CN105973804B - VOC substance online test method in a kind of gas based on UV photodissociation - Google Patents
VOC substance online test method in a kind of gas based on UV photodissociation Download PDFInfo
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Abstract
The present invention provides VOC substance online test method in a kind of gas based on UV photodissociation, comprising the following steps: S1: opening the ultraviolet lamp in oxidation unit；S2: opening sampler, adjusts flow regulator, gas is made to continue through oxidation unit with certain flow；S3: when recording t at any one time, the pressure P of the gas after the oxidation that second measuring device measures2, temperature T2And CO2Concentration C2；It is recorded in t-tRWhen the moment, the pressure P of the gas before the oxidation corresponding with second measuring device that first measuring device measures1, temperature T1、CO2Concentration C1；S4: when calculating any moment t, the molar concentration of the total organic carbon of VOC substance in the gasThe beneficial effects of the present invention are, after testing gas respectively before oxidation, the corresponding temperature of the gas, pressure and CO2Concentration, using the concentration that can obtain VOC substance is calculated, which is not only simple in structure, operating cost is low, and measurement accuracy is high.
Description
Technical field
The present invention relates to VOC in VOC substance detecting method in a kind of gas more particularly to a kind of gas based on UV photodissociation
Substance online test method.
Background technique
VOC substance, i.e. volatile organic compounds can cause very big pollution if exceeded release to atmospheric environment, harm
The health of people.
Patent document CN 2570774Y, discloses a kind of closed cycle total organic carbon analytical equipment, and the device is by sample
Automatic quantitive sampling device removes CO2Device, oxidation unit, reactant sampling device, gas dewatering device, air pump, infrared-gas
Analyzer, instrument measurement and control unit composition, for detecting the content of total organic carbon in waterbody, in the detection process, are removed
CO2It is cumbersome with the step of being removed water in gas, moreover, this device is only applicable to the concentration of VOC in detection water quality, can not use
The concentration of VOC in detection gas.
And existing detection VOC gas concentration technology mainly utilizes mass spectrum, gas-chromatography, photoionization detection method and hydrogen
Flame ion (FID) detection method.Although mass spectrum, gas chromatographic detection technology detect more accurate, instrument and equipment price ratio
It is higher, more complex, time-consuming is operated, measurement cost is higher；Sample gas is carried out electricity using hydrogen flame by hydrogen flame ionization detector
From, it is therefore desirable to it is equipped with hydrogen cylinder, and is needed to frequently replace, instrument needs to use in explosion-proof environment, and it is very high to security requirement,
Higher operating costs；Using ultraviolet lamp come ionization of sample gas, molecule is ionized as with plus-minus electric photoionization detector
Ion, they are experienced to form electric current by charge sensor, and instrument cost is lower, but in the process due to excitation molecule
It is quenched, the compound and foreign substance trapped electron of cation and electronics makes the reduction of detection cell electron concentration, and different ultraviolet
Lamp have to detection VOC substance it is more highly selective so that photoionization detection method detection numerical precision is not high, in consideration of it, anxious
VOC substance online test method in the gas that one kind is easy to operate, measurement accuracy is high need to be developed.
In view of the above drawbacks, creator of the present invention obtains the present invention by prolonged research and practice finally.
Summary of the invention
To solve the above problems, the technical solution adopted by the present invention is, VOC in a kind of gas based on UV photodissociation is provided
Substance online test method, which comprises the following steps: S1: the ultraviolet lamp in oxidation unit is opened, reaches one
A stable state；S2: opening sampler, adjusts flow regulator, continues through gas with certain flow described
Oxidation unit；S3: when recording t at any one time, the pressure P of the gas after the oxidation that second measuring device measures2、
Temperature T2And CO2Concentration C2；It is recorded in t-tRWhen the moment, first measuring device is measuring with the second measuring device phase
The pressure P of the gas before corresponding oxidation1, temperature T1、CO2Concentration C1, wherein tRIndicate the gas from first measurement
Device is moved to the time of second measuring device；S4: when calculating any moment t, VOC substance is total organic in the gas
The molar concentration of carbon
Further, if the VOC substance is pure material, the mass concentration C of the total organic carbon of this VOC substanceMAre as follows:
In formula, C indicates the molar concentration of the total organic carbon of the VOC substance, MrIndicate mole matter of the VOC substance
Amount, k indicate the carbon atom number that the VOC substance contains.
