium alloy heat conduction disk bottom and aluminium alloy heat conduction puts, a temperature sensor is fixed on aluminium alloy heat conduction disk bottom aluminium alloy heat conduction cover outside surface top respectively, and the glass sample bottle is positioned on the aluminium alloy heat conduction disk of heat-conducting layer inside; The heat that the resistance heating wire produces heats the sample in the glass sample bottle by aluminium alloy heat conduction disk and aluminium alloy heat conduction cover, and thermofin and bowl cover prevent that jointly heat from distributing, and the silicone rubber seal sheet prevents that the head space Volatile Gas in the glass sample bottle from leaking.
13. head space gas generating unit according to claim 1, it is characterized in that, sample and head space Volatile Gas thermostat temperature are 55 ± 0.1 ℃, and 2 temperature sensors that are fixed in aluminium alloy heat conduction disk bottom and aluminium alloy heat conduction cover outside surface top detect the interior temperature variation of glass sample bottle; If the temperature survey mean value of 2 temperature sensors is higher than 55 ℃, then computing machine cuts off the power supply the resistance heating wire by the signal transmission with umbilical cable; If this temperature survey mean value is lower than 55 ℃, then computing machine switches on the resistance heating wire by the signal transmission with umbilical cable; Therefore, even environment temperature reaches 45 ℃, this head space gas generating unit still only heats, and does not freeze.
14. head space gas generating unit according to claim 1 is characterized in that, capacity is that 180 milliliters glass sample bottle and silicone rubber seal sheet all buied from the market, and each glass sample bottle and silicone rubber seal sheet only use once, do not produce cross-infection.
15. the described auto injection jacking gear of head space gas generating unit according to claim 1 and claim 2, it is characterized in that the cup end disk bottom of head space gas generating unit is agreed with along diametric 2 draw-in grooves in the rim, support garden of diametric 2 claws and auto injection jacking gear; Before the gas headspace sampling, operating personnel aim at 2 draw-in grooves with 2 claws earlier, rotate 5 ° of head space gas generating units then, and cup end disk just is fixed together with support disk, and both vertical centres overlap; Otherwise operating personnel can take the head space gas generating unit away from support disk fast; Head space gas generating unit and support disk fixing or take process away and all can in 10 seconds, finish.
16. the described auto injection jacking gear of head space gas generating unit according to claim 1 and claim 2, it is characterized in that, during the gas headspace sampling, under the control of computing machine, support disk is done the rise and fall campaign with the head space gas generating unit, and the maximum perpendicular displacement is 20 millimeters.
17. head space gas generating unit according to claim 1 and the described test box of claim 2, it is characterized in that, when the head space gas generating unit rises, be fixed on the sample introduction needle of air admission hole below in gas sensor array annular working chamber in the constant temperature oven thereby pierce through silicone rubber seal sheet on the glass sample bottle, thereby touch the head space Volatile Gas.
18. test box according to claim 2 is characterized in that, the voltage of four road D.C. regulated power supplies is respectively 5V, 10V, 12V and 36V; Wherein, 5V is the heating voltage of 16 gas sensors, and 10V is the operating voltage of gas sensor, and 12V is the operating voltage of 3 two-position two-way solenoid valves, vacuum pump, fan and stepper motors, and 36V is the heating voltage of test box and head space gas generating unit; 5V and 10V are linear power supply, and 12V and 36V are Switching Power Supply.
19. test box according to claim 2, it is characterized in that, vacuum pump is worked in a continuous manner, computing machine is by the energising and the outage of data collecting card and signal transmission and umbilical cable control two-position two-way solenoid valve 3,4 and 5, to control the through and off of gas sensor array annular working chamber and head space Volatile Gas, pure air and surrounding air respectively.
20. test box according to claim 2 is characterized in that, head space Volatile Gas sampling volume is 50 milliliters, by flowmeter and computing machine accurate measurement; During the gas headspace sampling, under the effect of computing machine, two-position two-way solenoid valve 3,4 and 5, the pure air passage is disconnected, head space Volatile Gas in the glass sample bottle is aspirated by vacuum pump, via sample introduction needle, with the flow of the 600 ml/min gas sensor array annular working chamber of flowing through, be discharged into the atmosphere from outlet port then.
21. test box according to claim 2, it is characterized in that, by two-position two-way solenoid valve 3,4 and 5 and the conversion and the control of throttling valve 7 and 8, make that the interior head space Volatile Gas sampling flow of glass sample bottle is 600 ml/min, the pure air flow is 600 ml/min, and ambient air is respectively 600 ml/min and 6000 ml/min; Flow is the surrounding air flushing of 6000 ml/min, the one, make the preliminary fast recovery of gas sensor; The 2nd, the heat that accumulation produces when taking away indoor 16 gas sensors of gas sensor array annular working and working simultaneously; The 3rd, wash away the scent molecule that is adsorbed on gas sensor array annular working chamber and the gas inner-walls of duct.
22. pure air bottle according to claim 1 and the described test box of claim 2, it is characterized in that, pure air is with 600 ml/min, oppositely be blown into gas sensor array annular working chamber by gas pipeline, throttling valve 8 and two-position two-way solenoid valve 5 from venthole, and finally be discharged to the atmosphere, thereby make 16 gas sensors when repeatedly sampling, all be in the steady state (SS) of repetition from sample introduction needle.
23. computing machine according to claim 1 is characterized in that, the data collecting card that is inserted on the computer motherboard is 16 way word signals with 16 A/D conversions with gas sensor array 16 tunnel analog signal conversion that perception obtains to smell; This 16 way word signal is kept on the hard disc of computer as a data file, is the olfactory analog instrument carries out qualitative and quantitative analysis to smell foundation; The time span that is recorded data is 60 seconds.
