CN106053652A - Method and device for monitoring methane or non-methane hydrocarbon - Google Patents

Method and device for monitoring methane or non-methane hydrocarbon Download PDF

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Publication number
CN106053652A
CN106053652A CN201610446104.4A CN201610446104A CN106053652A CN 106053652 A CN106053652 A CN 106053652A CN 201610446104 A CN201610446104 A CN 201610446104A CN 106053652 A CN106053652 A CN 106053652A
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China
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methane
gas
concentration
total hydrocarbon
detector
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CN201610446104.4A
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Chinese (zh)
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王勇军
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上海市计算技术研究所
上海上计群力分析仪器有限公司
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Priority to CN201610446104.4A priority Critical patent/CN106053652A/en
Publication of CN106053652A publication Critical patent/CN106053652A/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/025—Gas chromatography

Abstract

The invention relates to the field of gas monitoring, and discloses a method and a device for monitoring methane or non-methane hydrocarbon. The method comprises the steps of (1) filling a total hydrocarbon detector with standard gas, and establishing a total hydrocarbon concentration curve; enabling the standard gas to pass through a catalytic oxidation device, then filling a methane detector with the standard gas, and establishing a methane concentration curve; (2) heating sample gas, and then filling the total hydrocarbon detector with the heated sample gas; heating the to-be-detected sample gas, enabling the heated sample gas to pass through the catalytic oxidation device, and then filling the methane detector with the sample gas; (3) obtaining the concentration value of total hydrocarbon and the concentration value of methane, namely, the concentration value of the non-methane hydrocarbon in the sample gas according to the step (1) and the step (2). The catalytic oxidation device is used for oxidizing all hydrocarbon gases except the methane in the gas into water and carbon dioxide, so that the concentration signal of the methane can be directly detected; the method has the advantage of detecting the methane or the non-methane hydrocarbon in the gas in real time, and is convenient and simple in data processing, thus having very high market competitiveness and application value.

Description

Monitoring methane, the method and device of NMHC

Technical field

The present invention relates to gas-monitoring field, particularly to a kind of method and device monitoring methane, NMHC.

Background technology

In recent years due to high speed development, the quickening of industrialization and urbanization process of domestic economy, vehicle guaranteeding organic quantity is anxious Sharp increase adds, and the industry such as the primary pollution source petrochemical industry of volatile organic matter, automobile, household electrical appliances, fine chemistry industry increases very fast, and volatility has Machine solvent usage amount is big, causes VOC (volatile organic compounds is called for short VOCs) discharge Amount is big, and VOCs refers at normal temperatures, and boiling point is at the various organic compound of 50 DEG C～260 DEG C.VOCs presses its chemical constitution, permissible Be further divided into: alkanes, aromatic hydrocarbons, esters, aldehydes and other etc..Identified at present has kind more than 300.Modal have Benzene,toluene,xylene, styrene, trichloro ethylene, chloroform, trichloroethane, diisocyanate (TDI), two isocyanide toluene esters Deng, the Hydrocarbon that its ground atom is combined by carbon, hydrogen and oxygen, VOCs discharge capacity is crossed conference and is caused photochemical smog to be polluted sternly Weight, and then produce a series of secondary pollution.In these secondary pollutions, ozone accounts for the largest percentage.Numerous research tables Bright, ozone has extremely strong hazardness to human body, material, crops.It addition, VOCs rises in troposphere photochemical oxidation circulates To the most crucial effect, it is city and the important as precursors thing of region secondary gaseous contaminant, controls light directly or indirectly The formation speed of oxidant and efficiency, have very important impact to atmospheric oxidn potentiality.

At present China incorporates overall control index to the discharge of VOCs, especially, total to the methane in VOCs, non-methane The monitoring of hydrocarbon and benzene homologues is listed in important with uncontrollable discharge in a organized way of industrial park, China each place stationary source Monitoring index.On market, the analysis method to methane, non-methane typically uses HJ/T 38-1999 " non-in Concentration in Fixed Pollutants Source Mensuration-the gas chromatography of methane total hydrocarbon " chromatography, the method mainly by use chromatograph twin columns, dual detector realize between Every property monitoring.But this monitoring method has the disadvantage that owing to this monitoring method needs in total hydrocarbon by chromatographic column Methane carries out separating the purpose that could realize monitoring methane concentration, and this allows for existing on the time monitoring methane, non-methane Certain discontinuity, thus cause the problems such as Monitoring Data is inaccurate.