Further, if the VOC substance is mixture, the mass concentration C of the total organic carbon of this VOC substanceMAre as follows:
In formula, C indicates the molar concentration of the total organic carbon of the VOC substance, and m indicates the group contained in the VOC substance
Divide number, niIndicate the amount of the substance of the i-th component, kiIndicate the number of carbon atom in the i-th component, MiIndicate mole of the i-th component
Quality.
Further, the flow regulator includes flow control valve and flowmeter, and the sampler, flow are adjusted
Valve, flowmeter and first measuring device are sequentially connected.
Further, the ultraviolet lamp is placed vertically in the oxidation unit.
Further, the entrance of the oxidation unit is lower than the outlet of the oxidation unit.
Further, a thermometer is equipped in the oxidation unit.
Further, first measuring device is connected with measure and control device respectively with second measuring device.
Further, when the molar concentration C of the total organic carbon of the VOC substance is more than discharge standard, the measure and control device
It controls warning device and issues alarm command.
Further, on the inner wall of the oxidation unit be coated with catalyst layer, the catalyst layer be titanium dioxide layer,
The composite layer of one or more of nano oxidized zinc layers and tungstic acid layer.
Compared with the prior art the beneficial effects of the present invention are:
1. VOC substance online test method of the present invention, described after testing the gas respectively before oxidation
The corresponding temperature of gas, pressure and gas concentration lwevel can obtain total organic carbon in VOC substance using simple computation
Molar concentration, which is not only simple in structure, operating cost is low, and measurement accuracy is high；
2. the ultraviolet lamp is placed vertically, it can either guarantee that the temperature in the oxidation unit is uniform, and can guarantee institute
The ultraviolet irradiation intensity stated in oxidation unit is consistent, is all aoxidized during moving from bottom to top conducive to the gas；
3. being equipped with third thermometer in the oxidation unit, the third thermometer can be used in oxygen described in indirect monitoring
Disguise the state of the response situation and the ultraviolet lamp in setting；
4. the setting of the measure and control device realizes intelligentized data monitoring and treatment process, saved the time, increase
The applicability of the device；
5. the warning device issues report when the molar concentration C of VOC substance is more than the standard that VOC substance allows to discharge
Alert order, reminds operator to take appropriate measures；
6. being coated with catalyst layer on the inner wall of the oxidation unit, the catalyst layer can accelerate VOC substance
Oxidation.
Detailed description of the invention
Fig. 1 is the functional block diagram of VOC substance on-line measuring device in a kind of gas based on ultraviolet lamp of the present invention；
Fig. 2 is a kind of structure of VOC substance on-line measuring device in the gas based on ultraviolet lamp in the embodiment of the present invention one
Schematic diagram；
Fig. 3 is a kind of structure of VOC substance on-line measuring device in the gas based on ultraviolet lamp in the embodiment of the present invention four
Schematic diagram；
Fig. 4 is a kind of structure of VOC substance on-line measuring device in the gas based on ultraviolet lamp in the embodiment of the present invention five
Schematic diagram；
Fig. 5 is the structural schematic diagram of measure and control device of the present invention；
Fig. 6 is the structural schematic diagram of oxidation unit of the present invention.
Specific embodiment
Below in conjunction with attached drawing, the forgoing and additional technical features and advantages are described in more detail.
Embodiment one
Referring to Fig. 1, its function knot for VOC substance on-line measuring device in a kind of gas based on ultraviolet lamp of the present invention
Structure block diagram.
VOC substance on-line measuring device in a kind of gas based on ultraviolet lamp, including sampler 1, for gas into
Row continuous sampling；Flow regulator 2 is connect with the sampler 1, for making the gas pass through certain flow Q；
Oxidation unit 4, for being aoxidized to the gas entered in it；First measuring device 3 is set to the flow regulator
Between 2 and the oxidation unit 4, for measuring the temperature, pressure and the CO that aoxidize the preceding gas2Concentration；Second measuring device
5, for measure oxidation after the gas temperature, pressure and CO2Concentration.Wherein, the preferred sampling pump of sampler 1；
A ultraviolet lamp 41 is equipped in the oxidation unit 4, under the irradiation of the ultraviolet lamp 41, the VOC substance can be oxidized
For CO2；The Q is that benzene is all oxidized the flow being passed through in the oxidation unit 4.
