CN110411973A - A kind of method of non-methane total hydrocarbons concentration in detection gas - Google Patents
A kind of method of non-methane total hydrocarbons concentration in detection gas Download PDFInfo
- Publication number
- CN110411973A CN110411973A CN201910812908.5A CN201910812908A CN110411973A CN 110411973 A CN110411973 A CN 110411973A CN 201910812908 A CN201910812908 A CN 201910812908A CN 110411973 A CN110411973 A CN 110411973A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- methane
- gas
- oxidation
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 33
- 238000001514 detection method Methods 0.000 title claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 61
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 61
- 230000003647 oxidation Effects 0.000 claims abstract description 60
- 239000002808 molecular sieve Substances 0.000 claims abstract description 52
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 52
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000012360 testing method Methods 0.000 claims abstract description 13
- 238000001745 non-dispersive infrared spectroscopy Methods 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 23
- 238000005516 engineering process Methods 0.000 abstract description 16
- MEKDPHXPVMKCON-UHFFFAOYSA-N ethane;methane Chemical compound C.CC MEKDPHXPVMKCON-UHFFFAOYSA-N 0.000 abstract description 14
- 239000007789 gas Substances 0.000 description 37
- 239000000463 material Substances 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000012544 monitoring process Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000003705 background correction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- -1 embodiment 6 Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
Abstract
The invention discloses a kind of methods of non-methane total hydrocarbons concentration in detection gas.Described method includes following steps: under test gas is passed through medium temperature selective catalytic oxidation column, catalysis oxidation is carried out under conditions of 260~380 DEG C, using the concentration of carbon dioxide in gas of the NDIR instrument detection after catalysis oxidation, the concentration of NMHC under test gas is obtained through conversion；The composition of the catalyst loaded in gating catalytic oxidation column is as follows: including carrier and the active metal being carried on carrier；Carrier is molecular sieve；Active metal is palladium；The mass content of active metal is 0.1~10% in catalyst.The present invention is based on the technologies of catalysis oxidation-NDIR to detect non-methane total hydrocarbons, by the gating catalytic oxidation of methane ethane mixed gas as model reaction (most dysoxidizable in non-methane total hydrocarbons is ethane), catalyst used by confirming has efficiently is selectively convertered the ability of NMHC (such as ethane) without converting methane, the application being completely suitable in non-methane total hydrocarbons detection very much.
Description
Technical field
The present invention relates to a kind of methods of non-methane total hydrocarbons concentration in detection gas, belong to gas-monitoring field.
Background technique
In environmental monitoring field, total volatile organic compounds (Total Volatile Organic Compounds,
TVOCs) by the World Health Organization (WHO, 1989) to its is defined as: fusing point lower than room temperature and boiling point between 50~260 DEG C
Volatile organic compounds general name.Non-methane total hydrocarbons (Non-Methane Hydrocarbon, NMHC) is typically referred to except first
The general name of hydrocarbon (wherein be mainly C2~C8) other than alkane, except nytron beyond the region of objective existence is contained, further include alcohol, aldehyde, acid,
The hydrocarbon derivatives such as ester, ketone and C8The above volatile organic matter.Total volatile organic compounds (TVOCs) and non-
Methane total hydrocarbon (NMHC) is two different concepts, and the scope that total volatile organic compounds is covered in definition is greater than non-methane
Total hydrocarbon, i.e., whether there is or not the differences for adding methane concentration.Currently, NMHC is a kind of main surrounding air and industrial factory circle source emission gas
The substantially situation of polluted gas concentration can be obtained by NMHC concentration value for the pollution level index of body, be conducive to as environment prison
It surveys and provides a kind of fast and convenient measurement index with environmental law enforcement.Due to atmosphere organic pollutant discharge gradually by government,
The sensitivity of the monitoring instrument of society and the extensive concern of the public, total volatile organism and non-methane total hydrocarbons, convenience and
The performances such as safety are all the emphasis of environmental protection administration and the concern of monitoring instrument manufacturer all the time.At present in non-methane total hydrocarbons
Determination method in, the analysis method generallyd use includes gas chromatography, fluorimetry, capillary electrophoresis etc..
Wherein, because high sensitivity and linear extent that hydrogen flame ionization detector (FID) is to hydrocarbon organic matter to be had, use chromatography
Post separation methane and NMHC add fid detector (GC+FID) method to be a kind of hand of the domestic non-methane total hydrocarbons monitoring generallyd use
Section.However, containing not caused by the interference of high-purity hydrogen safety issue existing for GC+FID method, environmental gas, " equivalent carbon effect "
The error of saturated bond or the low caused detectable concentration of hetero atom organic matter response, to be unable to continuous sampling analysis etc. many lacks
Point seriously restricts its application that NMHC is monitored in different disposal of pollutants sources.