Summary of the invention

The purpose of embodiment of the present invention is to provide a kind of method and device monitoring methane, NMHC so that Methane, NMHC in gas can monitor out in real time, and convenient data processing is simple, has the stronger market competitiveness And using value.

For solving above-mentioned technical problem, embodiments of the present invention provide a kind of side monitoring methane, NMHC Method, comprising the steps of (1) if being passed through total hydrocarbon detector after calibrating gas heating different for carried interest total hydrocarbon concentration, obtaining each First response value of stock calibrating gas, first response value total hydrocarbon concentration in signature criteria gas；If by dense for carried interest methane Spend different calibrating gas heating after catalytic oxidizing equipment, be passed through methane detector, obtain the second sound of each stock calibrating gas Should be worth, second response value methane concentration in signature criteria gas；(2) dense with the total hydrocarbon in some strands of calibrating gas respectively Degree, the first response value set up total hydrocarbon concentration curve；Methane is set up with the methane concentration in some strands of calibrating gas, the second response value Concentration curve；(3) it is passed through total hydrocarbon detector after being heated by testing sample gas, obtains the of total hydrocarbon concentration in testing sample gas Three response values, the 3rd response value is used for characterizing the total hydrocarbon concentration in gas to be measured；By the heating of testing sample gas through catalysis oxygen Being passed through methane detector after gasifying device, obtain the 4th response value of testing sample gas, the 4th response value is used for characterizing gas to be measured Methane concentration in body；(4) according to the 3rd response value, the 4th response value and total hydrocarbon concentration curve, methane in step 2 in step 3 Concentration curve obtains the concentration value of total hydrocarbon in testing sample gas and the concentration value of methane；The concentration of total hydrocarbon in testing sample gas Value deducts the concentration value of NMHC during the concentration value of methane is testing sample gas in testing sample gas.

Embodiments of the present invention additionally provide a kind of device monitoring methane, NMHC, and this device is applied to State monitoring methane, the method for NMHC, including: sampling pump, injection port, flow controller, auto injection regulation valve, carrier gas Pipeline, heating compartment, hydrocarbon selective oxidation device, total hydrocarbon detector, methane detector and terminal unit；Wherein, sampling Pump is arranged between the import of injection port and carrier gas source, and flow controller one end is connected to control injection port with the outlet of injection port Gas concentration, the other end of flow controller is connected via one end of carrier gas channel and auto injection regulation valve, auto injection The other end of regulation valve is connected with the import of heating compartment via carrier gas channel, and the outlet of heating compartment includes and hydrocarbon selective The first the second outlet exporting and being connected with total hydrocarbon detector that the import of oxidation unit is connected, hydrocarbon selective oxidation device Outlet be connected with methane detector, total hydrocarbon detector is connected with terminal unit with methane detector.

In terms of existing technologies, the method is by each leading into catalysis oxygen after being heated by gas for embodiment of the present invention Gasifying device and total hydrocarbon detector, above-mentioned catalytic oxidizing equipment all hydrocarbon gas in addition to methane in gas are oxidized to water and Carbon dioxide, the gas through catalytic oxidizing equipment directly can detect the concentration signal of methane, separately by methane detector Outward, total hydrocarbon detector can directly detect THC concentration signal in air；And obtained by above-mentioned subtracting of two concentration NMHC concentration value.The method can reach the purpose of the methane in real-time detected gas, NMHC, and at data Reason is convenient, simple, has the stronger market competitiveness and using value.

Further, the heating-up temperature in step 1 and step 3 is 140 DEG C～180 DEG C, to ensure the water in monitoring gas Divide and exist with water vapour, prevent from monitoring the condensation of gas.

Further, step 2 also includes correcting total hydrocarbon concentration curve and the step of methane concentration curve zero point, this step bag Include: being passed through total hydrocarbon detector after zero gas heating of constant flow rate, obtain the 5th response value in zero gas, the 5th response value is used for Characterize the total hydrocarbon concentration in zero gas；After zero gas heating, after catalytic oxidizing equipment, it is passed through methane detector, obtains in zero gas The 6th response value, the 6th response value be used for characterize the methane concentration in zero gas；Wherein, the 5th response value, the 6th response value are divided Yong Yu not correct total hydrocarbon concentration curve, the zero point of methane concentration curve, so that the data of monitoring are more accurate.

