CN105527375A - Device and method for detecting sulfur dioxide in experiment environment - Google Patents

Device and method for detecting sulfur dioxide in experiment environment Download PDF

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Publication number
CN105527375A
CN105527375A CN201510595605.4A CN201510595605A CN105527375A CN 105527375 A CN105527375 A CN 105527375A CN 201510595605 A CN201510595605 A CN 201510595605A CN 105527375 A CN105527375 A CN 105527375A
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sensor
air chamber
controller
signal
gas
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施小平
连广浒
阚相如
朱义族
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Zhejiang Gongshang University
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Zhejiang Gongshang University
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Abstract

The invention discloses a device and method for detecting sulfur dioxide in an experiment environment. The device comprises a controller, a memory, a base plate, an air chamber which has the rectangular section and is arranged on the base plate, a tail gas treatment device which is arranged on the base plate, a support which is arranged on the base plate, a guiding structure which is arranged on the support and a transverse screw which is arranged on the support. The top of the inner wall of the air chamber is provided with a frequency-adjustable supersonic generator and several fans blowing air down and the inner side wall of the air chamber is orderly provided with at least two gas sensitive membranes and a heating wire metal mesh for supporting the gas sensitive membranes from top to bottom. The device and method have high sensitivity, good stability, short response time and good selectivity to sulfur dioxide, can detect a trace amount of sulfur dioxide gas with a lower concentration and can effectively guarantee human body health.

Description

Sulphuric dioxide pick-up unit and detection method in experimental situation
Technical field
The present invention relates to Environmental security technical field, especially relate to a kind of can fast, accurately in test experience room environmental sulfur dioxide concentration experimental situation in sulphuric dioxide pick-up unit and detection method.
Background technology
Sulphuric dioxide (SO2) is common oxysulfide, one of Air Pollutant Discharge.This gas can be sprayed during volcanic explosion, in many industrial processs, also can produce sulphuric dioxide.Because coal and oil all contain sulphur compound usually, therefore sulphuric dioxide can be generated during burning.When sulphuric dioxide is soluble in water, sulphurous acid (principal ingredient of acid rain) can be formed.If sulphuric dioxide is oxidized further, usually in the presence of a catalyst, just efficiently sulfuric acid can be generated rapidly.Sulphuric dioxide is water white transparency gas, irritant stink, water-soluble, ethanol and ether.
At present low-concentration sulfur dioxide detection method is mainly relied on to the method for instrumental analysis, as vapor-phase chromatography etc.Although above-mentioned detection method can the concentration of trace sulfur dioxide in testing environment accurately, the deficiencies such as ubiquity sense cycle length, cost intensive; And need the those of skill in the art's operating instrument equipment through professional training, the scene of trace sulfur dioxide in environment that cannot realize accurately is detected fast.
Therefore, the detection system for trace sulfur dioxide used at present exists that sensitivity is low, poor selectivity, poor stability or can not the problem of Long-Time Service.
Chinese patent Authorization Notice No.: CN101846610A, authorized announcement date on September 29th, 2010, disclose a kind of gas-detecting device and gas detecting system, it comprises quartz plate, first electrode, second electrode and adsorbed layer, described quartz plate has relative first surface and second surface, described first electrode is formed at first surface, described second electrode is formed at second surface, described adsorbed layer is formed at the first electrode surface, described adsorbed layer is made up of iridium-iridium dioxide nanometer rods, for adsorbing gas to be detected, change to make the quality of gas-detecting device, thus obtain the concentration of gas to be detected.It is slow to there is detection speed in this invention, the deficiency that accuracy of detection is low.
Summary of the invention
The present invention is that the sense cycle in order to overcome gas detection method of the prior art is long, cost is high, the deficiency of apparatus expensive, provide a kind of can fast, accurately in test experience room environmental sulfur dioxide concentration experimental situation in sulphuric dioxide pick-up unit and detection method.
To achieve these goals, the present invention is by the following technical solutions:
Sulphuric dioxide pick-up unit in a kind of experimental situation, comprises controller, storer, base plate, is located at air chamber, exhaust gas processing device and bracing frame that xsect on base plate is rectangular, is located at the guide frame on bracing frame and cross lead screw;
Described air chamber inwall top is provided with frequency-adjustable ultrasonic generator and for several fans to canyon, air chamber madial wall be from top to bottom provided with successively at least 2 layers of gas sensitization film, for support gas sensitization film the wire netting be made up of heating wire, be positioned at wire netting bottom and air chamber be divided into upper and lower two-part horizontal baffle, air chamber inner bottom part is provided with ultrasonic receiver, supporting plate, detection head and the track along splint upper surface Spiral distribution, and detection head is provided with MQ-2 sensor, MQ-135 sensor and SO 2 sensor; Gas sensitization film is provided with several through holes, and the air chamber inwall corresponding with gas sensitization film location is provided with some air guide vertical slots;
Cross lead screw one end is connected with the rotating shaft of the first motor be located on bracing frame, described air chamber is provided with the opening for inserting horizontal baffle, horizontal baffle outer end is provided with web joint, detection head bottom is provided with the second motor for driving detection head orbital motion, web joint is connected with wire rod thread, web joint and guide frame are slidably connected, and the air chamber being positioned at horizontal baffle upper and lower is respectively equipped with one group of draft tube and escape pipe; Draft tube and escape pipe are equipped with solenoid valve; Hermetically-sealed construction is provided with between opening and horizontal baffle; Exhaust gas processing device is connected with the escape pipe on air chamber top; The draft tube on horizontal baffle top is provided with flowmeter;
Controller is electrically connected with frequency-adjustable ultrasonic generator, ultrasonic receiver, flowmeter, storer, each electric fan, each solenoid valve, wire netting, the first motor, the second motor, MQ-2 sensor, MQ-135 sensor and SO 2 sensor respectively.
Gas sensitization film is used for adsorption experiment room gas, and gas sensitization film has gas inrichment, can by gas sensitization film successively ultrasonic cleaning 15min in HNO3 (1: 1), acetone and distilled water, and the electrode after cleaning dries for subsequent use under being placed in room temperature; Mixed with polyglycol solution by cider by a certain percentage, evenly obtain potpourri with sonic oscillation, drawing 5 μ L massfractions with micro syringe is the potpourri of 5%Nafion, drips and is applied to gas sensitization film surface, dry stand-by under room temperature.
