The integrated olfactory analog instrument of a kind of hyperchannel and biological fermentation process on-line analysis
Technical field
The present invention-a kind of hyperchannel olfactory analog instrument and biological fermentation process on-line analysis-relate to computing machine, precision measurement, control automatically, precision optical machinery, biofermentation, bio-reactor, analytical chemistry, applied mathematics field, mainly solve olfactory analog instrument integration, miniaturization and robotization, the detection online of many biological fermentation process, remote visualization and on-line analysis problem.
Background technology
The purpose that biological fermentation process detects online, controls and optimizes is that the mode with less expensive obtains high value added product.The biological fermentation process influence factor is intricate, is Nonlinear Random Process.For example, to fermentation liquor dissolved oxygen DO (DO) concentration, pH value, throughput, temperature and fermentation tail gas composition and concentration (O
2and CO
2) etc. parameter detect online, can grasp in time the microbial growth and metabolism situation, change control strategy (for example feed supplement mode and opportunity), adjust external environment condition, to optimize thalli growth and product building-up process.Now, sweat computer control and the optimization system such as amino acid, beer, penicillin, comprise temperature, glucose control of additive raw material and optimization system, obtained practical application.
Fermentation tail gas is online detect with the importance of analyzing just just as the gas by detecting people's exhalation judge its health whether extremely.Tail gas O
2and CO
2content paramagnetic oxygen analyzer commonly used and infrared CO
2analyser is measured respectively.Development along with computing machine and sensor technology, the methods such as laser nephelometer, biology sensor, high performance liquid chromatography can realize substrate concentration, thalline activity and concentration, the isoparametric online detection of production concentration, some devices and instrument are commercially produced, but have the problems such as reliability is low, poor stability.
Mass spectrometer is a kind of typical fermentation tail gas analytical instrument, and some mass spectrometer is connected with computer data processing system and can carries out online the detection and analysis to a plurality of fermentation tanks simultaneously, is mainly used at present tail gas O
2, CO
2the online detection.The major defect of mass spectrometric analysis method is that (1) instrument price is very expensive.For example, the U.S. produces MAX300-LG mass spectrometer price more than 1,000,000 yuans, is difficult to large-scale promotion application; (2) to organic volatile composition and NH
3, the inorganic gas sensitivity such as CO is not high, is difficult to really realize that Multiple components is online detects and analyze.
The overlapping a plurality of gas sensors of olfactory analog instrument utility form arrays, can carry out fast the smell qualitative and quantitative analysis, for example, determine taste compound classification, intensity, quality grade, true and false, freshness, adjustment formula for a product and technique, etc.Application comprises: spices and essence, tea, the evaluation of drinks material aroma quality, and the fruit maturity judgement, the meat products freshness is determined, ambient air monitoring, war gas detects, medical diagnosis on disease, and even bacterium and the analysis of blood smell, etc.In fact, absolute scentless material is non-existent.
Along with the progress of material science and accurate manufacturing process, with SnO
2for the sensitivity of MOS type gas sensor of representative has reached 1.0 * 10
-9v/V (1.0ppb), usual range is 1.0~10000ppm.A development trend of olfactory analog research is, at single gas sensitive device, has under the prerequisite of necessary sensitivity, and a plurality of gas sensors overlapping by performance form arrays, utilize emphatically data analysing method to improve the selectivity of instrument.
The olfactory analog instrument application has a extensive future, but current ability limited also.Document and the patent search result relevant with olfactory analog/Electronic Nose are as follows: (1) document.Former more than 60 pieces of nineteen ninety, more than 4000 pieces have been reached now.(2) patent.100 multinomial international monopolies and more than 20 domestic patents were mostly applied in recent years or authorized, and showed and had started to pay attention to olfactory analog domain knowledge property right protection both at home and abroad.(3) technical standard.By IHS international standard database is retrieved, do not find the product technology standard relevant with olfactory analog.Through to ISI and EI data base querying, do not find that the olfactory analog method is applied to the online document that detects and analyze of sweat.
Core-the gas sensor array of olfactory analog instrument is to organic volatile gas and NH such as alcohol, hydrocarbon, alkene, ester, aldehyde, ketone
3, O
2, the inorganic gas such as CO has very high sensitivity.SnO
2the semi-conductor type gas sensor is less than 10 seconds to fermentation tail gas from starting to touch the response time that reaches steady state (SS), directly with the output of 0~10V voltage signal, does not need secondary instrument to amplify, and this is very attractive to online detection of biological fermentation process.The olfactory analog method is by detecting online the numerous compositions of fermentation tail gas, by means of computing machine and data analysing method, determine fermentation tail gas composition and concentration, and then the parameters such as concentration of substrate, thalline activity and concentration, production concentration and DO, pH value, RQ are carried out to Tangent Model.