Further, in step 1, the temperature of catalytic oxidizing equipment is: 280 DEG C～320 DEG C, so that in monitoring gas All hydrocarbon gas in addition to methane are fully oxidized to water and carbon dioxide.

Further, in step 3, the flow of testing sample gas is 300ml/min～700ml/min.

Further, the composition of step 1 Plays gas is methane and propane.

Further, in step 1 Plays gas, the concentration of methane is: 10mg/m3～100mg/m3。

Further, in step 1 Plays gas, the concentration of propane is: 10mg/m3～100mg/m3。

Further, total hydrocarbon detector, methane detector are hydrogen flame ionization detector.

Accompanying drawing explanation

Fig. 1 is the flow chart of the method for the monitoring methane in first embodiment of the invention, NMHC；

Fig. 2 is the analysis chromatogram spectrogram of the calibrating gas in the matched group in first embodiment of the invention；

Fig. 3 is the analysis chromatogram spectrogram of the calibrating gas in the experimental group in first embodiment of the invention；

Fig. 4 is monitoring methane, the internal structure schematic diagram of NMHC device in second embodiment of the invention.

Detailed description of the invention

For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with the accompanying drawing each reality to the present invention The mode of executing is explained in detail.But, it will be understood by those skilled in the art that in each embodiment of the present invention, In order to make reader be more fully understood that, the application proposes many ins and outs.But, even if there is no these ins and outs and base Many variations and amendment in following embodiment, it is also possible to realize the application each claim technical side required for protection Case.

First embodiment of the present invention relates to a kind of method monitoring methane, NMHC, comprises the steps of (1) if being passed through total hydrocarbon detector after calibrating gas heating different for carried interest total hydrocarbon concentration, the first of each stock calibrating gas is obtained Response value, first response value total hydrocarbon concentration in signature criteria gas；If by calibrating gas different for carried interest methane concentration Heating is passed through methane detector after catalytic oxidizing equipment, obtains the second response value of each stock calibrating gas, the second response value Methane concentration in signature criteria gas；(2) build with the total hydrocarbon concentration in some strands of calibrating gas, the first response value respectively Vertical total hydrocarbon concentration curve；Methane concentration curve is set up with the methane concentration in some strands of calibrating gas, the second response value；(3) will It is passed through total hydrocarbon detector after the heating of testing sample gas, obtains the 3rd response value of total hydrocarbon concentration in testing sample gas, the 3rd Response value is used for characterizing the total hydrocarbon concentration in gas to be measured；The heating of testing sample gas is passed through first after catalytic oxidizing equipment Alkane detector, obtains the 4th response value of testing sample gas, and the 4th response value is for characterizing the methane concentration in gas to be measured； (4) obtain to be measured according to the 3rd response value, the 4th response value in step 3 with total hydrocarbon concentration curve, methane concentration curve in step 2 The concentration value of total hydrocarbon and the concentration value of methane in sample gas；In testing sample gas, the concentration value of total hydrocarbon deducts testing sample gas The concentration value of NMHC during the concentration value of methane is testing sample gas in body.

Catalytic oxidizing equipment in present embodiment uses hydrocarbon selective catalytic oxidation, is that a kind of extraction hydrogen is former Son and the reaction plus one or more oxygen atoms, result causes the generation of the product of several different C/H and C/O ratio.By In various different conditions, oxidation reaction can be divided into selective oxidation and complete oxidation, and catalytic oxidation is due to energy Enough is carbon dioxide and water or selective oxidation by each organic molecular species at transiting metal surface complete oxidation.Its type reaction Equation is:

It should be noted that in the present embodiment, selective oxidation is it is crucial that catalyst and reaction condition.Catalyst needs Meet following three points:

1. there is under certain air-fuel ratio alap initiation temperature；

2. heat resistance is good；

3. activity height, Heat stability is good；

In the present embodiment, the catalyst used in catalytic oxidizing equipment is integral catalyzer, and it is by matrix, divides Dissipating carrier and the organic whole of activity composition, catalyst activity uses composition metal i.e. Pt alloy, has anti-poisoning and anti-sintering Performance；Catalyst matrix uses the FeCrAl alloy substrate based on lamellar, and it has good heat conductivility and high-temperature hot Stability.