Frequency-adjustable ultrasonic generator and ultrasonic receiver are for driving the vibrations of gas sensitization film amplitude peak, and wire netting is used for heated air sensitive membrane, thus make that the gas that adsorbs in gas sensitization film is as much as possible to be come out; Wire netting is used for heated air sensitive membrane, and each fan is used for the gas come out from gas sensitization film through overbaking to blow to air chamber bottom, is convenient to each sensor and detects; Horizontal baffle is used for partitioned air chambers upper and lower, thus facilitates air chamber upper and lower to carry out gas enrichment and sensor cleaning simultaneously; Bracing frame, guide frame, cross lead screw and the first motor move horizontally for driving horizontal baffle, thus make controller will be divided into upper and lower two parts by the first Electric Machine Control horizontal baffle in air chamber or make air chamber recover as a whole; Supporting plate provides support to track, and track provides the guiding moving to supporting plate different parts to detection head, and MQ-2 sensor and MQ-135 sensor are respectively used to testing environment signal, and SO 2 sensor is for detecting sulfur dioxide gas signal; Second motor is for driving detection head along rail moving.Flowmeter is used for the laboratory air of fixing quantity gas coming through sensitive membrane.
Because sensor all has cross sensitivity to detected object gas, therefore the present invention adopts MQ-2 sensor and MQ-135 sensor as aiding sensors, SO 2 sensor is as the master reference detecting sulfur dioxide gas, the signal that MQ-2 sensor, MQ-135 sensor and SO 2 sensor detect is merged, obtain sensor fusion signal signal (t), thus both remained the Detection Information of master reference, remain again the signal difference information between main force's sensor and aiding sensors, improve accuracy of detection.
Therefore, the present invention there is highly sensitive, good stability and the response time short, to sulphuric dioxide, there is good selectivity, the trace sulfur dioxide gas that concentration is lower can be detected, thus effectively ensure the feature that people are healthy.
As preferably, described track comprises substrate, is located at two spaced grooves of upper surface of base plate, and described groove floor is provided with the tooth bar arranged at equal intervals; Be provided with bottom described detection head two with the gear of fit depressions; The rotating shaft of described second motor is connected with the coupling shaft be located between two gears.
As preferably, described substrate is provided with the first baffle plate, the second baffle relative with the first baffle plate; First baffle plate, second baffle are provided with corresponding guide chute; The coupling shaft two ends of described gear are provided with the outrigger shaft of guide chute for inserting the first baffle plate, second baffle; Detection head lower surface is provided with several balls with the first baffle plate, second baffle upper surface Structure deformation.The setting of guide chute, outrigger shaft and ball, make the stability of detection head better, friction force is less.
As preferably, support frame as described above comprises the U-shaped frame that Open Side Down, is located at the L shape frame of air chamber front and rear; Described guide frame is be located at two crossbeams between U-shaped frame and two L shape framves; Described web joint is rectangular, and web joint bottom is provided with for 2 through holes through two crossbeams, and web joint top is provided with the screw hole for coordinating with cross lead screw.
As preferably, in gas sensitization film, be provided with the cavity that several are spaced apart, in cavity, be provided with the carbon nano-tube of stretching out outside gas sensitization film upper and lower surface; Exhaust gas processing device is spirit lamp.Cavity and carbon nano-tube add the adsorptive power of gas sensitization film to gas.
In experimental situation, a detection method for sulphuric dioxide pick-up unit, comprises the steps:
(6-1) solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe is all opened, in air chamber bottom, helium is filled with by draft tube, to MQ-2 sensor, MQ-135 sensor and SO 2 sensor cleaning 10 to 20 minutes, after cleaning, the solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe all cuts out;
(6-2) solenoid valve that controller controls on the draft tube on air chamber top and escape pipe is opened, laboratory air to be detected is filled with to air chamber by draft tube, the flow of flowmeter testing laboratory gas, the laboratory air that exhaust gas processing device process exports from escape pipe; Each gas sensitization film adsorbed gas, when the flow of laboratory air reaches L, controller controls the closed electromagnetic valve on the draft tube on air chamber top and escape pipe;
(6-3) controller controls the first driven by motor cross lead screw and rotates, and cross lead screw drives horizontal baffle to move horizontally outside air chamber by web joint, and when horizontal baffle the inner being moved to contact with opening position, controller controls the first motor and quits work;
(6-4) the adjustable ultrasonic generator of controller controlled frequency sends ultrasound wave, ultrasonic receiver receives ultrasound wave, controller controlled frequency is adjustable, and ultrasonic generator sends hyperacousticly increases frequency gradually from 5Hz and increase, until when the amplitude of ultrasonic making ultrasonic receiver receive is maximum, controller controlled frequency is adjustable, and hyperacoustic frequency that ultrasonic generator sends keeps stable;
Ultrasound wave drives the vibrations of gas sensitization film, and controller controls wire netting energising, and wire netting is the heating of gas sensitization film, and controller controls each electric fan work, and the gas of gas sensitization film absorption enters air chamber bottom; After 5 to 8 minutes, controller controls wire netting power-off, and each electric fan quits work, and frequency-adjustable ultrasonic generator and ultrasonic receiver quit work;
(6-5) controller controls the first driven by motor cross lead screw rotation, cross lead screw drives horizontal baffle to move horizontally in air chamber by web joint, when horizontal baffle outer end being moved to contact with opening position to contact, controller controls the first motor and quits work;
(6-6) controller passes through the second driven by motor detection head along rail moving, MQ-2 sensor, MQ-135 sensor and SO 2 sensor detect gas signal, controller receives detection signal S1 (t) of SO 2 sensor, detection signal S2 (t) of MQ-2 sensor, detection signal S3 (t) of MQ-135 sensor; Controller utilizes formula signal (t)=S1 2(t)+(S1 (t)-S2 (t)) 2+ (S1 (t)-S3 (t)) 2calculating sensor merges signal signal (t);
(6-7) be previously stored with accidental resonance model and sulfur dioxide concentration forecast model in storer, inputted by signal (t) in accidental resonance model, controller calculates the output signal-to-noise ratio SNR during resonance of accidental resonance model,
SNR is inputted in sulfur dioxide concentration forecast model, obtain the sulfur dioxide concentration of the laboratory air be detected.