A lot of biofermentations are accomplished scale production, no matter are in laboratory, or, at workshop, are usually that a plurality of fermentation tanks move simultaneously.For the olfactory analog method is applied to, a plurality of biological fermentation process are online to be detected and analyzes, and needs the key issue solved to be:
(i), gas sensor selection, replacing and on-line correction
The biofermentation exhaust gas component is mainly O
2and CO
2.We think, these two kinds of compositions have only reflected the side that biological fermentation process changes, or a presentation.In fact, biological fermentation process just more deeply, has more completely been portrayed in the variation of numerous micro constitutents, and the online basis of detecting and analyze this process is the diversity of gas sensor array component units.The today reduced gradually in commercialization TGS gas sensor kind, this discovery of the diversity of same type gas sensor had both brought challenge, also provided opportunity.Moreover, after working long hours, due to environmental change, " baseline wander ", " poisoning " etc. reason, gas sensor on-line correction and replacing problem have just occurred.
(ii), the accurate method of sampling of hyperchannel fermentation tail gas head space and device
Mostly the fermentation tail gas amount is advantage.Adverse condition is, a sweat often continues a couple of days and even tens of days, and gas sensor Long contact time tail gas can produce " paralysis " and even " poisoning " phenomenon; Fermentation site environment air is often unholiness; Ambient temperature and humidity changes.Therefore, detect online when realizing many fermentation tanks, we need invention multichannel tail gas head space accurate sampling and switching device shifter automatically, guarantee repeatedly the repeatability to many fermentation tank tail gas samplings.
(iii), olfactory analog instrument integration, miniaturization and robotization
The olfactory analog instrument is a kind of in the numerous detecting instruments of sweat.The olfactory analog instrument should be easy to connect with fermentation tank and other external equipment, plug and play, and easy to operate, volume is little, realizes the integrated and robotization of component units.For example, gas sensor array, automatic sample handling system, power supply, control module, data collecting card, main frame, display should be integrated in a test box, in case of necessity can external large screen display.
(iv), the simultaneously online detection of multiple ferment process, status predication and remote visualization
Development hyperchannel gas circuit automatically switches and integrating device, adopts the Internet network interface card that remote data is transmitted; In order not only to avoid data excessive but also reach the purpose of the undistorted sampling of multiple ferment process, find out hyperchannel optimum sampling time interval, realize the Data Dynamic local enlargement display, comprise that single gas sensor response is visual; The gas sensor array Whole Response is visual; Tail gas O
2, CO
2, NH
3, the composition such as ethanol, lactic acid is visual; Substrate, thalline and production concentration visual.
It is application background that the product sweats such as amino acid, microbiotic, biomaterial, industrial spirit are take in the present invention, realizes a kind of many biological fermentation process based on the olfactory analog instrument online detection and analytical approach simultaneously.
Summary of the invention
The present invention is (referring to number of patent application: 200710036260.4) in existing patent of invention " a kind of small automatic machine sense of smell instrument and smell analytical approach ", " a kind of olfactory analog instrument and multiple smell qualitative and quantitative analysis method " (referring to number of patent application: 201010115026.2) and " a kind of instrument of the olfactory analog towards biological fermentation process and on-line analysis " (referring to number of patent application: on basis 201110182955.X), invent the integrated olfactory analog instrument of a kind of hyperchannel and method, to solve many biological fermentation process online detection and problem analysis simultaneously.
To achieve these goals, the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-mainly solve gas sensor selection, replacing and the on-line correction of olfactory analog instrument; The accurate sampling of hyperchannel fermentation tail gas head space is with integrated; Olfactory analog instrument integration, miniaturization and robotization; Multiple ferment process is online the detection simultaneously; Status predication and remote visualization problem.
The integrated olfactory analog instrument of hyperchannel comprises gas sensor array and gas sensor array constant temperature operating room thereof; The accurate automatic sampling system of hyperchannel fermentation tail gas; Computer control and analytic system, this three is integrated in a test box, the online detection and analysis when realizing many biological fermentation process are many fermentation tanks.