It is seen that, reaction condition is other hydro carbons sufficiently catalytic reaction of needs in monitoring gas in addition to methane, and Methane concentration can not change, and its key parameter index is temperature and reaction holdup time.Because methane is simplest hydro carbons, methane The structure of molecule is positive four sides structure, more stable, the fully oxidized reaction of methane, the mode that need to light just oxidable reaction conversions For CO2And H2O, under controlling heating-up temperature and catalysts conditions, methane is not easy oxidation reaction very much.The most non-first The sufficiently catalytic reaction of alkane total hydrocarbon, and methane keeps original concentration.

It is noted that in the present embodiment, the organic detection of nytron uses fid detector (i.e. Hydrogen flame ionization detector), it is typical destructiveness, mass flow rate sensitive detector.Fid detector is raw with hydrogen and air burning The flame become is the energy, when carbohydrate organic compounds enters flame, at high temperature produces chemi-ionization, and base flow is compared in ionization generation The ion stream of high several orders of magnitude, under the orientation of high voltage electric field, these positively charged ions and electronegative electronics Move to negative pole and positive pole respectively, form ion stream, faint ion stream (10-12A～10-8A) through high resistant (106Ω～1011 Ω) amplify, become the signal of telecommunication being directly proportional to the Hydrocarbon amount entered, therefore can be according to the size of signal to hydrocarbonization Close Organic substance and carry out quantitative analysis.NMHC detection is the nytron outside flame ionization ditector deduction methane Thing total amount, in terms of carbon.Its embodiment be in a road sample gas (i.e. air) except the hydrocarbon oxidation catalyst oxygen of methane content Turn to carbon dioxide and water constituent, quantitative by the methane in FID2 detector detection sample gas；In another road all hydrocarbon By FID1 detection quantitatively, total hydrocarbon concentration deducts methane concentration and is NMHC concentration compound (i.e. total hydrocarbon), specifically supervises Survey step as shown in Figure 1:

Set up total hydrocarbon concentration calibration curve

During actual monitoring gas, if the calibrating gas that carried interest total hydrocarbon concentration is different can be selected to be heated to 160 Being passed through total hydrocarbon detector after DEG C, wherein, total hydrocarbon concentration is arranged within limits, if i.e. can get what total hydrocarbon detector produced A dry total hydrocarbon concentration response signal value, then with the total hydrocarbon concentration in above-mentioned some strands of calibrating gas as Y-axis, several total hydrocarbons dense Degree response signal value is that X-axis sets up total hydrocarbon concentration calibration curve.

It should be noted that present embodiment to being passed through the number of share of stock of calibrating gas, concentration does not limits, people in the art Member can select number of share of stock and the concentration of calibrating gas as required.

Set up methane concentration calibration curve

If it addition, the calibrating gas again selecting carried interest methane concentration different is passed through catalysis oxidation dress after being heated to 160 DEG C Put, through catalysis oxidation calibrating gas be passed in methane detector, wherein, methane concentration within limits, Obtain several methane concentration response signal value that methane detector produces, with the methane concentration in above-mentioned some strands of calibrating gas It is that X-axis sets up methane concentration calibration curve for Y-axis, several methane concentration response signal value.

It should be noted that present embodiment to being passed through the number of share of stock of calibrating gas, concentration does not limits, people in the art Member can select number of share of stock and the concentration of calibrating gas as required.

The composition being passed through calibrating gas in present embodiment in step 1 is methane and propane, and wherein, the concentration of methane is: 10mg/m3～100mg/m3, the concentration of propane is: 10mg/m3～100mg/m3。

It should be noted that and set up total hydrocarbon concentration calibration curve and methane concentration calibration curve regardless of tandem, permissible First set up total hydrocarbon concentration calibration curve, it is also possible to first set up methane concentration calibration curve.

Correction total hydrocarbon concentration calibration curve, the zero point of methane concentration calibration curve

In order to correct total hydrocarbon concentration calibration curve and the zero point of methane concentration calibration curve so that the data of gas-monitoring are more Add is accurate, in the present embodiment, can select the zero of one constant flow rate (can select uninterrupted as required) It is passed through total hydrocarbon detector after gas (i.e. carbon-free hydrogen compound) heating, obtains total hydrocarbon detector and the total hydrocarbon concentration of zero gas is responded signal Value, total hydrocarbon concentration response signal value is used for characterizing the total hydrocarbon concentration in zero gas；Can select (permissible for additionally one constant flow rate Select uninterrupted as required) zero gas heating after through catalytic oxidizing equipment, zero gas through catalysis oxidation is passed through methane Detector, i.e. obtains the methane detector methane concentration response signal value to zero gas, and methane concentration response signal value is used for characterizing Methane concentration in zero gas；Wherein, the total hydrocarbon concentration response signal value of above-mentioned zero gas, methane concentration response signal value may be used for Correct above-mentioned total hydrocarbon concentration curve, the zero point of methane concentration curve, after completing aligning step, total hydrocarbon detector, methane detector Automatically generate total hydrocarbon concentration calibration trace, methane concentration calibration trace.