Prior art discloses the methods using catalysis method detection non-methane total hydrocarbons, but its method is examined using FID
Methane is surveyed, TVOCs is converted into methane using catalysis technique, then detected with FID and generate methane, and then obtain NMHC concentration, this
Kind method, which remains unchanged, uses the concentration of GC+FID detection methane, does not get rid of the inherent shortcoming of GC+FID detection method substantially, such as just
Victory, safety and the disadvantages such as economy is low, high economy, efficient detection to current environmental monitoring field demand
TVOCs and NMHC still has certain difficulty.
The monitoring technology of non-methane total hydrocarbons (NMHC) based on " catalysis oxidation-NDIR " technology is using highly selective, high
NMHC catalysis oxidation is carbon dioxide and water, then by mature at present in certain temperature range by the catalyst of stability
Non-linear infrared (NDIR) measurement generate gas concentration lwevel, to extrapolate the concentration of NMHC.Utilize NDIR detector
Technology has following advantage: it is small in size, it is easily carried；It is highly-safe, without H in FID2Assist bring hidden safely
Suffer from；Economy is high, and compared to fid detector, NDIR technology can substantially reduce testing cost；Detection process is quick, compared to GC+
The disengaging time of chromatographic column is up to the shortcomings that a few minutes in FID method, and catalysis oxidation NDIR technology can accomplish real-time monitoring；It surveys
High sensitivity is measured, mature NDIR sensor detects CO at present2The sensitivity of concentration is up to 1ppm (0.536mg/m3, in terms of C) with
Under；The target organic in NMHC can be completely converted into CO by catalytic oxidation technologies2, effectively evaded FID/PID
The error of detectable concentration caused by response difference to different types of organic matter has superior full spectrum detectability.
The key core technologies of catalysis oxidation-NDIR technology are that the selection of catalysis material is determined and is synthetically prepared.Catalysis
Can material reach corresponding requirements, generally require and meet following condition: (1) catalytic selectivity is high, by NMHC complete oxidation
For CO2, while retaining methane, and there is wide temperature operating window；(2) stability is good, and long-time service, which remains to remain height, urges
Change activity and selectivity；(3) environment resistant interference performance is strong, and for various concentration, the gas of different component is able to maintain
NMHC is converted CO by relevant temperature section2Catalysis oxidation ability.
Catalysis oxidation-NDIR the technology used for NMHC detection selects catalysis oxidation material in NMHC detection to have one
Fixed challenge such as selectively realizes the complete catalysts oxidation of NMHC.Although methane is as a kind of hydrocarbon the most stable
Matter, but in the organic matter containing similar chemical characters such as ethane, propane, by NMHC within the scope of certain temperature complete oxidation
For CO2, and retaining methane converts it not, is the key that technology and challenge.It therefore, can if developing a kind of catalysis material
Possessing makes NMHC complete oxidation and retains the not oxidized ability of methane, then its selective oxidation that can be applied to NMHC and inspection
It surveys analysis and is used as catalysis material.
Summary of the invention
The object of the present invention is to provide a kind of method of non-methane total hydrocarbons concentration in detection gas, the method for the present invention is to be based on
Catalysis oxidation-NDIR technology realizes the detection of non-methane total hydrocarbons, can be complete by non-methane total hydrocarbons in certain temperature range
While being converted into carbon dioxide entirely, selective does not convert methane completely, the interference for avoiding methane from detecting NMHC；Then sharp
The quality of non-methane total hydrocarbons is scaled with the concentration of non-dispersion infrared (NDIR) the technology measurement carbon dioxide of current maturation
Concentration.
Specifically, in detection gas provided by the invention non-methane total hydrocarbons concentration method, include the following steps:
By under test gas by medium temperature selective catalytic oxidation column, catalysis oxidation is carried out under conditions of 260~380 DEG C,
Using the concentration of carbon dioxide in gas of the NDIR sensor detection after catalysis oxidation, obtained under test gas through conversion
The concentration of NMHC；
The composition of the catalyst loaded in the medium temperature selective catalytic oxidation column is as follows:
Including carrier and the active metal being carried on the carrier；
The carrier is molecular sieve；
The active metal is palladium；
In the catalyst, the mass content of the active metal is 0.1~10%, preferably 0.2~1% or 0.5%.