In the present invention, oxidation mechanism of the VOC substance in the oxidation unit 4 are as follows: the gas is continuously entered equipped with height
The oxidation unit 4 of strong ultraviolet lamp, under the irradiation of the ultraviolet lamp 41, VOC substance is CO by direct photolysis2, in addition to this, institute
It states containing oxygen and hydrone in gas, under the irradiation of ultraviolet lamp, oxygen is oxidized to O3, the O of generation3It also can be by VOC substance
It is converted into CO2；The O-H key of hydrone is directly interrupted and is generated with strong oxidizing property by the photon energy in ultraviolet lamp rich in 185nm
OH, meanwhile, O3Also it can be acted on hydrone and generate more OH, the oxidizing potential of OH is 2.8eV, and oxidability is only
Inferior to fluorine, VOC substance is easily oxidized to CO by the OH of generation2。
VOC on-line measuring device of the invention, commonly used in detection Paint Factory, the workshops such as chemical plant VOC substance it is dense
Degree, avoids it in process of production, causes in workshop that VOC substance is exceeded, is detrimental to health.
VOC substance on-line measuring device of the invention, after testing the gas before oxidation, the gas is corresponding
Temperature, pressure and gas concentration lwevel, the molar concentration of total organic carbon in VOC substance can be obtained using simple computation,
The device is not only simple in structure, operating cost is low, and measurement accuracy is high.
Referring to Fig. 2, its knot for VOC substance on-line measuring device in the gas based on ultraviolet lamp a kind of in the present embodiment
Structure schematic diagram.
The flow regulator 2, including flow control valve 21 and flowmeter 22, the sampler 1, flow control valve
21, flowmeter 22 and first measuring device 3 are sequentially connected.For ensure the gas from the import of the oxidation unit 4 to
Outlet is all oxidized, and with difficulty by the substance of ultraviolet oxidation, on the basis of benzene, it is whole in the oxidation unit 4 to measure it
It is oxidized the flow Q being passed through, the substance that other are easily oxidized than benzene passes through the flow tune on the basis of the flow Q that benzene is passed through
Section valve 21 cooperates the flowmeter 22, and adjusting charge flow rate is Q, in such manner, it is possible to ensure into described in the oxidation unit 4
VOC substance in gas is CO by complete photodissociation2。
First measuring device 3 includes first pressure gauge 31, the first thermometer 32 and the first NDIR-CO2Sensor 33,
The sampler 1, flow adjust regulating valve 21, flowmeter 22, first pressure gauge 31, the first thermometer 32 and the first NDIR-
CO2Sensor 33 is sequentially connected, the first NDIR-CO2Sensor 33 is connected with the inlet of the oxidation unit 4, and described
One pressure gauge 31, the first thermometer 32 and the first NDIR-CO2Sensor 33 is respectively used to test the gas and enters the oxidation
Pressure, temperature and the CO of 4 foregoing description gas of device2Concentration.
Second measuring device 5 includes sequentially connected second pressure gauge 51, second temperature meter 52 and the 2nd NDIR-
CO2Sensor 53, the second pressure gauge 51 are connected with the exit of the oxidation unit 4, and the gas is most afterwards through described
Two NDIR-CO2Sensor 53 is directly emptied, wherein the second pressure gauge 51, second temperature meter 52 and the 2nd NDIR-
CO2Sensor 53 is respectively used to test the gas pressure of the gas, temperature and described after the oxidation unit 4 oxidation
CO in gas2Concentration.