Because sensor all has cross sensitivity to detected object gas, therefore the present invention adopts MQ-2 sensor and MQ-135 sensor as aiding sensors, SO 2 sensor is as the master reference detecting sulfur dioxide gas, the detection signal that the detection signal of SO 2 sensor is S1 (t), the detection signal of MQ-2 sensor is S2 (t), MQ-135 sensor is S3 (t); The present invention utilizes formula
Signal (t)=S1 2(t)+(S1 (t)-S2 (t)) 2+ (S1 (t)-S3 (t)) 2the signal that MQ-2 sensor, MQ-135 sensor and SO 2 sensor detect is merged, obtain sensor fusion signal signal (t), thus both remained the Detection Information of master reference, remain again the signal difference information between main force's sensor and aiding sensors, improve accuracy of detection.
As preferably, described step (6-1) is replaced by following step:
(7-1) solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe was all opened, and is filled with helium by draft tube in air chamber bottom, to MQ-2 sensor, MQ-135 sensor and SO 2 sensor cleaning 8 to 10 minutes;
(7-2) be filled with to air chamber bottom the laboratory air that known sulfur dioxide concentration is S by draft tube, the laboratory air that exhaust gas processing device process exports from escape pipe; The flow of flowmeter testing laboratory gas, the laboratory air that exhaust gas processing device process exports from escape pipe; Each gas sensitization film adsorbed gas, when the flow of laboratory air reaches L, controller controls the closed electromagnetic valve on the draft tube on air chamber top and escape pipe;
Controller passes through the second driven by motor detection head along rail moving, MQ-2 sensor, MQ-135 sensor and SO 2 sensor detect gas signal, MQ-2 sensor, MQ-135 sensor and SO 2 sensor detect gas signal, controller receives detection signal S1 (t) of SO 2 sensor, detection signal S2 (t) of MQ-2 sensor, detection signal S3 (t) of MQ-135 sensor;
(7-3) n the sample value S11 be spacedly distributed of S1 (t) chosen by controller, S12 ..., S1n, choose n the sample value S21 be spacedly distributed of S2 (t), S22 ..., S2n, choose n the sample value S31 be spacedly distributed of S3 (t), S32 ..., S3n;
Utilize formula
Di 2=(S1i-S) 2+ (S2i-S) 2+ (S3i-S) 2, i=1,2 ..., n, calculated difference distance di 2;
Utilize following formula A = ( S 11 - S ) 2 ( S 12 - S ) 2 . . . ( S 1 n - S ) 2 , B = ( S 21 - S ) 2 ( S 22 - S ) 2 . . . ( S 2 n - S ) 2 , C = ( S 31 - S ) 2 ( S 32 - S ) 2 . . . ( S 3 n - S ) 2 , D = d 1 2 d 2 2 . . . dn 2 Compute matrix A respectively, B, C and D; Minimum threshold e is provided with in storer;
(7-4) as A+B+C=D and in A data have 82%≤e at least and in D, data have 82%≤e at least time, the solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe is all opened, in air chamber bottom, helium is filled with by draft tube, to MQ-2 sensor, MQ-135 sensor and SO 2 sensor cleaning 10 to 20 minutes, after cleaning, the solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe all cuts out, and proceeds to step (6-2);
Otherwise, proceed to step (7-1).
Step (7-2) to (7-4) is the trimming process to MQ-2 sensor, MQ-135 sensor and SO 2 sensor, only have and meet A+B+C=D and in A, data have 82%≤e at least and in D, data have the MQ-2 sensor of the correcting condition of 82%≤e, MQ-135 sensor and SO 2 sensor at least just for detecting gas to be detected, otherwise need repetition trimming process, thus improve the precision of sensor detection.
As preferably, the computation process of described output signal-to-noise ratio SNR comprises the steps:
The computation process of described output signal-to-noise ratio SNR comprises the steps:
Signal (t) is inputted one deck accidental resonance model
in;
Wherein, V (x, t, α) is potential function, the movement locus that x (t) is Brownian Particles, and t is run duration, and α is particle transient motion acceleration, D 2for external noise intensity, N (t) grasps noise in being, for periodic sinusoidal signal, A 1be signal amplitude, f is signal frequency, for phase place; A, b are the constant of setting; If
Controller calculates the first order derivative of V (x, t, α) for x, second derivative and three order derivatives, and makes equation equal 0, obtains two layers of accidental resonance model:
Setting noise intensity D 2=0, signal (t)=0, N (t)=0; Calculate A 1critical value be
By A 1critical value substitute in one deck accidental resonance model, and set X 0(t)=0, sn 0=0, with quadravalence jade for asking rain Ge Kuta Algorithm for Solving one deck accidental resonance model, obtain
x m 1 ( t ) = x m ( t ) + 1 / 6 [ ( k 1 ) m + ( 2 - 2 ) ( k 2 ) m + ( 2 + 2 ) ( k 3 ) m + ( k 4 ) m ] ,
M=0,1 ..., N-1; And calculate:
(k 1) m=4(aαx m-1(t) 2-bαx m-1(t) 3+sn m-1(t))
( k 2 ) m = 4 [ a ( αx m - 1 ( t ) + ( k 1 ) m - 1 3 ) - b ( αx m - 1 ( t ) + ( k 1 ) m - 1 3 ) 3 + sn m - 1 ]
( k 3 ) m = 4 [ a ( αx m - 1 ( t ) + ( k 2 ) m - 1 3 ) - b ( αx m - 1 ( t ) + 2 - 1 3 ( k 1 ) m - 1 + 2 - 2 3 ( k 2 ) m - 1 ) 3 + sn m + 1 ]
( k 4 ) n = 4 [ a ( 3 αx m - 1 ( t ) + ( k 3 ) m - 1 ) - b ( αx m - 1 ( t ) - 2 3 ( k 2 ) m - 1 + 2 + 2 3 ( k 3 ) m - 1 ) 3 + sn m + 1 ]
Wherein, x mt m order derivative that () is x (t), sn m-1the value of m-1 order derivative at t=0 place of S (t), sn m+1the m+1 order derivative being S (t), in the value at t=0 place, obtains x 1(t), x 2(t) ..., x m+1the value of (t);
Controller is to x 1(t), x 2(t) ..., x m+1t () carries out integration, obtain x (t), and obtains x (t) produces accidental resonance moment position x in the double-deck stochastic system of one deck accidental resonance model and two layers of accidental resonance model composition 1value and x 1corresponding resonance moment t 1, optimum transient motion acceleration alpha 1, and and t 1and α 1corresponding noise D 1, D 1for D 2in a value;
Controller utilizes formula S N R = 2 ( ΔU 2 4 a 3 / 27 b D 1 ) 3 e - ( Δ U ) 3 / D 1 2 Calculate the signal to noise ratio snr that double-deck stochastic resonance system exports; Wherein, Δ U=a 2/ 4b.