Be fixed wtih in gas sensor array constant temperature operating room by TGS-8xx and two types of TGS-2xxx, totally 16 arrays that gas sensor forms, be positioned at the test box upper right side.
The accurate automatic sampling system of hyperchannel fermentation tail gas is positioned at the test box lower right, comprises minipump, pressure maintaining valve, first to the 8th totally 8 two-position two-way solenoid valve I-2-1-1, I-2-1-2, I-2-1-3, I-2-1-4, I-2-1-5, I-2-2, I-2-3, I-2-9, first throttle valve I-2-8, the second throttling valve I-2-4, flowmeter, 8 connections for bbreather pipe, fermentation tail gas admission line, pure air/oxygen intake pipe road, surrounding air admission line, exhaust emission pipe.
Computer control and analytic system comprise computer motherboard, 16 passage 16 A/D data collecting cards, D.C. regulated power supply, control module, hard disk, network interface card and video cards, display, are positioned at the test box left side.
Gas sensor array constant temperature operating room is connected with the accurate automatic sample handling system of hyperchannel fermentation tail gas by gas pipeline; Gas sensor array constant temperature operating room is connected with analytic system with computer control by circuit with the accurate automatic sample handling system of hyperchannel fermentation tail gas.
During the fermentation tail gas Head-space sampling, under the accurate automatic sample handling system effect of hyperchannel fermentation tail gas, the fermentation tail gas of a plurality of fermentation tanks enters gas sensor array constant temperature operating room with flow and the official hour interval of 500 ml/min successively; Within a sampling period, to the 30 seconds fermentation tail gas Head-space sampling time of a fermentation tank, therefore gas sensor array produces responsive response, and after the low-pass filtering pre-service, computer control and analytic system are on-the-spot accordingly carries out Tangent Model to biological fermentation process; Test data realizes remote transmission and remote visualization by the Internet net.
The integrated olfactory analog instrument of hyperchannel of the present invention can detect 5 fermentation tanks at most simultaneously, can carry out on-line analysis to 5 kinds of biological fermentation process simultaneously.
From the appearance, test box front right below is glass rotameter scale screen, for the online fermentation tail gas Head-space sampling flow that shows; Test box front left top is 3.5 " * 3.5 " display, for showing many bar responses of gas sensor array curve online, show gas sensor array constant temperature operating room temperature variation online, showing predicting the outcome of each fermentation tank online; Test box lower rear along continuous straight runs 8 the import/exhaust holes that distributing; Wherein, 5 fermentation tail gas mouths are connected with 5 fermentation tanks respectively by respectively with 5 1000 milliliters of tail gas bottles of pipeline (commercial glass sample bottle), plug and play; 1 pure air/oxygen air admission hole is connected with pure air/welding bottle; 1 ambient air inlet and 1 outlet port are separately arranged;
If section is only tested a sweat sometime, the olfactory analog instrument only is connected with a fermentation tank, and gaseous species and fluctuations in discharge cycle are 300 seconds, comprises (1) recovery, 215 seconds, and 6000 ml/min surrounding airs; (2) Accurate Calibration, 40 seconds, 500 ml/min pure air/oxygen, (3) balance, 5 seconds; (4) fermentation tail gas Head-space sampling, 30 seconds, 500 ml/min fermentation tail gas; (5) transition, 10 seconds, 500 ml/min surrounding airs;
If two sweats of section test sometime, be that the olfactory analog instrument is connected with 2 fermentation tanks, gaseous species and fluctuations in discharge cycle are 270 seconds, but two fermentation tank measurements are spaced apart 540 seconds, be within first 270 seconds, to detect first fermentation tank, within latter 270 seconds, detect second fermentation tank; With only testing a sweat, compare, the time interval here changes just: (1) surrounding air tentatively recovers, and 185 seconds, 6000 ml/min surrounding airs, all the other time intervals remain unchanged;
If three sweats of section test sometime, be that the olfactory analog instrument is connected with 3 fermentation tanks, gaseous species and fluctuations in discharge cycle are 240 seconds, but three fermentation tank measurements are spaced apart 720 seconds, within 0~240 second, detect first fermentation tank, within 241~480 seconds, detect second fermentation tank, within 481~720 seconds, detect the 3rd fermentation tank; With only testing a sweat, compare, the time interval here changes just: (1) surrounding air tentatively recovers, and 155 seconds, 6000 ml/min surrounding airs, all the other time intervals remain unchanged;
If four sweats of section test sometime, be that the olfactory analog instrument is connected with four fermentation tanks, gaseous species and fluctuations in discharge cycle are 210 seconds, but four fermentation tank measurements are spaced apart 840 seconds, within 0~210 second, detect first fermentation tank, within 211~420 seconds, detect second fermentation tank, within 421~630 seconds, detect the 3rd fermentation tank, within 631~840 seconds, detect the 4th fermentation tank; With only testing a sweat, compare, the time interval here changes just: (1) surrounding air tentatively recovers, and 125 seconds, 6000 ml/min surrounding airs, all the other time intervals remain unchanged;
If five sweats of section test sometime, be that the olfactory analog instrument is connected with five fermentation tanks, gaseous species and fluctuations in discharge cycle are 180 seconds, but five fermentation tank measurements are spaced apart 900 seconds, within 0~180 second, detect first fermentation tank, within 181~360 seconds, detect second fermentation tank, within 361~540 seconds, detect the 3rd fermentation tank, within 541~720 seconds, detect the 4th fermentation tank, within 721~900 seconds, detect the 5th fermentation tank; With only testing a sweat, compare, the time interval here changes just: (1) surrounding air tentatively recovers, and 95 seconds, 6000 ml/min surrounding airs, all the other time intervals remain unchanged.