If the first NDIR-CO2Sensor 33 and the 2nd NDIR-CO2The volume of pipeline and institute between sensor 53
The volume summation for stating the cavity in oxidation unit 4 is VR, then the gas is in the first NDIR-CO2Sensor 33 and described
Two NDIR-CO2The time t moved between sensor 53R=VR/Q。
At any one time when t, the pressure P of the gas after recording the oxidation that second measuring device measures2, temperature
T2And CO2Concentration C2, then in t moment, CO in gas described in 4 exit of oxidation unit2Substance amountAfter before oxidation, the gas is from the first NDIR-CO2Sensor 33 is moved to described second
NDIR-CO253 time of sensor is tR, it is recorded in t-tRWhen the moment, what first measuring device measured measures with described second
The pressure P of the gas before the corresponding oxidation of device1, temperature T1、CO2Concentration C1。
Continuous sampling air inlet is identical with throughput out, and according to equation for ideal gases, the gas is entering oxidation dress
CO before setting 4, in the gas2Substance amountBy time tR, VOC substance in the gas
It is completely converted into CO2, at this point, CO in the gas2Substance amountThen at any one time t when, the gas
The CO that VOC substance converts in body2Substance amount n=n2(t)-n1(t-tR), then the CO that VOC substance converts in the gas2's
Molar concentrationMeasured CO2Molar concentration C be the VOC object
The concentration of the total organic carbon of matter.
Embodiment two
VOC substance on-line measuring device in a kind of gas based on ultraviolet lamp as described above, the present embodiment are different from
Place is that the position of the first pressure gauge 31 and first thermometer 32 can be interchanged, 51 He of second pressure gauge
The position of the second temperature meter 52 can be interchanged.
Embodiment three
VOC substance on-line measuring device in a kind of gas based on ultraviolet lamp as described above, the present embodiment are different from
Place is that the ultraviolet lamp 41 is placed vertically in the oxidation unit 4, in this way, can either guarantee in the oxidation unit 4
Temperature it is uniform, and can guarantee that the ultraviolet irradiation intensity in the oxidation unit 4 is consistent, be conducive to the gas from bottom to top
It is all aoxidized in mobile process.
The entrance of the oxidation unit 4 is lower than the outlet of the oxidation unit 4, since the quality of VOC substance is than air
Quality weight, in this way, when continuous ventilation, the gas from bottom to top it is mobile compared to moving from top to bottom for, slow down movement
Rate, keep gas residence time in the oxidation unit 4 longer, increase the time of oxidation.
Example IV
VOC substance on-line measuring device in a kind of gas based on ultraviolet lamp as described above, the present embodiment are different from
It points out to be, as shown in figure 3, being equipped with a thermometer in the oxidation unit 4, this temperature is calculated as third thermometer 42, described
State of the third thermometer 42 for response situation and the ultraviolet lamp 41 in oxidation unit 4 described in indirect monitoring.If described
The temperature value that third thermometer 42 is shown is excessively high, considers from secure context, need to suspend detection, in the oxidation unit 4
When temperature is in the range of the device is normally born, it can be detected；If the third thermometer 42 is detected in long-time
During, shown by temperature always all in lower state, then illustrate the ultraviolet lamp 41 occur aging phenomenon or
The ultraviolet lamp 41 is in idle state.
Embodiment five
VOC substance on-line measuring device in a kind of gas based on ultraviolet lamp as described above, the present embodiment are different from
Place is, in conjunction with shown in Fig. 4 and Fig. 5, Fig. 5 is the structural schematic diagram of measure and control device, and the VOC on-line measuring device also wraps
Include a measure and control device 6, the measure and control device 6 includes governor circuit, display module and data processing module, the display module and
The data processing module is connected with the governor circuit respectively；First measuring device 3 and second measuring device 5 are divided
It is not connected with the governor circuit in the measure and control device 6, specifically, the first pressure gauge 31, the first thermometer 32, first
NDIR-CO2Sensor 33, second pressure gauge 51, second temperature meter 52 and the 2nd NDIR-CO2Sensor 53 respectively with the master control
Circuit is connected, the first pressure gauge 31, the first thermometer 32, the first NDIR-CO2Sensor 33, second pressure gauge 51, second
Thermometer 52 and the 2nd NDIR-CO2Sensor 53 is respectively by the P of reading1、C1、T1、P2、C2、T2Data transfer give the master control
Circuit, then formula is pressed through the data processing moduleAfter processing, through described
Governor circuit is transferred to the display module and is shown, is save the cost, this reality since data processing is simpler in the present invention
It applies in example, the preferred PLC controller of the measure and control device 6.