Moreover, it is noted that to total hydrocarbon concentration calibration curve, the zero point of methane concentration calibration curve correction regardless of Sequencing, can first proofread the zero point of methane concentration calibration curve, it is also possible to first proofread the zero point of total hydrocarbon concentration calibration curve.

The monitoring of testing sample gas

By the testing sample gas that sampling pump extraction flow is 500ml/min, wherein, in the present embodiment, to be measured Sample gas is the air in air, and uses omnidistance high temperature, and the size of temperature can ensure that in sample gas, moisture steams with water Vapour exists, and prevents sample from condensing；A part of testing sample gas constant inflow hydrocarbon selective oxidation device can be catalyzed oxygen Change, directly monitor methane content by methane detector, form concentration-response signal value, and according to methane concentration calibration curve meter Calculate display methane concentration value；Another part testing sample gas constant inflow total hydrocarbon detector, directly detects total hydrocarbon concentration, is formed Concentration-response signal value, and calculate display total hydrocarbon concentration value according to total hydrocarbon calibration curve；Total hydrocarbon concentration value deducts methane concentration value I.e. can get NMHC concentration value.

It is noted that in the present embodiment, the temperature of catalytic oxidizing equipment is maintained at 300 DEG C.

In order to detect and test the performance of catalytic oxidizing equipment, it was demonstrated that have and other hydrocarbon component in addition to methane is had Having the function of catalysis oxidation, applicant has done following experiment:

Experimental apparatus

Instrument: GC2000III gas chromatograph

Detection: flame ionisation detector (FID)

The model of chromatographic column: GDX-104

Six-way valve auto injection

Experiment parameter

The composition of examination criteria gas: CH4、C2H4、C2H6、C2H2, AIR (spirit)

Clack box temperature: 60 DEG C, detector FID temperature: 180 DEG C

The concentration of calibrating gas: 10ppm

Specific experiment step

Calibrating gas being divided into 2 strands, respectively experimental group and matched group, wherein the calibrating gas in matched group is entering Before entering the monitoring of GC2000III gas chromatograph, catalytic oxidizing equipment is not installed, obtains analysis chromatogram spectrogram as shown in Figure 2.

Calibrating gas in experimental group installs catalytic oxidizing equipment before entering the monitoring of GC2000III gas chromatograph, and Heating-up temperature in catalytic oxidizing equipment is set to 300 DEG C, obtains analysis chromatogram spectrogram as shown in Figure 3.

Experimental result

Contrast experiment's group and the chromatogram spectrogram of matched group, it is seen that, the calibrating gas in experimental group is through catalysis oxidation After device, catalytic oxidizing equipment is by the C in calibrating gas2H4、C2H6、C2H2With air catalytic oxidation Cheng Shui and CO2, and CH4Dense Degree does not changes.

In sum, in experimentation, this catalytic oxidizing equipment is entirely capable of removing other hydrocarbon component beyond methane.

Compared with prior art, in present embodiment, the method is by each leading into catalysis oxidation dress after being heated by gas Putting and total hydrocarbon detector, all hydrocarbon gas in addition to methane in gas are oxidized to water and dioxy by above-mentioned catalytic oxidizing equipment Changing carbon, the gas through catalytic oxidizing equipment directly can detect the concentration signal of methane by methane detector, it addition, always Hydrocarbon detector can directly detect THC concentration signal in air；And obtain non-methane by above-mentioned subtracting of two concentration Total hydrocarbon concentration value.The method can reach the purpose of the methane in real-time detected gas, NMHC, and data process side Just, simply, there is the stronger market competitiveness and using value.