With the first two-position two-way solenoid valve I-2-1-1, the second two-position two-way solenoid valve I-2-1-2, the 3rd two-position two-way solenoid valve I-2-1-3, the 4th two-position two-way solenoid valve I-2-1-4, the 5th two-position two-way solenoid valve I-2-1-5 totally 5 two-position two-way solenoid valves realize 5 switchings between fermentation tank; Measure some fermentation tanks and mean corresponding two-position two-way solenoid valve conducting, all the other 4 two-position two-way solenoid valves disconnect; The 7th two-position two-way solenoid valve I-2-3 of these 5 two-position two-way solenoid valves and the 6th two-position two-way solenoid valve I-2-2 that controls pure air/oxygen break-make, the air break-make that controls environment and controlling together with the 8th two-position two-way solenoid valve I-2-9 of gas flow size, realize between fermentation tail gas, pure air/oxygen, three kinds of gases of surrounding air and 6000 ml/min, two kinds of flows of 500 ml/min between switching.
Pressure maintaining valve between fermentation tank and gas sensor array constant temperature operating room makes the gaseous tension of the gas sensor array constant temperature operating room that flows through be always normal pressure, i.e. 0.1MPa.
It is online that test data passes to Internet by network interface card, realizes remote transmission, remote visualization and remote monitoring; Show online gas sensor response curve and gas sensor array constant temperature operating room temperature variation by video card and 3.5 " * 3.5 " display; The large screen display that 3.5 " * 3.5 " displays that test box carries and user provide for oneself can select one and use.
In each data sampling cycle, finish to stop to the fermentation tail gas Head-space sampling from the fermentation tail gas Head-space sampling starts, and totally 30 seconds, the voltage response curves of computer control and 16 gas sensors of analytic system blotter; After the fermentation tail gas Head-space sampling finishes, from 16 voltage response curves of blotter, extract steady state voltage response maximal value, average gradient and integrated value as response component; In one-shot measurement, from 16 gas sensors, obtain 48 response component.
16 voltage response curves of the online demonstration of computer control and analytic system; In 16 steady state voltage response maximal value curves, the currency of arbitrary surpasses 5.0V, sends alarm; If the currency of many steady state voltage response maximal value curves surpasses 7.0V, send the seriously early warning of undesired, possible microbiological contamination of biological fermentation process.
The user can be according to the integrated olfactory analog instrument of hyperchannel, utilizes that the Internet net is long-range to be shown, follow the tracks of and monitor a plurality of sweats.
A complete fermentation tail gas sampling comprises the steps: with analytic process
(1), surrounding air tentatively recovers
The 7th two-position two-way solenoid valve I-2-3 and the 8th two-position two-way solenoid valve I-2-9 connect, all the other two-position two-way solenoid valves disconnect, under the swabbing action of minipump I-2-7, surrounding air flows through the 7th two-position two-way solenoid valve I-2-3,8 connection for bbreather pipe I-2-5, pressure maintaining valve I-2-6, gas sensor array I-1-1 and gas sensor array annular working chamber I-1-2, minipump I-2-7, the 8th two-position two-way solenoid valve I-2-9 successively with the flow of 6000 ml/min, finally is discharged in atmosphere.