As preferably, controller calculates and obtains the averaged amplitude value SS of signal (t) in testing process, described A 1≤ 0.47SS, the 9.3SS≤D in one deck accidental resonance model and two layers of accidental resonance model 2≤ 19.5SS; A and b all≤SS.
To A 1, D 2with the restriction of a and b span, guarantee that one deck accidental resonance model and two layers of accidental resonance model have good sensitivity, thus make the signal to noise ratio snr of output more accurate.
As preferably, sulfur dioxide concentration forecast model is sulfur dioxide concentration W=3.7+0.06 × SNR.
Therefore, the present invention has following beneficial effect: (1) is highly sensitive, good stability and the response time short, to sulphuric dioxide, there is good selectivity, the trace sulfur dioxide gas that concentration is lower can be detected, thus effective guarantee people are healthy; (2) simple to operate, testing cost is low.
Accompanying drawing explanation
Fig. 1 is a kind of theory diagram of the present invention;
Fig. 2 is a kind of cut-open view of air chamber of the present invention;
Fig. 3 is a kind of vertical view of sulphuric dioxide pick-up unit in experimental situation of the present invention;
Fig. 4 is a kind of structural representation of web joint of the present invention;
Fig. 5 is a kind of cross-sectional structure schematic diagram of track of the present invention;
Fig. 6 is a kind of vertical view of track of the present invention;
Fig. 7 is a kind of process flow diagram of embodiments of the invention.
In figure: controller 1, base plate 2, air chamber 3, bracing frame 4, guide frame 5, cross lead screw 6, fan 7, gas sensitization film 8, wire netting 9, horizontal baffle 10, supporting plate 11, track 12, detection head 13, first motor 14, web joint 15, second motor 16, solenoid valve 17, exhaust gas processing device 18, MQ-2 sensor 20, MQ-135 sensor 21, SO 2 sensor 22, draft tube 23, escape pipe 24, storer 25, substrate 121, groove 122, gear 123, coupling shaft 124, first baffle plate 125, second baffle 126, guide chute 127, outrigger shaft 128, U-shaped frame 41, L shape frame 42, crossbeam 51, through hole 151, screw hole 152, ball 129, ultrasonic generator 26, ultrasonic receiver 27, flowmeter 28.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment is as shown in Figure 1 and Figure 2 sulphuric dioxide pick-up unit in a kind of experimental situation, comprise controller 1, storer 25, base plate 2, be located at air chamber 3, exhaust gas processing device 18 and bracing frame 4 that xsect on base plate is rectangular, be located at the guide frame 5 on bracing frame and cross lead screw 6;
As shown in Figure 2, air chamber inwall top is provided with frequency-adjustable ultrasonic generator 26 and for 5 fans 7 to canyon, air chamber madial wall is provided with 2 layers of gas sensitization film 8 from top to bottom successively, for supporting the wire netting 9 be made up of heating wire of gas sensitization film, be positioned at wire netting bottom and air chamber be divided into upper and lower two-part horizontal baffle 10, air chamber inner bottom part is provided with ultrasonic receiver 27, supporting plate 11, detection head 13 and the track 12 along splint upper surface Spiral distribution, detection head is provided with MQ-2 sensor 20, MQ-135 sensor 21 and SO 2 sensor 22, gas sensitization film is provided with 5 through holes, the air chamber inwall corresponding with gas sensitization film location is provided with 8 air guide vertical slots,
As shown in Figure 3, cross lead screw one end is connected with the rotating shaft of the first motor 14 be located on bracing frame, air chamber is provided with the opening for inserting horizontal baffle, horizontal baffle outer end is provided with web joint 15, detection head bottom is provided with the second motor 16 for driving detection head orbital motion, web joint is connected with wire rod thread, and web joint and guide frame are slidably connected, and the air chamber being positioned at horizontal baffle upper and lower is respectively equipped with one group of draft tube 23 and escape pipe 24; Draft tube and escape pipe are equipped with solenoid valve 17; Hermetically-sealed construction is provided with between opening and horizontal baffle; Exhaust gas processing device is connected with the escape pipe on air chamber top; The draft tube on horizontal baffle top is provided with flowmeter 28;
As shown in Figure 1, controller is electrically connected with frequency-adjustable ultrasonic generator, ultrasonic receiver, flowmeter, storer, each electric fan, each solenoid valve, wire netting, the first motor, the second motor, MQ-2 sensor, MQ-135 sensor and SO 2 sensor respectively.
As shown in Figure 5, Figure 6, track comprises substrate 121, is located at two of upper surface of base plate spaced grooves 122, and groove floor is provided with the tooth bar arranged at equal intervals; Be provided with bottom detection head two with the gear 123 of fit depressions; The rotating shaft of the second motor is connected with the coupling shaft 124 be located between two gears.