The setting of the measure and control device 6, realizes intelligentized data monitoring and treatment process, has saved the time, increases
The applicability of the device.
Embodiment six
VOC substance on-line measuring device in a kind of gas based on ultraviolet lamp as described above, the present embodiment are different from
Place is, in conjunction with shown in Fig. 4 and Fig. 5, the VOC on-line measuring device further includes a warning device 43, the alarm dress
It sets 43 to be connected with the governor circuit in the measure and control device 6, when the VOC object that the data processing module is handled
When the molar concentration C of the total organic carbon of matter is more than the standard that VOC substance allows to discharge, the governor circuit controls the alarm dress
43 sending police instruction orders are set, the warning device 43 is alarmed in the form of acousto-optic, if the form of buzzing or flash of light is alarmed, is mentioned
Awake operator takes appropriate measures.
Embodiment seven
VOC substance on-line measuring device in a kind of gas based on ultraviolet lamp as described above, the present embodiment are different from
Place is, the catalyst layer 7 that can be activated by ultraviolet light, the catalyst are coated on the inner wall of the oxidation unit 4
Layer 7 can accelerate the oxidation of VOC substance, wherein the catalyst layer is titanium dioxide layer, nano oxidized zinc layers and three oxidations
The composite layer of one or more of tungsten layer.
Embodiment eight
The detection method of VOC substance on-line measuring device in a kind of gas based on ultraviolet lamp as described above, including with
Lower step:
S1: the ultraviolet lamp in oxidation unit is opened, a stable state is reached；
S2: opening sampler, adjusts flow regulator, and gas is made to continue through the oxidation dress with certain flow
It sets；
S3: when recording t at any one time, the pressure P of the gas after the oxidation that second measuring device measures2、
Temperature T2And CO2Concentration C2；It is recorded in t-tRWhen the moment, first measuring device is measuring with the second measuring device phase
The pressure P of the gas before corresponding oxidation1, temperature T1、CO2Concentration C1, wherein tRIndicate the gas from first measurement
Device is moved to the time of second measuring device；
S4: when calculating any moment t, the molar concentration of the total organic carbon of VOC substance in the gas
VOC substance online test method of the invention, after testing the gas before oxidation, the gas is corresponding
Temperature, pressure and gas concentration lwevel, the molar concentration of total organic carbon in VOC substance can be obtained using simple computation,
The device is not only simple in structure, operating cost is low, and measurement accuracy is high.
Embodiment nine
VOC substance online test method in gas as described above based on UV photodissociation, the present embodiment are different from place
It is, if the VOC substance is pure material, the mass concentration C of the total organic carbon of this VOC substanceMAre as follows:
In formula, C indicates the molar concentration of the total organic carbon of the VOC substance, MrIndicate mole matter of the VOC substance
Amount, k indicate the carbon atom number that the VOC substance contains.
When such as VOC substance being toluene, the molar concentration of the toluene measured according to VOC on-line measuring device is C, by above-mentioned
The mass concentration C of toluene can be obtained in formulaM=C × 92/7=13C.
Embodiment ten
VOC substance online test method in gas as described above based on UV photodissociation, the present embodiment are different from place
It is, if the VOC substance is mixture, the mass concentration C of the total organic carbon of this VOC substanceMAre as follows:
In formula, C indicates the molar concentration of the total organic carbon of the VOC substance, and m indicates the group contained in the VOC substance
Divide number, niIndicate the amount of the substance of the i-th component, kiIndicate the number of carbon atom in the i-th component, MiIndicate mole of the i-th component
Quality.
If the component number contained in VOC substance is 3 kinds, the 1st group is divided into benzene (C6H6), the amount n of corresponding substance1, mole
Mass M1, the number k of C atom that contains1Respectively 1mol, 78.11g/mol, 6；2nd group is divided into acetone (C3H6O), corresponding
The amount n of substance2, molal weight M2, the number k of C atom that contains2Respectively 2mol, 58.08g/mol, 3；3rd component is positive oneself
Alkane (C6H14), the amount n of corresponding substance3, molal weight M3, the number k of C atom that contains3Respectively 1mol, 86.17g/mol,
6, the molar concentration of the total organic carbon of the VOC substance measured according to VOC on-line measuring device is C, calculates the total organic of VOC substance
The mass concentration C of carbonMAre as follows:
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, under the premise of not departing from the method for the present invention, can also make several improvement and supplement, these are improved and supplement also should be regarded as
Protection scope of the present invention.
