CN103808820B - A kind of Freon gas detection alarm device and detection method thereof - Google Patents
A kind of Freon gas detection alarm device and detection method thereof Download PDFInfo
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Abstract
The invention belongs to technical field of analysis and detection, be specifically related to a kind of Freon gas detection alarm device. The invention discloses a kind of Freon gas detection alarm device, it comprises detection analytical system, air-channel system, control system and electric power system, and detection analytical system, air-channel system, control system interconnect, and electric power system is powered to three. Fluorine of the present invention Lyons gas-monitoring alarm has good separating effect, measures the features such as accurate, antijamming capability is strong, reproducible, to F-1301, F-11, F-12 and F-22 can qualitative analysis again can quantitative analysis, the know-why advanced person who adopts, reasonable in design, working service is convenient, and standardization, generalization degree are high.
Description
Technical field
The invention belongs to technical field of analysis and detection, be specifically related to a kind of Freon gas detection alarm device and detection method thereof.
Background technology
Freon is also referred to as fluorochlorohydrocarbon (CFCs), be several fluorine chloromethanes and the fluorine chloric ethane of being manufactured by the mankind completely, modal is fluoro trichloromethane (F-11), dichlorodifluoromethane (F-12), trifluorotrichloroethane (F-113), BTM (F-1301). Freon is at room temperature gas or volatile liquid, stable chemical nature, and tool combustibility and utmost point hypotoxicity, be not widely used in cold-producing medium, extinguishing chemical, cleaning agent and aerosol propellant etc. Quite stable after freon is discharged in atmosphere, almost non-degradable in troposphere, make their concentration in the atmosphere of troposphere sharply increase. Freon is chemically inactive gas in the atmosphere of troposphere, but in stratosphere, is subject to UV-irradiation, and photodissociation discharges chlorine atom, and ozone reaction generates C10 molecule, circulation catalysis loss ozone. In addition still very strong greenhouse gases of freon. According to Montreal Convention and complementary treaty thereof, the production of freon all stops, does not also stop but using.
At present, the equipment of domestic monitoring freon is as refrigrant leakage survey meter, and generally taking semiconductor as probe, analyzing total freon, can not be qualitative; Use in multiple freon (as cold-producing medium, extinguishing chemical) environment at some, this class refrigrant leakage survey meter can not that freon leakage of real-time report, needs the follow-up program of investigating one by one, takes time and effort; External freon monitoring mostly adopts gas chromatography or gas-chromatography-electron capture to detect (GC-ECD) method, and gas-chromatography instrument body is long-pending heavy, expensive and be not suitable for portable inspectiont, simultaneously in gas chromatography, chromatographic column often adopts capillary column and Bio-sil packed column, but because the general freon that detects in atmospheric sample is of a great variety, the chromatographic column product on market to detecting F-1301, F-12 compared with separating in the short period, F-11 effect is all undesirable.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of portable Freon gas detection alarm device and detection method thereof, to overcome the deficiencies in the prior art.
The invention discloses a kind of Freon gas detection alarm device, it comprises detection analytical system, air-channel system, control system and electric power system, and detection analytical system, air-channel system, control system interconnect, and electric power system is powered to three; It is characterized in that described air-channel system is divided into sample gas gas circuit and carrier gas gas circuit, wherein said sample gas gas circuit is that sample gas enters threeway by air pump, one tunnel enters described halogen sensor through vapour lock, magnetic valve 1, magnetic valve 2, dehydrogenation pipe, and a road is through vapour lock access ten-way valve; Described carrier gas gas circuit be carrier gas after electronic pressure controller voltage stabilizing, enter threeway, a road through vapour lock access ten-way valve for analyzing, a road through vapour lock access ten-way valve for carrier gas blowback; Described detection analytical system is made up of electron capture detector unit and halogen sensor unit, wherein said electron capture detector unit comprises that electron capture detector comprises quantity tube, chromatogram pre-column, chromatogram principal post and electron capture detector, described quantity tube, chromatogram pre-column access ten-way valve by tracheae respectively with chromatogram principal post and are connected, and chromatogram principal post accesses electron capture detector by tracheae; Described chromatogram principal post comprises carrier, column jecket and fixer, described column jecket length >=1600mm; Described carrier is 80～100 order DG-2; Described fixer is ApiezonL fixer, and it is coated with stain amount is 3.2%-4.0%.