Substrate is provided with the first baffle plate 125, the second baffle 126 relative with the first baffle plate; First baffle plate, second baffle are provided with corresponding guide chute 127; The coupling shaft two ends of gear are provided with the outrigger shaft 128 of guide chute for inserting the first baffle plate, second baffle; Detection head lower surface is provided with the multiple balls 129 with the first baffle plate, second baffle upper surface Structure deformation.
As shown in Figure 3, bracing frame comprises the U-shaped frame 41 that Open Side Down, is located at the L shape frame 42 of air chamber front and rear; Guide frame is be located at two crossbeams 51 between U-shaped frame and two L shape framves; As shown in Figure 4, web joint is rectangular, and web joint bottom is provided with for 2 through holes 151 through two crossbeams, and web joint top is provided with the screw hole 152 for coordinating with cross lead screw.
Be provided with multiple cavity spaced apart in gas sensitization film, in cavity, be provided with the carbon nano-tube of stretching out outside gas sensitization film upper and lower surface.Exhaust gas processing device is spirit lamp.
As shown in Figure 7, in a kind of experimental situation, the detection method of sulphuric dioxide pick-up unit, comprises the steps:
Step 100, sensor cleaning and correction
Step 110, sensor cleans
The solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe is all opened, and is filled with helium, cleans 10 minutes to MQ-2 sensor, MQ-135 sensor and SO 2 sensor by draft tube in air chamber bottom;
Step 120, sensor calibration
Be filled with to air chamber bottom the laboratory air that known sulfur dioxide concentration is S, the laboratory air that exhaust gas processing device process exports from escape pipe by draft tube; The flow of flowmeter testing laboratory gas, the laboratory air that exhaust gas processing device process exports from escape pipe; Each gas sensitization film adsorbed gas, when the flow of laboratory air reaches 10 liters, controller controls the closed electromagnetic valve on the draft tube on air chamber top and escape pipe;
Controller passes through the second driven by motor detection head along rail moving, MQ-2 sensor, MQ-135 sensor and SO 2 sensor detect gas signal, controller receives detection signal S1 (t) of SO 2 sensor, detection signal S2 (t) of MQ-2 sensor, detection signal S3 (t) of MQ-135 sensor;
Step 130, n=20 the sample value S11 be spacedly distributed of S1 (t) chosen by controller, S12, ..., S1n, chooses n the sample value S21 be spacedly distributed of S2 (t), S22, ..., S2n, chooses n the sample value S31 be spacedly distributed of S3 (t), S32, ..., S3n;
Utilize formula
Di 2=(S1i-S) 2+ (S2i-S) 2+ (S3i-S) 2, i=1,2 ..., n, calculated difference distance di 2;
Utilize following formula A = ( S 11 - S ) 2 ( S 12 - S ) 2 . . . ( S 1 n - S ) 2 , B = ( S 21 - S ) 2 ( S 22 - S ) 2 . . . ( S 2 n - S ) 2 , C = ( S 31 - S ) 2 ( S 32 - S ) 2 . . . ( S 3 n - S ) 2 , D = d 1 2 d 2 2 . . . dn 2 Compute matrix A respectively, B, C and D; Minimum threshold e is provided with in storer;
Step 140, as A+B+C=D and in A every item number according to have 82%≤e at least and in D, every item number certificate has 82%≤e at least time, the solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe is all opened, in air chamber bottom, helium is filled with by draft tube, 10 minutes are cleaned to MQ-2 sensor, MQ-135 sensor and SO 2 sensor, proceeds to step 200;
Otherwise, proceed to step 110;
Step 200, the adsorbed gas of gas sensitization film
The solenoid valve that controller controls on the draft tube on air chamber top and escape pipe is opened, laboratory air to be detected is filled with to air chamber by draft tube, the flow of flowmeter testing laboratory gas, the laboratory air that spirit lamp burning exports from escape pipe, removes harmful gas from having; Each gas sensitization film adsorbed gas, when the flow of laboratory air reaches L, controller controls the closed electromagnetic valve on the draft tube on air chamber top and escape pipe;
Step 300, takes out boiling water flat partition board
Controller controls the first driven by motor cross lead screw and rotates, and cross lead screw drives horizontal baffle to move horizontally outside air chamber by web joint, and when horizontal baffle the inner being moved to contact with opening position, controller controls the first motor and quits work;
Step 400, vibrations and heated air sensitive membrane, and the gas that gas sensitization film discharges is blowed to air chamber bottom
Controller controlled frequency is adjustable, and ultrasonic generator sends ultrasound wave, ultrasonic receiver receives ultrasound wave, controller controlled frequency is adjustable, and ultrasonic generator sends hyperacousticly increases frequency gradually from 5Hz and increase, until when the amplitude of ultrasonic making ultrasonic receiver receive is maximum, controller controlled frequency is adjustable, and hyperacoustic frequency that ultrasonic generator sends keeps stable;
Ultrasound wave drives the vibrations of gas sensitization film, and controller controls wire netting energising, and wire netting is the heating of gas sensitization film, and controller controls each electric fan work, and the gas of gas sensitization film absorption enters air chamber bottom; After 5 to 8 minutes, controller controls wire netting power-off, and each electric fan quits work, and frequency-adjustable ultrasonic generator and ultrasonic receiver quit work;
Step 500, closed horizontal baffle
Controller controls the first driven by motor cross lead screw and rotates, and cross lead screw drives horizontal baffle to move horizontally in air chamber by web joint, and when horizontal baffle outer end being moved to contact with opening position to contact, controller controls the first motor and quits work;
Step 600, each sensor detects gas signal and obtains sensor fusion signal
Controller passes through the second driven by motor detection head along rail moving, MQ-2 sensor, MQ-135 sensor and SO 2 sensor detect gas signal, controller receives detection signal S1 (t) of SO 2 sensor, detection signal S2 (t) of MQ-2 sensor, detection signal S3 (t) of MQ-135 sensor; Controller utilizes formula signal (t)=S1 2(t)+(S1 (t)-S2 (t)) 2+ (S1 (t)-S3 (t)) 2calculating sensor merges signal signal (t);
Step 700, calculates and obtains the sulfur dioxide concentration of laboratory air that detects
Be previously stored with accidental resonance model and sulfur dioxide concentration forecast model in storer, inputted by signal (t) in accidental resonance model, controller calculates the output signal-to-noise ratio SNR during resonance of accidental resonance model,
SNR is inputted in sulfur dioxide concentration forecast model sulfur dioxide concentration W=3.7+0.06 × SNR, obtain the sulfur dioxide concentration of the laboratory air be detected.