Second embodiment of the present invention relates to a kind of device monitoring methane, NMHC, and this device is applied to Stating monitoring methane, the method for NMHC in the first embodiment, this device includes: sampling pump, injection port, flow-control Device, auto injection regulation valve, carrier gas channel, heating compartment, hydrocarbon selective oxidation device, total hydrocarbon detector, methane detector And terminal unit；Wherein, sampling pump is arranged between the import of injection port and carrier gas source, flow controller one end and injection port Outlet be connected the gas concentration to control injection port, the other end of flow controller regulates via carrier gas channel and auto injection One end of valve is connected, and the other end of auto injection regulation valve is connected with the import of heating compartment via carrier gas channel, heating compartment Outlet the first outlet of including being connected with the import of hydrocarbon selective oxidation device and be connected with total hydrocarbon detector second Outlet, the outlet of hydrocarbon selective oxidation device is connected with methane detector, and total hydrocarbon detector sets with terminal with methane detector Standby connected.Wherein, carrier gas source includes calibrating gas carrier gas source, zero airborne source of the gas and testing sample gas carrier source.

Specifically, the using method of the device in present embodiment is as follows: first take the gas in carrier gas source with sampling pump Body, the gas through sampling pump is entered in flow controller through injection port, and then is controlled the stream of gas by flow controller Amount size, automatic sampling valve extracts the gas of constant flow rate automatically by carrier gas channel, through the gas of automatic sampling valve extraction Entering heating compartment via carrier gas channel to heat, the gas through heating compartment heating is partly into hydrocarbon selective oxygen Gasifying device, another part gas enters total hydrocarbon detector, and it is laggard that the gas through hydrocarbon selective oxidation device is catalyzed oxidation Enter methane detector, last total hydrocarbon detector, methane detector to total hydrocarbon in gas, methane signal response value at terminal unit On show.

It is noted that total hydrocarbon detector, methane detector can be hydrogen flame ionization detector.

During actual monitoring, monitoring gas in methane, NMHC device by 4 tunnel sample gas Vavle switching controls System, the control of calibrating gas valve, sample gas sampling pump, two-way FID flame ionization ditector and two-way assist gas control system, urge Changing oxygen converting unit and heating compartment composition, this device internal structure is as shown in Figure 4.

Wherein, in accompanying drawing 4, the function of all parts is as follows:

Valve 1: calibrating gas and zero gas select sample introduction, for the calibrating function of instrument, to set up the calibration curve of gas；

Valve 2: for the selection sample introduction of calibrating gas and sample gas；

Valve 3, valve 4, valve 5, valve 6: be 4 road sample gas switching valves, constitute Multi-way analysis system, and use selected stream Sample blowback wash the system of other stream；

Heating compartment 7 (not showing in figure): keep the monitoring temperature of sample gas to remain at 160 DEG C.

Pump 8: for high temperature samples pump, sample gas uses omnidistance high temperature, to ensure that in sample gas, moisture exists with water vapour, Prevent sample from condensing；

FID1 (hydrogen flame ionization detector) 9: be total hydrocarbon composition in detection sample gas；

FID2 (hydrogen flame ionization detector) 10: be methane content in detection sample gas；

Catalysis oxidation 11: be the hydrocarbon oxidation catalyst of all non-methane compositions in air is aoxidized carbon dioxide and Water.

It should be noted that in the present embodiment, this monitoring device arranges 4 tunnel sample gas Vavle switching and controls, this Sample can be concurrently accessed 4 monitoring points, tunnel so that monitoring cost by the input of software monitoring capable of circulation 4 road sample gas Decreasing, present embodiment only illustrates arranging as a example by 4 tunnel sample gas Vavle switching control, and certainly, arranges 1 road sample air valve Switching control (i.e. monitoring the methane in 1 road sample gas, NMHC concentration) is also possible, and present embodiment should be with This is limited, and those skilled in the art can select the number that sample gas Vavle switching controls the most flexibly.

It will be understood by those skilled in the art that the respective embodiments described above are to realize the specific embodiment of the present invention, And in actual applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.