In some preferred embodiments, described freon chromatogram column length is preferably 1600mm;
In some preferred embodiments, described ApiezonL painting stain amount is 3.2%;
In some preferred embodiments, described column jecket is stainless steel tube, its external diameter φ 3mm, wall thickness 0.5mm.
In some preferred embodiments, described control system is mainly made up of ARM, MCU, data acquisition, pump valve control, communication, is integrated on surface-mounted integrated circuit; Described ARM adopts the EP9315 processor of the ARM920T kernel of 200MHz dominant frequency; Described MCU is 8 single-chip microcomputer PIC16F886, and it is communicated by letter with ARM by RS-232 interface; Described data acquisition completes analog acquisition by AD7794 chip, and it is communicated by letter with MCU by SPI interface; Described pump valve control is controlled by MCU, by high power valve TIP122 electric current of make-and-break, according to the requirement of gas circuit sequential, dynamically controls; Described communication is completed by MCU, ARM, and MCU uploading data is to ARM, and ARM connects ten-way valve and electronic pressure controller, controls ten-way valve switch by ARM, sets the force value of electronic pressure controller.
The detection method of described Freon gas detection alarm device, comprises the following steps:
Carrier gas is connected on nitrogen cylinder pressure-reducing valve, and opening nitrogen cylinder main valve and regulating pressure-reducing valve dividing potential drop table output pressure is 0.3Mpa;
Switch on power, instrument starts automatically, enters preheat mode, enters monitoring state after half an hour;
Fluorine of the present invention Lyons gas-monitoring alarm adopts dual detector design, there is good separating effect, measure the features such as accurate, antijamming capability is strong, reproducible, to F-1301, F-11, F-12 and F-22 can qualitative analysis again can quantitative analysis, the know-why advanced person who adopts, reasonable in design, working service is convenient, and standardization, generalization degree are high; Develop voluntarily chromatography column, utilized multiple fluorine Lyons difference of distribution coefficient or adsorption capacity in chromatography column to be isolated, realized multiple fluorine Lyons is differentiated; Adopt the two splitter designs of chromatogram pre-column and chromatogram principal post, ensured that data are accurate, extended the service life of chromatography column; Wiring board is taked high insulation resistance design, has got rid of components and parts noise jamming, takes micro-gallon technology, has realized receiving and has pacified the micro-gallon of level, the sensitivity that has improved instrument; Adopt automatic zero set technology, adjust in real time baseline, instrument baseline value is stable, and drift in time, does not have Accumulated deviation, has reduced measure error, has improved stability of instrument, has ensured the reappearance of data.
Brief description of the drawings
Fig. 1 is structural representation of the present invention.
Fig. 2 is process of gas path figure of the present invention.
Fig. 3 is circuit control system block diagram of the present invention.
Fig. 4 is software flow pattern of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further elaborated, should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described. In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalences fall within the application's appended claims limited range equally.
Term of the present invention " electron capture detector ", " ECD detector ", " ECD " and " electronic detectors " are synonym technical term, can be equal to replacement.
The preparation of embodiment 1 freon chromatographic column
The making flow process of chromatographic column is specifically implemented
(1) material: stainless steel tube (external diameterWall thickness 0.5mm), DG-2 (80-100 order), ApiezonL(apiczon-L), acetone
(2) gc column tube system is done: intercept external diameterMono-of the stainless steel tube length 1600mm of wall thickness 0.5mm, fracture is concordant shaped, without burr, without closing up or enlarging, by helically wound materials in the tube gc column tube chromatographic column internal diameter
(3) clean: chromatographic column body is immersed in industrial cleaners and pure water mixed liquor, cleans about half an hour with ultrasonic cleaner, then clean 40 minutes with supersonic wave cleaning machine, with putting into again oven for drying after pure water drip washing totally. Blow off impurity in tube wall with compressed air.
(4) chromatograph packing material processing: DG-2 (80-100 order), through the processing of sieving, takes 10g; Acetone 20ml, takes Apiezon L, is dissolved in acetone, has stirred; Dissolve completely, pour 10gDG-2 into beaker, stir and make acetone cover DG-2 completely; In ventilating kitchen, dry for subsequent use.