(2), pure air/oxygen Accurate Calibration
At the 6th two-position two-way solenoid valve I-2-2, connect, all the other two-position two-way solenoid valves all disconnect, pure air/oxygen flows through the second throttling valve I-2-4, the 6th two-position two-way solenoid valve I-2-2,8 connection for bbreather pipe I-2-5, pressure maintaining valve I-2-6, gas sensor array I-1-1, minipump I-2-7, first throttle valve I-2-8, flowmeter I-2-10 with the flow of 500 ml/min successively from pure air/welding bottle IV, then be discharged in atmosphere, last 40 seconds; In this process, gas sensor array I-1-1 is able to Accurate Calibration.
(3), balance
In the balance period in 5 seconds, all 8 two-position two-way solenoid valves all disconnect, and the gas in gas sensor array annular working chamber I-1-2 remains static.
(4), fermentation tail gas Head-space sampling
Only have and fermentation tank II-i(i=1 to be detected, 2,3,4,5) corresponding two-position two-way solenoid valve I-2-1-i connects, all the other two-position two-way solenoid valves all disconnect, minipump I-2-7 is the flow suction gas sensor array annular working chamber I-1-2 with 500 ml/min by the fermentation tail gas in corresponding tail gas bottle III-i, make it to skim over rapidly the sensitive membrane surface of gas sensor array I-1-1, then pass through first throttle valve I-2-8, flowmeter I-2-10, be discharged to atmosphere from outlet port; When the sampling time reaches 30 seconds, fermentation tail gas Head-space sampling process finishes.
(5), transition
After fermentation tail gas Head-space sampling process finishes, gas sensor array I-1-1 enters the transitional period that the head space Volatile Gas of lasting 10 seconds and surrounding air replace; The 7th two-position two-way solenoid valve I-2-3 still connects, and all the other two-position two-way solenoid valves all disconnect, and minipump I-2-7 sucks gas sensor array annular working chamber I-1-2 with the flow of 500 ml/min by surrounding air.
(6), fermentation tank switching
During step (4) fermentation tail gas Head-space sampling, only have the two-position two-way solenoid valve I-2-1-i corresponding with fermentation tank II-i to be detected to connect, all the other two-position two-way solenoid valves corresponding with not detecting the survey fermentation tank disconnect; At this moment, control the 6th two-position two-way solenoid valve I-2-2, the air that the controls environment/filtrated air break-make of pure air/oxygen break-make the 7th two-position two-way solenoid valve I-2-3, control the 8th two-position two-way solenoid valve I-2-9 that 6000 ml/min and 500 ml/min gas flows change and all disconnect.
(7), sweat on-line analysis and prediction
In fermentation tail gas is flowed through the process of gas sensor array annular working chamber I-1-2, gas sensor array I-1-1 produces responsive response to fermentation tail gas, and these responsive responses are by being delivered to computer control and analytic system I-3 for the signal transmission with control cables; Computer control and analytic system I-3 obtain the response vector of one 3 * 16 dimension by data collecting card, after the pre-service such as filtering, dimensionality reduction, computer control and analytic system I-3 within fermentation tail gas Head-space sampling process finishes 10 seconds, provide sweat normally whether, whether microbiological contamination wait early warning, tail gas O
2, CO
2, NH
3deng ingredient prediction; The parameter estimation such as dissolved oxygen DO (DO), respiratory quotient (RQ); Substrate, thalline and production concentration estimate and the thalline activity analysis, and by test data with analysis result demonstration in real time with by the teletransmission of Internet net.
(8), repeating step (1)~(7), realize the continuous several times sampling to a plurality of fermentation tanks; A complete sampling period continues 5~15 minutes.
The online detection of a plurality of biological fermentation process is completed by the olfactory analog instrument automatically with analysis.
The accompanying drawing explanation
Fig. 1 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-olfactory analog instrument outward appearance and component units schematic diagram.
Fig. 2 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and the biological fermentation process on-line analysis-olfactory analog instrument back side (back) schematic diagram.
Fig. 3 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-olfactory analog instrument front schematic view.
Fig. 4 is that the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-olfactory analog instrument are at biological fermentation process test site position view.
Fig. 5 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-olfactory analog instrument gas circuit schematic diagram.
Fig. 6 is for example, gas circuit schematic diagram when a fermentation tank (the 1st) is detected of the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-olfactory analog instrument.