Sulfur dioxide concentration forecast model utilizes step 100 to detect various concentration known to 700 to be respectively W1, W2 ..., the sulfur dioxide gas of W100, obtains the output signal-to-noise ratio SNR1 corresponding with often kind of sulfur dioxide concentration, SNR2 ..., SNR100; Utilize point (W1, SNR1), (W2, SNR2),, (W100, SNR100) does a little in rectangular coordinate system, obtain the formula of the matched curve of each point, the formula of matched curve is converted, obtains sulfur dioxide concentration forecast model of the present invention.
The computation process of described output signal-to-noise ratio SNR comprises the steps:
Signal (t) is inputted one deck accidental resonance model
in;
Wherein, V (x, t, α) is potential function, the movement locus that x (t) is Brownian Particles, and t is run duration, and α is particle transient motion acceleration, D 2for external noise intensity, N (t) grasps noise in being, for periodic sinusoidal signal, A 1be signal amplitude, f is signal frequency, for phase place; A, b are the constant of setting; If
Wherein, controller calculates and obtains the averaged amplitude value SS of signal (t) in testing process, described A 1≤ 0.47SS, the 9.3SS≤D in one deck accidental resonance model and two layers of accidental resonance model 2≤ 19.5SS; A and b all≤SS.
Controller calculates the first order derivative of V (x, t, α) for x, second derivative and three order derivatives, and makes equation equal 0, obtains two layers of accidental resonance model:
Setting noise intensity D 2=0, signal (t)=0, N (t)=0; Calculate A 1critical value be
By A 1critical value substitute in one deck accidental resonance model, and set X 0(t)=0, sn 0=0, with quadravalence jade for asking rain Ge Kuta Algorithm for Solving one deck accidental resonance model, obtain
x m 1 ( t ) = x m ( t ) + 1 / 6 [ ( k 1 ) m + ( 2 - 2 ) ( k 2 ) m + ( 2 + 2 ) ( k 3 ) m + ( k 4 ) m ] ,
M=0,1 ..., N-1; And calculate:
(k 1) m=4(aαx m-1(t) 2-bαx m-1(t) 3+sn m-1(t))
( k 2 ) m = 4 [ a ( αx m - 1 ( t ) + ( k 1 ) m - 1 3 ) - b ( αx m - 1 ( t ) + ( k 1 ) m - 1 3 ) 3 + sn m - 1 ]
( k 3 ) m = 4 [ a ( αx m - 1 ( t ) + ( k 2 ) m - 1 3 ) - b ( αx m - 1 ( t ) + 2 - 1 3 ( k 1 ) m - 1 + 2 - 2 3 ( k 2 ) m - 1 ) 3 + sn m + 1 ]
( k 4 ) n = 4 [ a ( 3 αx m - 1 ( t ) + ( k 3 ) m - 1 ) - b ( αx m - 1 ( t ) - 2 3 ( k 2 ) m - 1 + 2 + 2 3 ( k 3 ) m - 1 ) 3 + sn m + 1 ]
Wherein, x mt m order derivative that () is x (t), sn m-1the value of m-1 order derivative at t=0 place of S (t), sn m+1the m+1 order derivative being S (t), in the value at t=0 place, obtains x 1(t), x 2(t) ..., x m+1the value of (t);
Controller is to x 1(t), x 2(t) ..., x m+1t () carries out integration, obtain x (t), and obtains x (t) produces accidental resonance moment position x in the double-deck stochastic system of one deck accidental resonance model and two layers of accidental resonance model composition 1value and x 1corresponding resonance moment t 1, optimum transient motion acceleration alpha 1, and and t 1and α 1corresponding noise D 1, D 1for D 2in a value; D 2with a function of 0.01 loop cycle stepping in [0,1] scope, D 2value and time correlation, be aware of t 1moment, D 1just determine.
Controller utilizes formula S N R = 2 ( ΔU 2 4 a 3 / 27 b D 1 ) 3 e - ( Δ U ) 3 / D 1 2 Calculate the signal to noise ratio snr that double-deck stochastic resonance system exports; Wherein, Δ U=a 2/ 4b.
Should be understood that the present embodiment is only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.

Claims (10)

1. sulphuric dioxide pick-up unit in an experimental situation, it is characterized in that, comprise controller (1), storer (25), base plate (2), be located at air chamber (3), exhaust gas processing device (18) and bracing frame (4) that xsect on base plate is rectangular, be located at the guide frame (5) on bracing frame and cross lead screw (6);
Described air chamber inwall top is provided with frequency-adjustable ultrasonic generator (26) and for several fans (7) to canyon, air chamber madial wall is provided with at least 2 layers of gas sensitization film (8) from top to bottom successively, for supporting the wire netting (9) be made up of heating wire of gas sensitization film, be positioned at wire netting bottom and air chamber be divided into upper and lower two-part horizontal baffle (10), air chamber inner bottom part is provided with ultrasonic receiver (27), supporting plate (11), detection head (13) and the track (12) along splint upper surface Spiral distribution, detection head is provided with MQ-2 sensor (20), MQ-135 sensor (21) and SO 2 sensor (22), gas sensitization film is provided with several through holes, and the air chamber inwall corresponding with gas sensitization film location is provided with some air guide vertical slots,
Cross lead screw one end is connected with the rotating shaft of the first motor (14) be located on bracing frame, described air chamber is provided with the opening for inserting horizontal baffle, horizontal baffle outer end is provided with web joint (15), detection head bottom is provided with the second motor (16) for driving detection head orbital motion, web joint is connected with wire rod thread, web joint and guide frame are slidably connected, and the air chamber being positioned at horizontal baffle upper and lower is respectively equipped with one group of draft tube (23) and escape pipe (24); Draft tube and escape pipe are equipped with solenoid valve (17); Hermetically-sealed construction is provided with between opening and horizontal baffle; Exhaust gas processing device is connected with the escape pipe on air chamber top; The draft tube on horizontal baffle top is provided with flowmeter (28);
Controller is electrically connected with frequency-adjustable ultrasonic generator, ultrasonic receiver, flowmeter, storer, each electric fan, each solenoid valve, wire netting, the first motor, the second motor, MQ-2 sensor, MQ-135 sensor and SO 2 sensor respectively.