(5) chromatography column: a little silica wool is filled in to chromatographic column body, fill in chromatographic column body with the copper wire net volume (rolling tightly) that is rolled into bar-shaped length 6～8mm as far as possible again, this end is connected glass filter ball with plastic tube, connect again vavuum pump, the other end connects funnel with transit joint, start vavuum pump, filler (is coated with to the DG-2 of stain, must be through the processing of sieving) add funnel to suck in column jecket, now must constantly strike the column jecket each several part that shakes with oscillator, filler is evenly filled up in pipe as far as possible, then fill in the mouth of pipe with a little silica wool, use again steel wire net volume (long 6～8mm) to fill in the mouth of pipe, attention copper wire net volume can not exert oneself very much to fill in, in case crush the carrier of column jecket oral area.
(6) aging: populated chromatographic column is put into baking oven, logical nitrogen in post, nitrogen pressure is set 0.2～0.25MPa, and oven temperature is set 150 DEG C, and ageing time 7～8 hours is closed nitrogen after naturally cooling.
Chromatographic column manufacturing conditions and result
Monitoring fluorine Lyons analytical cycle is more short more favourable, adopts 80～100 order DG-2(silica gel) add 3.2%ApiezonL(macromolecule saturated hydrocarbon mixtures) splitter of fixer, the material of splitter is stainless steel tube (external diameterWall thickness 0.5mm), column length 1600mm, 150 DEG C of aging temperatures are the optimal selections of chromatographic column.
The separate authentication test of embodiment 2 freon chromatographic columns
Analysis condition: ECD detector, 70 DEG C of column temperatures, carrier gas is High Purity Nitrogen, presses as 0.2MPa before post;
Standard Gases: F-1301(24ppm), F-12(52ppm), F-11(25ppm) mixed mark;
Open instrument power source, before High Purity Nitrogen post, press and be adjusted to 0.2MPa, column temperature is set as to 70 DEG C, the constant rear stable 2h of column temperature, enters Standard Gases analysis.
Separating effect:
| Signal peak | F-1301 | F-12 | F-11 | |
| Appearance time (s) | 73 | 95 | 232 | |
| Peak area | 1016 | 351 | 284 | 2115 |
The prepared post of embodiment 1 and commercially available post, check Standard Gases, and result is as following table:
Embodiment 3 Freon gas detection alarm devices
A kind of Freon gas detection alarm device, it comprises detection analytical system, air-channel system, control system and electric power system 320mm × 410mm × 220 (L × H × W), detection analytical system, air-channel system, control system interconnect, and electric power system is powered to three; (Fig. 1)
3.1 air-channel system designs
Air-channel system is divided into 2 tunnels, and 1 tunnel is sample gas, and another 1 tunnel is carrier gas (High Purity Nitrogen), is mainly made up of sampling pump, threeway, sample vapour lock, nitrogen vapour lock, pressure controller, ten-way valve etc. Air-channel system flow chart is shown in Fig. 2.
A, sample gas enter threeway piece by air pump, and a road enters halogen sensor through vapour lock, magnetic valve and dehydrogenation pipe, the Token Holder of this sensor the concentration information of F22 in sample gas; One tunnel access ten-way valve.
Note: sample gas relies on the switching timesharing of synchronizeing of magnetic valve 1 and magnetic valve 2 to enter dehydrogenation pipe with nitrogen blowback, and magnetic valve is two-position three-way valve, simultaneously action.
B, carrier gas (being generally High Purity Nitrogen), after pressure controller voltage stabilizing, enter threeway piece, and a road is for analyzing, and a road is for blowback.
C, when ten-way valve is in figure when dotted line position: be sampling process, sample gas is full of quantity tube.
1) sample gas → ten-way valve → quantity tube → sample gas emptying 1
2) nitrogen analysis → ten-way valve → chromatogram pre-column → ten-way valve → nitrogen blowback → magnetic valve 2
3) nitrogen blowback → ten-way valve → chromatogram principal post → ECD → analysis emptying
When ten-way valve is in figure when solid line position: be analytic process, the direct emptying of sample gas.