Fig. 7 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-gas sensor array and gas sensor array annular working chamber schematic diagram thereof.
Fig. 8 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and the biological fermentation process on-line analysis-olfactory analog instrument one time fermentation procedural test result schematic diagram to the rhzomorph C that insures.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Fig. 1 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-olfactory analog instrument I outward appearance and component units schematic diagram.The instrument outward appearance is rectangular parallelepiped, can see 3.5 " * 3.5 " LCDs I-3-1 and flowmeter I-2-10 from front.Component units comprises the gas sensor array constant temperature I-1 of operating room, the accurate automatic sample handling system I-2 of hyperchannel fermentation tail gas and computer control and analytic system I-3; Wherein, the gas sensor array constant temperature I-1 of operating room is positioned at olfactory analog instrument I(hereinafter to be referred as test box) upper right side, the gas sensor array I-1-1 that inside is fixed wtih gas sensor array annular working chamber I-1-2 and is comprised of 16 TGS-8xx, TGS-2xxx type gas sensor; The accurate automatic sample handling system I-2 of hyperchannel fermentation tail gas is positioned at the test box lower right; Computer control and analytic system I-3 are positioned at the test box left side, comprise mainboard, data collecting card, D.C. regulated power supply, control module, hard disk, network interface card and video card.
Available gas sensor comprises TGS813, TGS816, TGS821, TGS822, TGS826, TGS830, TGS831, TGS832, TGS880, TGS2600, TGS2602, TGS2603, TGS2610, TGS2611, TGS2620, TGS2442 now.TGS2444。
Fig. 2 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-olfactory analog instrument I schematic rear view.Here, 5 fermentation tail gas mouths, pure air/oxygen port, surrounding air/filtrated air mouth, outlet port, supply socket, external-connection displayer socket, Internet interface, mouse socket, keyboard socket and 2 USB socket can be seen.
Fig. 3 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-olfactory analog instrument front schematic view, and 3.5 " * 3.5 " LCDs I-3-1 and flowmeter I-2-10 are visible.
Fig. 4 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and the biological fermentation process on-line analysis-olfactory analog instrument I position view in the biological fermentation process test site.Comprise, 5 fermentation tank II-1, II-2, II-3, II-4, II-5,5 1000 milliliters tail gas bottle III-1, III-2, III-3, III-4, III-5(users provide for oneself) and pure air/welding bottle IV(user provide for oneself).Olfactory analog instrument I all is connected by pipeline with 5 fermentation tanks with pure air/welding bottle IV, 5 tail gas bottles with 5 tail gas bottles, olfactory analog instrument I.For avoiding polluting, gas pipeline is the 3mm stainless-steel tube preferably, also is convenient to bending simultaneously.1000 milliliters of tail gas bottle III-1, III-2, III-3, III-4, III-5 are commercial glass flask, effect is to collect fermentation tail gas, with the accurate automatic sample handling system I-2 of hyperchannel fermentation tail gas that guarantees olfactory analog instrument I, can within the 30 second time of fermentation tail gas Head-space sampling, be drawn into enough fermentation tail gas.
The integrated olfactory analog instrument of hyperchannel of the present invention I can meet at most 5 fermentation tank II-1, II-2, II-3, II-4, II-5, that is to say, can carry out online the detection and analysis to 5 biological fermentation process simultaneously.The present invention recommends to detect 1~2 fermentation tank simultaneously, and major consideration is gas sensor length release time and fermentation tank sense cycle.
When sweat is done to precision measurement, recommendation pure air of the present invention and filtrated air; When general detection and environmental pollution are not serious, the environment for use air gets final product; For cost saving, available oxygen replaces pure air.
As previously mentioned, while measuring 1,2,3,4,5 fermentation tank simultaneously, gas sensor length release time is 215 seconds, 185 seconds, 155 seconds, 125 seconds, 95 seconds successively, and the sense cycle of a fermentation tank is 5 minutes, 9 minutes, 12 minutes, 14 minutes and 15 minutes successively.It is considered herein that, although the fermentation tail gas odour intensity is not bery strong, gas sensor length release time should not be less than 90 seconds, and the sense cycle of a fermentation tank should not be greater than 15 minutes.Otherwise, the baseline of gas sensor easily drifts about, and the variation of sweat can not be detected in time.