Claims (10)

1. the method monitoring methane, NMHC, it is characterised in that comprise the steps of
(1) if being passed through total hydrocarbon detector after calibrating gas heating different for carried interest total hydrocarbon concentration, each stock calibrating gas is obtained First response value, described first response value is for characterizing the total hydrocarbon concentration in described calibrating gas；
If calibrating gas heating different for carried interest methane concentration is passed through methane detector after catalytic oxidizing equipment, obtain each Second response value of stock calibrating gas, described second response value is for characterizing the methane concentration in described calibrating gas；
(2) total hydrocarbon concentration curve is set up with the total hydrocarbon concentration in described some strands of calibrating gas, described first response value respectively；With Methane concentration, described second response value in described some strands of calibrating gas set up methane concentration curve；
(3) it is passed through total hydrocarbon detector after being heated by testing sample gas, obtains the 3rd sound of total hydrocarbon concentration in testing sample gas Should be worth, described 3rd response value is used for characterizing the total hydrocarbon concentration in described gas to be measured；
The heating of described testing sample gas is passed through methane detector after catalytic oxidizing equipment, obtains described testing sample gas 4th response value of body, described 4th response value is for characterizing the methane concentration in described gas to be measured；
(4) according to the 3rd response value, the 4th response value and the total hydrocarbon concentration curve described in step 2, methane concentration song in step 3 Line obtains the concentration value of total hydrocarbon in testing sample gas and the concentration value of methane；In testing sample gas, the concentration value of total hydrocarbon deducts The concentration value of NMHC during the concentration value of methane is testing sample gas in testing sample gas.
Monitoring methane the most according to claim 1, the method for NMHC, it is characterised in that in step 1 and step 3 Heating-up temperature be 140 DEG C～180 DEG C.
Monitoring methane the most according to claim 1, the method for NMHC, it is characterised in that step 2 also includes correction Described total hydrocarbon concentration curve and the step of described methane concentration curve zero point, this step includes:
After zero gas heating of constant flow rate, it is passed through total hydrocarbon detector, obtains the 5th response value of described zero gas, described 5th sound The total hydrocarbon concentration for characterizing described zero gas should be worth；
After described zero gas heating, after catalytic oxidizing equipment, it is passed through methane detector, obtains the 6th response of described zero gas Value, described 6th response value is used for characterizing the methane concentration of described zero gas；
Wherein, described 5th response value, described 6th response value are respectively used to correct described total hydrocarbon concentration curve, methane concentration song The zero point of line.
Monitoring methane the most according to claim 1, the method for NMHC, it is characterised in that catalysis oxidation in step 1 The temperature of device is: 280 DEG C～320 DEG C.
Monitoring methane the most according to claim 1, the method for NMHC, it is characterised in that testing sample in step 3 The flow of gas is 300ml/min～700ml/min.
Monitoring methane the most according to claim 1, the method for NMHC, it is characterised in that standard described in step 1 The composition of gas is methane and propane.
Monitoring methane the most according to claim 6, the method for NMHC, it is characterised in that standard described in step 1 In gas, the concentration of methane is: 10mg/m3～100mg/m3。
Monitoring methane the most according to claim 6, the method for NMHC, it is characterised in that standard described in step 1 In gas, the concentration of propane is: 10mg/m3～100mg/m3。
9. the device monitoring methane, NMHC, it is characterised in that be applied to any one of described claim 1 to 8 Described monitoring methane, the method for NMHC, including: sampling pump, injection port, flow controller, auto injection regulation valve, Carrier gas channel, heating compartment, hydrocarbon selective oxidation device, total hydrocarbon detector, methane detector and terminal unit；
Wherein, described sampling pump is arranged between import and the carrier gas source of described injection port, described flow controller one end and institute The outlet stating injection port is connected to control the gas concentration of described injection port, and the other end of described flow controller is via described load Feed channel is connected with one end of described auto injection regulation valve, and the other end of described auto injection regulation valve is via described carrier gas pipe Road is connected with the import of described heating compartment, and the outlet of described heating compartment includes and the entering of described hydrocarbon selective oxidation device The first the second outlet exporting and being connected with described total hydrocarbon detector that mouth is connected, going out of described hydrocarbon selective oxidation device Mouth is connected with described methane detector, and described total hydrocarbon detector is connected with terminal unit with described methane detector.
Monitoring methane the most according to claim 9, the device of NMHC, it is characterised in that described total hydrocarbon detects Device, described methane detector are hydrogen flame ionization detector.
CN201610446104.4A 2016-06-20 2016-06-20 Method and device for monitoring methane or non-methane hydrocarbon CN106053652A (en)

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* Cited by examiner, † Cited by third party
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CN108982728A (en) * 2018-05-30 2018-12-11 上海市环境监测中心 A kind of optimization of surrounding air non-methane total hydrocarbons online monitoring instruments and calibration method
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