1) sample gas → ten-way valve → sample emptying 1
2) nitrogen analysis → ten-way valve → quantity tube → ten-way valve → chromatogram pre-column → ten-way valve → chromatogram principal post → ECD → analysis emptying
3) nitrogen blowback → ten-way valve → nitrogen blowback → magnetic valve 2
Chromatography column is the basis that instrument is distinguished multiple fluorine Lyons, and the product on market is all undesirable to the separating effect in several fluorine Lyons, must develop voluntarily the chromatography column that can meet the demands. Development group is through repeatedly proving, testing, final choice 80～100 order DG-2(silica gel) as carrier, add ApiezonL(macromolecule saturated hydrocarbon mixtures) fixer, make moulding by dipping, filling, the technique such as aging, by effective separation of signal peak, F-1301, F-12, F-11. Consider that sample gas kind is many, complicated component, the two splitters of chromatogram pre-column and chromatogram principal post are designed, macromolecule, high boiling organic matter are stayed in pre-column, prevent that it from entering chromatogram principal post and polluting principal post, impurity is removed in carrier gas blowback, ensure that data are accurate, extended the service life of chromatography column.
The design of 3.2 control systems
Control system mainly contains ARM host computer, MCU(microprogram control unit), data acquisition, pump valve control, communication, baseline automatic zero set composition, be integrated in wiring board. As shown in Figure 3.
1. ARM host computer
Host computer function is completed by ARM system, ARM adopts the EP9315 processor of the ARM920T kernel of 200MHz dominant frequency, this system operation WinCE small-scale operating system, low-power consumption, high-performance, possess 32MFLASH and 32MSDRAM memory, USB, 100M Ethernet interface, serial line interface, TFT interface etc. For storage Large Volume Data, in system, load especially the CF card memory of a slice 4G. The man-machine interface of instrument completes on ARM, slave computer (MCU) by serial line interface by data upload to ARM system, ARM system is through mode padding data storehouses such as computings, curve plotting, in order to inquiry.
2. MCU part
Control and testing board MCU adopts 8 single-chip microcomputer PIC16F886 of Microchip company, and this single-chip microcomputer is undertaken the task that observing and controlling and information are uploaded.
Analog acquisition---ECD signal, calorstat temperature, case internal gas pressure, halogen transducing signal.
Switching value control---sample pump, halogen valve, fan, ten-way valve, heater.
Information is uploaded---collection data after treatment are uploaded to ARM system in real time.
3. data acquisition
This instrument mainly gathers 4 tunnel analog quantitys, respectively ECD signal, calorstat temperature, case internal gas pressure, halogen transducing signal, these analog quantitys complete by the AD7794 chip of ANALOGDEVICE company, this chip is 24 6 passage fully differential A/D converters, gain is good with noiseproof feature, be applicable to the collection of this circuit analog quantity, this chip is communicated by letter with MCU by SPI interface, and MCU can obtain AD translation data.
4. pump valve control
Sample pump, halogen valve in instrument gas circuit are controlled by MCU, by high power valve TIP122 electric current of make-and-break, according to the requirement of gas circuit sequential, dynamically control.
5. communications portion
Communications portion is completed by MCU, ARM, and MCU uploading data is to ARM, and ARM connects ten-way valve and electronic pressure controller. Control ten-way valve by ARM and switch, set the force value of electronic pressure controller. ARM has a serial ports of outline.
Fluorine Lyons concentration in the technical monitoring air of instrument employing gas-chromatography, gas-chromatography has the parameter of a baseline, and the meaning of this parameter is: when detector is passed through in pure carrier gas, the current value that detector circuit detects, base current value, is referred to as baseline; While passing through detector with the carrier gas of micro-example gas, due to the existence of sample gas, current value change, be exactly on the basis of baseline, there is the characteristic peak of sample, the area at these characteristic peaks or highly represented the concentration of certain composition in sample gas, chromatogram that Here it is goes out peak figure. Baseline value is a most important parameter of the method, and unstability of base line goes out peak just unstable, and concentration calculates that deviation is huge. Therefore, keeping baseline stability is to ensure measurement data basis accurately.
The present invention applies 12 D/A converters, by the control action of MCU, has formed a closed-loop control system, adjusts in real time baseline, the height of steady baseline. Its principle is as follows: MCU detects current baseline value, compare with setting value, gained difference is sent into D/A converter after computing, the electric field strong and weak of the output control electronic detectors of D/A converter, thereby control the size of electric current, reached the object of controlling baseline. Establishment baseline fixed software, is judged the deviation of balance by software, and then controls the increase and decrease of D/A output, till such cyclic process is continued until that final stack result is in the error range of regulation. Through the effect of baseline automatic zero set, this instrument baseline value is more stable, and long-term stability is for being less than 1mV/24h, and not drift in time, there is no Accumulated deviation.