Fig. 5 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-olfactory analog instrument gas circuit schematic diagram.Comprise, 8 two-position two-way solenoid valves (i.e. an I-2-1-1, the 2nd I-2-1-2, the 3rd I-2-1-3, the 4th I-2-1-4, the 5th I-2-1-5, the 6th I-2-2, the 7th I-2-3, the 8th I-2-9), 8 connection for bbreather pipe I-2-5, pressure maintaining valve I-2-6, gas sensor array I-1-1 and the gas sensor array constant temperature I-1-2 of operating room thereof, minipump I-2-7, first throttle valve I-2-8, the second throttling valve I-2-4, flowmeter I-2-10.
5 two-position two-way solenoid valve I-2-1-1, I-2-1-2, I-2-1-3, I-2-1-4, I-2-1-5 control respectively the through and off of 5 fermentation tank II-1, II-2, II-3, II-4, II-5 fermentation tail gas, the 6th two-position two-way solenoid valve I-2-2 controls the through and off of pure air/oxygen, the control environment through and off of air/filtrated air of the 7th two-position two-way solenoid valve I-2-3, two-position two-way solenoid valve I-2-9 implements 6000 ml/min to the conversion between 500 ml/min gas flows.
The effect of pressure maintaining valve I-2-6 is, protection gas sensor array annular working chamber is in order to avoid be fermented tail gas or filtrated air or pure air/oxygen and break through because air pressure is too high.The effect of minipump I-2-7 and first throttle valve I-2-8 is the consistance of the fermentation tail gas flow while guaranteeing repeatedly the fermentation tail gas Head-space sampling.
Fig. 6 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-olfactory analog instrument gas circuit schematic diagram during to fermentation tank II-1 fermentation tail gas Head-space sampling.At this moment, the first two-position two-way solenoid valve I-2-1-1 of controlled fermentation tank II-1 is in conducting state, and all the other two-position two-way solenoid valves are all in off-state.The fermentation tail gas of fermentation tank II-1 flows through tail gas bottle III-1,8 connection for bbreather pipe I-2-5, pressure maintaining valve I-2-6 successively, gas sensor array I-1-1 and the gas sensor array constant temperature I-1-2 of operating room thereof, minipump I-2-7, first throttle valve I-2-8, flowmeter I-2-10, finally be discharged in atmosphere.
Fig. 7 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and biological fermentation process on-line analysis-gas sensor array I-1-1 and gas sensor array annular working chamber I-1-2 schematic diagram thereof.Fig. 7 (a) is gas sensor array I-1-1 distribution situation and gas sensor array annular working chamber base I-1-2-1 figure.Figure can find out thus, and 16 gas sensors of gas sensor array I-1-1 distribute ringwise, and an air admission hole and a venthole are arranged on gas sensor array annular working chamber base I-1-2-1.16 gas sensors are 20 ° of annular equal angles and distribute together with air admission hole, venthole.Fig. 7 (b) is gas sensor array annular working chamber lid I-1-2-2 figure, and a dividing plate I-1-2-3 separates air admission hole and venthole.Fig. 7 (c) is the sectional drawing of gas sensor array annular working chamber I-1-2, comprises base I-1-2-1, lid I-1-2-2, gas sensor array I-1-1 and 7 core ceramic socket I, tackifier, O RunddichtringO, screw.When fermentation tail gas, when gas sensor array annular working chamber I-1-2 flows, gas sensor array I-1-1 produces responsive response.
Fig. 8 is the integrated olfactory analog instrument of the present invention-a kind of hyperchannel and the biological fermentation process on-line analysis-olfactory analog instrument one time fermentation procedural test result schematic diagram to the rhzomorph C that insures.Because gas sensor array is comprised of 16 gas sensors, so, have 16 bar response curves.Within each sampling period of 5~15 minutes, only get the steady state voltage response maximal value of each gas sensor.In figure, first spike means that dissolved oxygen is abnormal, and second peak means the microbiological contamination of system possibility, finally in fermentation, proceeds to 60 hours and puts tank, i.e. artificial stuck fermentation process because of microbiological contamination.This example explanation, it is abnormal that the olfactory analog instrument just finds that when fermenting to 25 hours sweat occurs, approximately within 35 hours, finds in advance than the people, thereby can change technique or premature termination fermentation according to this detection and analysis result, with the reduction loss, boosts productivity.