24. computing machine according to claim 1 is characterized in that, with structurized neural network module software multiple smell is carried out qualitative and quantitative analysis simultaneously; The digitalized signature that sample is a smell sample is represented, is the response of gas sensor array; The structure of a neural network module is the single hidden layer of single output; A pair of neural network module is represented a kind of smell, wherein, previous neural network module is responsible for discerning a sample whether from the smell of representative, and under the prerequisite of confirming "Yes", the neural network module of a back correspondence is responsible for estimating the intensity and the concentration of this sample; The logarithm of neural network module equals the classification number of smell, and is corresponding one by one; During decision-making, be responsible in all neural network modules of identification, the neural network module of output valve maximum is determining the classification of the smell sample of a sample and correspondence thereof.
Analyze simultaneously 25. adopt the olfactory analog instrument of claim 1 that multiple smell is carried out qualitative, quantitative, it is characterized in that, may further comprise the steps:
(1) start, instrument preheating 30 minutes, two-position two-way solenoid valve 3 and 4 is connected, and two-position two-way solenoid valve 5 disconnects, and under the swabbing action of vacuum pump, surrounding air flows through gas sensor array annular working chamber by sample introduction needle with the flow of 6000 ml/min; Computing machine with the 30th minute when last gas sensor array the response of surrounding air is designated as original state;
(2) operating personnel earlier 10 milliliters of liquid state, solid-state or paste sample to be put into volume be 180 milliliters glass sample bottle, then this glass sample bottle is put into the heat conduction cover of head space gas generating unit, cover the silicone rubber seal sheet, tighten bowl cover then; Press the acknowledgement key on the computer keyboard, sample begins to be heated, and constant temperature picks up counting; Sample is under the effect of the heat that the resistance heating wire distributes by aluminium alloy heat conduction disk and aluminium alloy heat conduction cover, and accurately constant temperature is 30 minutes; In period, operating personnel are fixed on the head space gas generating unit on the support disk of auto injection jacking gear at this section;
(3) at sample constant temperature after 30 minutes, two-position two-way solenoid valve 5 is connected, and two-position two-way solenoid valve 3 and 4 disconnects, and pure air blows back into gas sensor array annular working chamber with the flow of 600 ml/min from vent port, be discharged to the atmosphere from sample introduction needle then, last 40 seconds; In this process, gas sensor array is able to accurately demarcate with pure air;
(4) two-position two-way solenoid valve 3,4 and 5 all disconnects, the balance period that gas sensor array entered for 5 seconds; During this period, the indoor gas of gas sensor array annular working remains static, the auto injection jacking gear of test box makes the head space gas generating unit rise 20 millimeters in 3 seconds, therefore the sample introduction needle that is fixed on below, gas sensor array annular working chamber passes the silicone rubber seal sheet, touches the head space Volatile Gas in the glass sample bottle;
(5) two-position two-way solenoid valve 3 is connected, two-position two-way solenoid valve 4 and 5 all disconnects, vacuum pump sucks gas sensor array annular working chamber with the flow of 600 ml/min via sample introduction needle with the head space Volatile Gas, make it to skim over rapidly gas sensor sensitive membrane surface, be discharged into the atmosphere from outlet port through throttling valve 7 then; When head space Volatile Gas sampling accumulation reached 50 milliliters, the gas headspace sampling process finished; This process lasted for 5 seconds;
(6) in the head space Volatile Gas is flowed through the process of gas sensor array annular working chamber, each gas sensor produces responsive response to tested smell, and these responsive responses are sent to computing machine by the signal transmission with umbilical cable; Computing machine obtains one 16 dimension response vector by 16 data collecting card, after structurized neural network module software analysis is handled, can obtain tested smell sample classification, intensity or key component concentration estimated value within 10 seconds, and show by the display of computing machine;
(7) after the gas headspace sampling process finished, gas sensor array entered head space Volatile Gas flow and reduces transitional period of increasing gradually with ambient air gradually, lasts 5 seconds; The head space gas generating unit is descending 20 millimeters within 3 seconds under the effect of auto injection jacking gear, and sample introduction needle finally withdraws from the glass sample bottle fully; Two-position two-way solenoid valve 3 is still connected, and two-position two-way solenoid valve 4 and 5 still all disconnects, and vacuum pump sucks gas sensor array annular working chamber with gas from sample introduction needle; Gas carries out the transition to the surrounding air of final 600 ml/min gradually from the head space Volatile Gas of initial 600 ml/min;
(8) after the transitional period end that the head space Volatile Gas reduces to increase gradually with surrounding air gradually, two-position two-way solenoid valve 3 and 4 is connected, two-position two-way solenoid valve 5 disconnects, vacuum pump sucks gas sensor array annular working chamber with surrounding air from sample introduction needle with the flow of 6000 ml/min, lasts 240 seconds; During this period, operating personnel take the head space gas generating unit of the tested mistake of sample away, change sample and glass sample bottle, place new head space gas generating unit;
(9) repeat (2)～(8), repeatedly sample, a complete sampling process continues 295 seconds;
Except that step (2) and (8), whole process is finished automatically by the olfactory analog instrument under the control of computing machine.
26. 6 head space gas generating units of an olfactory analog instrument configuration were measured 6 samples in 1 hour.
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Application publication date: 20100818 Assignee: SHANGHAI SHANGJIQUNLI ANALYTICAL INSTRUMENT Co.,Ltd. Assignor: East China University of Science and Technology Contract record no.: 2013310000079 Denomination of invention: Olfactory analog instrument and qualitative, quantitative and simultaneous analysis method of various gases Granted publication date: 20121121 License type: Common License Record date: 20130705 |
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