In ECD, finally form can measure be exactly free electron displacement produce weak current, conventionally the magnitude of this current value is that several peaces of receiving are received peace (nA) to tens, detect so little electric current, adopt custom circuit almost cannot reach, in extraneous interference and circuit, the noise of device has just flooded this signal. Circuit of the present invention adopts ultralow bias current operational amplifier, and its bias current is fA(10-15) level, the electric current that flows into this amplifier is extremely low, can not affect the sampling of nA level electric current. In addition, the insulation impedance of wiring board is not high, is generally mega-ohms, tens M Ω left and right, and therefore weak current also can be revealed by wiring board. On circuit, every loop that has tested electric current process, (insulation impedance can reach G Ω level and connect, and welding adopts the mode of joint welding to carry out, and avoids tested electric current to be bypassed as far as possible and reveals all to adopt the binding post of polytetrafluoroethylene (PTFE). The anti-paint brushing of high-quality three for whole circuit board, in protection against the tide, anti-salt fog, the etch-proof while, can also increase effective impedance, improve the precision of electric circuit inspection.
3.3 thermostatic control designs
Instrument insulating box is in-built chromatographic column, relevant gas circuit and electronic detectors, and these devices need to just can be played effectiveness under stationary temperature, therefore need measuring and controlling temp. Whole insulating box is incubated by heat-insulation layer, adopts two heating rods to heat at both direction, guarantees the uniformity of insulating box internal temperature. Temperature control circuit has been realized power line and the isolation of measuring control circuit, has not only ensured temperature-controlled precision but also safe and reliable, and Overtemperature protection circuit and temperature control failure alarm signal are provided simultaneously, guarantees reliability and the security of instrument. Temperature transducer is PT100 type temperature sensor, precision A level (± 0.1 DEG C). Insulating box heater is composed in parallel by two 24V heating rods, and microprogram control unit (MCU) changes by the break-make of controlling high power valve TIP122 the power being added on heating rod, thereby controls degree of heat, reaches temperature control object.
MCU, A/D(analog signal/data signal), a closed-loop system of the common composition of PT100, heater, MCU records PT100 signal (temperature information) by A/D converter, then with desired temperature comparison, drive high power valve, adopt pid algorithm to carry out closed-loop control.
3.4 electric power systems, referring to seeing Fig. 3
The specified 220VAC power supply of instrument, power supply voltage range 85～265VAC, frequency 50 ± 0.1Hz. External 220V power supply is through the military Switching Power Supply power supply of the backward 24V of instrument internal power-supply filter, and this output power of power supply is 200W, uses in order to the circuit that instrument internal is provided.
Heating member in insulating box (chromatogram case), ten-way valve motor, sample pump, halogen valve, fan etc. are directly by 24V Power supply.
Telemetry circuit plate and power inverter plate are also by 24V Power supply, and power supply DC/DC module converts in plate is 5V, the 3.3V, ± power supply such as 15V that on plate, circuit need to use.
The design of 3.5 softwares
The software of fluorine Lyons gas-monitoring alarm is to realize its technical indicator to design with using function. Establishment and the design flow diagram of software are shown in Fig. 4.
Scope of the present invention is not subject to the restriction of described specific embodiments, and described embodiment, only as the single example of illustrating various aspects of the present invention, also comprises method and the component of functional equivalent in the scope of the invention. In fact,, except content as herein described, those skilled in the art can easily grasp multiple improvement of the present invention with reference to description and accompanying drawing above. Within described improvement also falls into the scope of appended claims. Every section of bibliography mentioned above is listed in herein as a reference all in full.