A complete fermentation tail gas sampling of the present invention comprises the steps: with analytic process
(1), surrounding air tentatively recovers.The 7th two-position two-way solenoid valve I-2-3 and the 8th two-position two-way solenoid valve I-2-9 connect, all the other two-position two-way solenoid valves disconnect, under the swabbing action of minipump I-2-7, surrounding air flows through the 7th two-position two-way solenoid valve I-2-3,8 connection for bbreather pipe I-2-5, pressure maintaining valve I-2-6, gas sensor array I-1-1 and gas sensor array annular working chamber I-1-2, minipump I-2-7, the 8th two-position two-way solenoid valve I-2-9 successively with the flow of 6000 ml/min, finally is discharged in atmosphere.
(2), pure air/oxygen Accurate Calibration.At the 6th two-position two-way solenoid valve I-2-2, connect, all the other two-position two-way solenoid valves all disconnect, pure air/oxygen flows through the second throttling valve I-2-4, the 6th two-position two-way solenoid valve I-2-2,8 connection for bbreather pipe I-2-5, pressure maintaining valve I-2-6, gas sensor array I-1-1, minipump I-2-7, first throttle valve I-2-8, flowmeter I-2-10 with the flow of 500 ml/min successively from pure air/welding bottle IV, then be discharged in atmosphere, last 40 seconds; In this process, gas sensor array I-1-1 is able to Accurate Calibration.
(3), balance.In the balance period in 5 seconds, all 8 two-position two-way solenoid valves all disconnect, and the gas in gas sensor array annular working chamber I-1-2 remains static.
(4), fermentation tail gas Head-space sampling.Only have and fermentation tank II-i(i=1 to be detected, 2,3,4,5) corresponding two-position two-way solenoid valve I-2-1-i connects, all the other two-position two-way solenoid valves all disconnect, minipump I-2-7 is the flow suction gas sensor array annular working chamber I-1-2 with 500 ml/min by the fermentation tail gas in corresponding tail gas bottle III-i, make it to skim over rapidly the sensitive membrane surface of gas sensor array I-1-1, then pass through first throttle valve I-2-8, flowmeter I-2-10, be discharged to atmosphere from outlet port; When the sampling time reaches 30 seconds, fermentation tail gas Head-space sampling process finishes.
(5), transition.After fermentation tail gas Head-space sampling process finishes, gas sensor array I-1-1 enters the transitional period that the head space Volatile Gas of lasting 10 seconds and surrounding air replace; The 7th two-position two-way solenoid valve I-2-3 still connects, and all the other two-position two-way solenoid valves all disconnect, and minipump I-2-7 sucks gas sensor array annular working chamber I-1-2 with the flow of 500 ml/min by surrounding air.
(6), fermentation tank switching.During step (4) fermentation tail gas Head-space sampling, only have the two-position two-way solenoid valve I-2-1-i corresponding with fermentation tank II-i to be detected to connect, all the other two-position two-way solenoid valves corresponding with not detecting the survey fermentation tank disconnect.At this moment, control the 6th two-position two-way solenoid valve I-2-2, the air that the controls environment/filtrated air break-make of pure air/oxygen break-make the 7th two-position two-way solenoid valve I-2-3, control the 8th two-position two-way solenoid valve I-2-9 that 6000 ml/min and 500 ml/min gas flows change and all disconnect.
(7), sweat on-line analysis and prediction.In fermentation tail gas is flowed through the process of gas sensor array annular working chamber I-1-2, gas sensor array I-1-1 produces responsive response to fermentation tail gas, and these responsive responses are by being delivered to computer control and analytic system I-3 for the signal transmission with control cables; Computer control and analytic system I-3 obtain the response vector of one 3 * 16 dimension by data collecting card, after the pre-service such as filtering, dimensionality reduction, computer control and analytic system I-3 within fermentation tail gas Head-space sampling process finishes 10 seconds, provide sweat normally whether, whether microbiological contamination wait early warning, tail gas O
2, CO
2, NH
3deng ingredient prediction; The parameter estimation such as dissolved oxygen DO (DO), respiratory quotient (RQ); Substrate, thalline and production concentration estimate and the thalline activity analysis, and by test data with analysis result demonstration in real time with by the teletransmission of Internet net.
(8), repeating step (1)~(7), realize the continuous several times sampling to a plurality of fermentation tanks.A complete sampling period continues 5~15 minutes.From gas sensor, recover and these two factors considerations of fermentation tank sense cycle, the present invention recommends to detect online and two biological fermentation process of analysis with an olfactory analog instrument simultaneously.
The online detection of a plurality of biological fermentation process is completed by the olfactory analog instrument automatically with analysis.