2. sulphuric dioxide pick-up unit in experimental situation according to claim 1, it is characterized in that, described track comprises substrate (121), is located at two spaced grooves (122) of upper surface of base plate, and described groove floor is provided with the tooth bar arranged at equal intervals; Be provided with bottom described detection head two with the gear (123) of fit depressions; The rotating shaft of described second motor is connected with the coupling shaft be located between two gears (124).
3. sulphuric dioxide pick-up unit in experimental situation according to claim 2, is characterized in that, described substrate is provided with the first baffle plate (125), the second baffle (126) relative with the first baffle plate; First baffle plate, second baffle are provided with corresponding guide chute (127); The coupling shaft two ends of described gear are provided with the outrigger shaft (128) of guide chute for inserting the first baffle plate, second baffle; Detection head lower surface is provided with several balls (129) with the first baffle plate, second baffle upper surface Structure deformation.
4. sulphuric dioxide pick-up unit in experimental situation according to claim 1, is characterized in that, support frame as described above comprises the U-shaped frame (41) that Open Side Down, is located at the L shape frame (42) of air chamber front and rear; Described guide frame is two crossbeams (51) be located between U-shaped frame and two L shape framves; Described web joint is rectangular, and web joint bottom is provided with for 2 through holes (151) through two crossbeams, and web joint top is provided with the screw hole (152) for coordinating with cross lead screw.
5. sulphuric dioxide pick-up unit in the experimental situation according to claim 1 or 2 or 3 or 4, is characterized in that, be provided with the cavity that several are spaced apart in gas sensitization film, be provided with the carbon nano-tube of stretching out outside gas sensitization film upper and lower surface in cavity; Exhaust gas processing device is spirit lamp.
6. be applicable to a detection method for sulphuric dioxide pick-up unit in experimental situation according to claim 1, it is characterized in that, comprise the steps:
(6-1) solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe is all opened, in air chamber bottom, helium is filled with by draft tube, to MQ-2 sensor, MQ-135 sensor and SO 2 sensor cleaning 10 to 20 minutes, after cleaning, the solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe all cuts out;
(6-2) solenoid valve that controller controls on the draft tube on air chamber top and escape pipe is opened, laboratory air to be detected is filled with to air chamber by draft tube, the flow of flowmeter testing laboratory gas, the laboratory air that exhaust gas processing device process exports from escape pipe; Each gas sensitization film adsorbed gas, when the flow of laboratory air reaches L, controller controls the closed electromagnetic valve on the draft tube on air chamber top and escape pipe;
(6-3) controller controls the first driven by motor cross lead screw and rotates, and cross lead screw drives horizontal baffle to move horizontally outside air chamber by web joint, and when horizontal baffle the inner being moved to contact with opening position, controller controls the first motor and quits work;
(6-4) the adjustable ultrasonic generator of controller controlled frequency sends ultrasound wave, ultrasonic receiver receives ultrasound wave, controller controlled frequency is adjustable, and ultrasonic generator sends hyperacousticly increases frequency gradually from 5Hz and increase, until when the amplitude of ultrasonic making ultrasonic receiver receive is maximum, controller controlled frequency is adjustable, and hyperacoustic frequency that ultrasonic generator sends keeps stable;
Ultrasound wave drives the vibrations of gas sensitization film, and controller controls wire netting energising, and wire netting is the heating of gas sensitization film, and controller controls each electric fan work, and the gas of gas sensitization film absorption enters air chamber bottom; After 5 to 8 minutes, controller controls wire netting power-off, and each electric fan quits work, and frequency-adjustable ultrasonic generator and ultrasonic receiver quit work;
(6-5) controller controls the first driven by motor cross lead screw rotation, cross lead screw drives horizontal baffle to move horizontally in air chamber by web joint, when horizontal baffle outer end being moved to contact with opening position to contact, controller controls the first motor and quits work;
(6-6) controller passes through the second driven by motor detection head along rail moving, MQ-2 sensor, MQ-135 sensor and SO 2 sensor detect gas signal, controller receives detection signal S1 (t) of SO 2 sensor, detection signal S2 (t) of MQ-2 sensor, detection signal S3 (t) of MQ-135 sensor; Controller utilizes formula signal (t)=S1 2(t)+(S1 (t)-S2 (t)) 2+ (S1 (t)-S3 (t)) 2calculating sensor merges signal signal (t);
(6-7) be previously stored with accidental resonance model and sulfur dioxide concentration forecast model in storer, inputted by signal (t) in accidental resonance model, controller calculates the output signal-to-noise ratio SNR during resonance of accidental resonance model,
SNR is inputted in sulfur dioxide concentration forecast model, obtain the sulfur dioxide concentration of the laboratory air be detected.