Claims (9)
1. a Freon gas detection alarm device, it comprises detection analytical system, gas circuit systemSystem, control system and electric power system, detect analytical system, air-channel system, control system mutualConnect, electric power system is powered to three; It is characterized in that described air-channel system is divided into sample gas gasRoad and carrier gas gas circuit, wherein said sample gas gas circuit is that sample gas enters threeway by air pump, a roadEnter halogen sensor unit, a road through vapour lock, magnetic valve 1, magnetic valve 2, dehydrogenation pipeThrough vapour lock access ten-way valve; Described carrier gas gas circuit is that carrier gas is through electronic pressure controller voltage stabilizingAfter, entering threeway, a road is through vapour lock access ten-way valve for analyzing, and a road connects through vapour lockEnter ten-way valve for carrier gas blowback; Described detection analytical system by electron capture detector unit andHalogen sensor unit composition, wherein said electron capture detector unit comprises quantity tube, lookSpectrum pre-column, chromatogram principal post and electron capture detector, described quantity tube, chromatogram pre-column and chromatogramPrincipal post accesses ten-way valve by tracheae respectively and connects, and chromatogram principal post accesses electronics by tracheae and catchesObtain detector; Described chromatogram principal post comprises carrier, column jecket and fixer, described column jecket length>=1600mm; Described carrier is 80～100 order DG-2; Described fixer is that ApiezonL is solidDetermine liquid, it is coated with stain amount is 3.2%-4.0%;
The preparation method of described chromatogram principal post, comprises the following steps:
A) gc column tube system is done;
B) clean gc column tube;
C) chromatograph packing material processing;
D) chromatography column;
E) burin-in process;
Wherein, described chromatograph packing material is treated to 80-100 order DG-2 through the processing of sieving, and pours into and containsIn the acetone of ApiezonL, stir, then dry for subsequent use;
Described burin-in process is that populated chromatographic column is put into baking oven, logical nitrogen in post, nitrogenPressure setting 0.2～0.25MPa, oven temperature is set 150 DEG C, ageing time 7～8 hours,Naturally after cooling, close nitrogen.
2. Freon gas detection alarm device as claimed in claim 1, described in it is characterized in thatColumn jecket length is 1600mm.
3. Freon gas detection alarm device as claimed in claim 1, described in it is characterized in thatThe painting stain amount of ApiezonL fixer is 3.2%.
4. Freon gas detection alarm device as claimed in claim 1, described in it is characterized in thatColumn jecket is stainless steel tube, its external diameterWall thickness 0.5mm.
5. Freon gas detection alarm device as claimed in claim 1, described in it is characterized in thatControl system is mainly made up of ARM, MCU, data acquisition, pump valve control, communication, collectionBe formed on surface-mounted integrated circuit; Described ARM adopts the ARM920T kernel of 200MHz dominant frequencyEP9315 processor; Described MCU is 8 single-chip microcomputer PIC16F886, and it passes throughRS-232 interface is communicated by letter with ARM; Described data acquisition completes simulation by AD7794 chipAmount gathers, and it is communicated by letter with MCU by SPI interface; Described pump valve control is controlled by MCU,By high power valve TIP122 electric current of make-and-break, according to the requirement of gas circuit sequential, dynamically control;Described communication is completed by MCU, ARM, and MCU uploading data is to ARM, and ARM connectsTen-way valve and electronic pressure controller, control ten-way valve by ARM and switch, and sets electron pressureThe force value of controller.
6. Freon gas detection alarm device as claimed in claim 1, is characterized in that it alsoComprise insulating box, case is in-built chromatographic column, relevant gas circuit and electron capture detector.
7. Freon gas detection alarm device as claimed in claim 5, described in it is characterized in thatIn control system, 12 D/A converters and MCU have formed a closed-loop control system, D/AThe electric field strong and weak of the output control electron capture detector of converter, adjusts baseline in real time.
8. Freon gas detection alarm device as claimed in claim 5, described in it is characterized in thatSurface-mounted integrated circuit circuit adopts ultralow bias current operational amplifier, and its bias current is fA(10-15) level.
9. Freon gas detection alarm device as claimed in claim 5, described in it is characterized in thatThe loop that has tested electric current process in surface-mounted integrated circuit circuit, all adopts the wiring of polytetrafluoroethylene (PTFE)Post connects, and welding adopts the mode of joint welding.
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| CN104569203B (en) * | 2015-01-06 | 2016-06-29 | 南京特种气体厂有限公司 | A kind of ammonia monitoring, alarming based on chromatography and switched system and method |
| CN107817330B (en) * | 2017-11-01 | 2020-03-31 | 四方光电股份有限公司 | Detection value correction method and detection method of difluoromethane leakage detection device |
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| CN101324548B (en) * | 2008-07-25 | 2011-05-11 | 昆明理工大学 | Method for analyzing Freon 12 concentration |
| CN202676680U (en) * | 2012-07-07 | 2013-01-16 | 国家海洋局第一海洋研究所 | Device capable of detecting low-concentration freon in seawater |
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