Claims (10)
1. VOC substance online test method in a kind of gas based on UV photodissociation, which comprises the following steps:
S1: the ultraviolet lamp in oxidation unit is opened, a stable state is reached；
S2: opening sampler, adjusts flow regulator, gas is made to continue through the oxidation unit with certain flow；
S3: when recording t at any one time, the pressure P of the gas after the oxidation that the second measuring device measures2, temperature T2With
CO2Concentration C2；It is recorded in t-tRWhen the moment, before the oxidation corresponding with second measuring device that the first measuring device measures
The pressure P of the gas1, temperature T1、CO2Concentration C1, wherein tRIndicate that the gas is moved to institute from first measuring device
State the time of the second measuring device；
S4: when calculating any moment t, the molar concentration of the total organic carbon of VOC substance in the gas
2. VOC substance online test method in the gas according to claim 1 based on UV photodissociation, which is characterized in that if
When the VOC substance is pure material, then the mass concentration C of the total organic carbon of this VOC substanceMAre as follows:
In formula, C indicates the molar concentration of the total organic carbon of the VOC substance, MrIndicate the molal weight of the VOC substance, k table
Show the carbon atom number that the VOC substance contains.
3. VOC substance online test method in the gas according to claim 1 based on UV photodissociation, which is characterized in that if
When the VOC substance is mixture, then the mass concentration C of the total organic carbon of this VOC substanceMAre as follows:
In formula, C indicates the molar concentration of the total organic carbon of the VOC substance, and m indicates the component contained in the VOC substance
Number, niIndicate the amount of the substance of the i-th component, kiIndicate the number of carbon atom in the i-th component, MiIndicate mole matter of the i-th component
Amount.
4. VOC substance online test method in the gas according to claim 1 based on UV photodissociation, which is characterized in that institute
Stating flow regulator includes flow control valve and flowmeter, the sampler, flow control valve, flowmeter and described first
Measuring device is sequentially connected.
5. VOC substance online test method in the gas according to claim 1 based on UV photodissociation, which is characterized in that institute
Ultraviolet lamp is stated to place vertically in the oxidation unit.
6. VOC substance online test method in the gas according to claim 1 based on UV photodissociation, which is characterized in that institute
The entrance for stating oxidation unit is lower than the outlet of the oxidation unit.
7. VOC substance online test method in the gas according to claim 1 based on UV photodissociation, which is characterized in that institute
It states and is equipped with a thermometer in oxidation unit.
8. VOC substance online test method in the gas according to claim 1 based on UV photodissociation, which is characterized in that institute
The first measuring device is stated to be connected with measure and control device respectively with second measuring device.
9. VOC substance online test method in the gas according to claim 8 based on UV photodissociation, which is characterized in that when
When the molar concentration C of the total organic carbon of the VOC substance is more than discharge standard, the measure and control device control warning device issues report
Alert order.
10. VOC substance online test method in -9 any gases based on UV photodissociation according to claim 1, feature
It is, catalyst layer is coated on the inner wall of the oxidation unit, and the catalyst layer is titanium dioxide layer, nano zine oxide
The composite layer of layer and one or more of tungstic acid layer.
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| CN101315328A (en) * | 2008-07-17 | 2008-12-03 | 西北工业大学 | Gas concentration measuring apparatus and method |
| CN104614337A (en) * | 2015-01-06 | 2015-05-13 | 西安交通大学 | Portable multi-component mixed gas monitoring system |
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| CN101315328A (en) * | 2008-07-17 | 2008-12-03 | 西北工业大学 | Gas concentration measuring apparatus and method |
| CN104614337A (en) * | 2015-01-06 | 2015-05-13 | 西安交通大学 | Portable multi-component mixed gas monitoring system |
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