7. the detection method of sulphuric dioxide pick-up unit in experimental situation according to claim 1, it is characterized in that, described step (6-1) is replaced by following step:
(7-1) solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe was all opened, and is filled with helium by draft tube in air chamber bottom, to MQ-2 sensor, MQ-135 sensor and SO 2 sensor cleaning 8 to 10 minutes;
(7-2) be filled with to air chamber bottom the laboratory air that known sulfur dioxide concentration is S by draft tube, the laboratory air that exhaust gas processing device process exports from escape pipe; The flow of flowmeter testing laboratory gas, the laboratory air that exhaust gas processing device process exports from escape pipe; Each gas sensitization film adsorbed gas, when the flow of laboratory air reaches L, controller controls the closed electromagnetic valve on the draft tube on air chamber top and escape pipe;
Controller passes through the second driven by motor detection head along rail moving, MQ-2 sensor, MQ-135 sensor and SO 2 sensor detect gas signal, MQ-2 sensor, MQ-135 sensor and SO 2 sensor detect gas signal, controller receives detection signal S1 (t) of SO 2 sensor, detection signal S2 (t) of MQ-2 sensor, detection signal S3 (t) of MQ-135 sensor;
(7-3) n the sample value S11 be spacedly distributed of S1 (t) chosen by controller, S12 ..., S1n, choose n the sample value S21 be spacedly distributed of S2 (t), S22 ..., S2n, choose n the sample value S31 be spacedly distributed of S3 (t), S32 ..., S3n;
Utilize formula
Di 2=(S1i-S) 2+ (S2i-S) 2+ (S3i-S) 2, i=1,2 ..., n, calculated difference distance di 2;
Utilize following formula A = ( S 11 - S ) 2 ( S 12 - S ) 2 · · · ( S 1 n - S ) 2 , B = ( S 21 - S ) 2 ( S 22 - S ) 2 · · · ( S 2 n - S ) 2 , C = ( S 31 - S ) 2 ( S 32 - S ) 2 · · · ( S 3 n - S ) 2 ,
d 1 2 d 2 2 · · · dn 2 Compute matrix A respectively, B, C and D; Minimum threshold e is provided with in storer;
(7-4) as A+B+C=D and in A data have 82%≤e at least and in D, data have 82%≤e at least time, the solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe is all opened, in air chamber bottom, helium is filled with by draft tube, to MQ-2 sensor, MQ-135 sensor and SO 2 sensor cleaning 10 to 20 minutes, after cleaning, the solenoid valve that controller controls on the draft tube of air chamber bottom and escape pipe all cuts out, and proceeds to step (6-2):
Otherwise, proceed to step (7-1).
8. the detection method of sulphuric dioxide pick-up unit in experimental situation according to claim 1, it is characterized in that, the computation process of described output signal-to-noise ratio SNR comprises the steps:
Signal (t) is inputted one deck accidental resonance model
in;
Wherein, V (x, t, α) is potential function, the movement locus that x (t) is Brownian Particles, and t is run duration, and a is particle transient motion acceleration, D 2for external noise intensity, N (t) grasps noise in being, for periodic sinusoidal signal, A 1be signal amplitude, f is signal frequency, for phase place; A, b are the constant of setting; If
Controller calculates the first order derivative of V (x, t, α) for x, second derivative and three order derivatives, and makes equation equal 0, obtains two layers of accidental resonance model:
Setting noise intensity D 2=0, signal (t)=0, N (t)=0; Calculate A 1critical value be
By A 1critical value substitute in one deck accidental resonance model, and set X 0(t)=0, sn 0=0, with quadravalence jade for asking rain Ge Kuta Algorithm for Solving one deck accidental resonance model, obtain
x m 1 ( t ) = x m ( t ) + 1 / 6 [ ( k 1 ) m + ( 2 - 2 ) ( k 2 ) m + ( 2 + 2 ) ( k 3 ) m + ( k 4 ) m ] ,
M=0,1 ..., N-1; And calculate:
( k 1 ) m = 4 ( aαx m - 1 ( t ) 2 - bαx m - 1 ( t ) 3 + sn m - 1 ( t ) )
( k 2 ) m = 4 [ a ( αx m - 1 ( t ) + ( k 1 ) m - 1 3 ) - b ( αx m - 1 ( t ) + ( k 1 ) m - 1 3 ) 3 + sn m - 1 ]
( k 3 ) m = 4 [ a ( αx m - 1 ( t ) + ( k 2 ) m - 1 3 ) - b ( αx m - 1 ( t ) + 2 - 1 3 ( k 1 ) m - 1 + 2 - 2 3 ( k 2 ) m - 1 ) 3 + sn m + 1 ]
( k 4 ) n = 4 [ a ( 3 αx m - 1 ( t ) + ( k 3 ) m - 1 ) - b ( αx m - 1 ( t ) - 2 3 ( k 2 ) m - 1 + 2 + 2 3 ( k 3 ) m - 1 ) 3 + sn m + 1 ]
Wherein, x mt m order derivative that () is x (t), sn m-1the value of m-1 order derivative at t=0 place of S (t), sn m+1the m+1 order derivative being S (t), in the value at t=0 place, obtains x 1(t), x 2(t) ..., x m+1the value of (t);
Controller is to x 1(t), x 2(t) ..., x m+1t () carries out integration, obtain x (t), and obtains x (t) produces accidental resonance moment position x in the double-deck stochastic system of one deck accidental resonance model and two layers of accidental resonance model composition 1value and x 1corresponding resonance moment t 1, optimum transient motion acceleration a 1, and and t 1and a 1corresponding noise D 1, D 1for D 2in a value;
Controller utilizes formula S N R = 2 ( ΔU 2 4 a 3 / 27 b D 1 ) 3 e - ( Δ U ) 3 / D 1 2 Calculate the signal to noise ratio snr that double-deck stochastic resonance system exports; Wherein, Δ U=a 2/ 4b.
9. the detection method of sulphuric dioxide pick-up unit in experimental situation according to claim 8, it is characterized in that, controller calculates and obtains the averaged amplitude value SS of signal (t) in testing process, described A 1≤ 0.47SS, the 9.3SS≤D in one deck accidental resonance model and two layers of accidental resonance model 2≤ 19.5SS; A and b all≤SS.
10. the detection method of sulphuric dioxide pick-up unit in the experimental situation according to claim 6 or 7 or 8 or 9, it is characterized in that, sulfur dioxide concentration forecast model is sulfur dioxide concentration W=3.7+0.06 × SNR.
CN201510595605.4A 2015-09-17 2015-09-17 Device and method for detecting sulfur dioxide in experiment environment Pending CN105527375A (en)

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CN1687765A (en) * 2005-03-31 2005-10-26 浙江大学 Portable gas detector
CN103323359A (en) * 2013-06-09 2013-09-25 青岛大学 Method for detecting low-concentration carbon monoxide gas
JP2015040819A (en) * 2013-08-23 2015-03-02 株式会社Nttドコモ Gas measuring device and gas measuring method
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