In above-mentioned method, the molecular sieve can be ZSM Series Molecules sieve, Beta molecular sieve, MOR molecular sieve, Y type molecule
ZSM-5 molecular sieve in sieve, A type molecular sieve or X-type molecular sieve etc., preferably ZSM Series Molecules sieve.
In above-mentioned method, the catalyst further includes the promoter metal ingredient being carried on the molecular sieve；
The promoter metal is potassium, sodium, manganese, iron, cobalt, nickel, cerium, lanthanum, chromium, vanadium and tin at least one.
In above-mentioned method, the silica alumina ratio of the molecular sieve can be 20~80, preferably 25~50,25 or 50, having a size of
100nm~10 μm, such as having a size of 1~10 μm or so of micron-level molecular sieve, the nanometer fraction having a size of 100~1000nm or so
Son sieve.
In the method for the present invention, when the molecular sieve using different silica alumina ratios is used as carrier, and active metal is palladium, and quality contains
When amount is 0.2~1% (preferably 0.5%), the catalysis oxidation temperature that the catalyst is applicable in is different, specific as follows:
1) when the molecular sieve is the nanoscale ZSM-5 molecular sieve that silica alumina ratio is 25, the temperature of the catalysis oxidation is
260~360 DEG C；
2) when the molecular sieve is the micron order ZSM-5 molecular sieve that silica alumina ratio is 25, the temperature of the catalysis oxidation is
350~370 DEG C；
3) when the molecular sieve is the micron order ZSM-5 molecular sieve that silica alumina ratio is 50, the temperature of the catalysis oxidation is
300~340 DEG C；
4) when the molecular sieve is the micron order MOR molecular sieve that silica alumina ratio is 25, the temperature of the catalysis oxidation is 340
~360 DEG C.
In above-mentioned method, the mass concentration of NMHC is 1~1500mg/m in the under test gas3。
In above-mentioned method, needs to deduct the carbon dioxide (i.e. background concn) under test gas, then convert；It can
It measures in the following way: directly detecting the concentration of carbon dioxide under test gas using NDIR.
The catalyst that the method for the present invention uses can be prepared by conventional method, such as: equi-volume impregnating, Vaccum Permeating
The methods of stain method, ion-exchange, liquid-phase reduction load method.
The concentration of existing NDIR instrument detection carbon dioxide can be used in the method for the present invention.
The present invention is based on the technologies of catalysis oxidation-NDIR to detect non-methane total hydrocarbons, passes through the choosing of methane ethane mixed gas
Catalysis oxidation is selected as model reaction (most dysoxidizable in non-methane total hydrocarbons is ethane), it was confirmed that used catalyst has
It is efficiently selectively convertered very much the ability of NMHC (such as ethane) without converting methane, is completely suitable for detecting in non-methane total hydrocarbons
In application.In order to further verify the gating catalytic oxidation performance of such catalyzed conversion material, the present invention be additionally added propane,
Other typical non-methane total hydrocarbons such as benzene, toluene and ethyl acetate represent pollutant, same living with very excellent catalysis oxidation
Property.
Detailed description of the invention
Fig. 1 is the work of the methane ethane catalysis oxidation of micron order Pd/ZSM-5 (50) catalysis material in the embodiment of the present invention 1
Linearity curve figure.
Fig. 2 is the work of the methane ethane catalysis oxidation of nanoscale Pd/ZSM-5 (25) catalysis material in the embodiment of the present invention 2
Linearity curve figure.
Fig. 3 is the work of the methane ethane catalysis oxidation of micron order Pd/ZSM-5 (25) catalysis material in the embodiment of the present invention 3
Linearity curve figure.
Fig. 4 is the activity of the methane ethane catalysis oxidation of micron order Pd/MOR (25) catalysis material in the embodiment of the present invention 4
Curve graph.
Fig. 5 is the work of the methane ethane catalysis oxidation of micron order Pd/ZSM-5 (200) catalysis material in comparative example 1 of the present invention
Linearity curve figure.
Fig. 6 is the flow chart that the method for NMHC concentration is surveyed the present invention is based on catalysis oxidation-NDIR technology.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Catalyst as used in the following examples is prepared by the following method:
At room temperature, 0.1g palladium acetylacetonate is dissolved in 1mL trioctylphosphine phosphorus, under the atmosphere of nitrogen protection solution by
Gradually become orange from yellow, then solution instilled into 9mL trioctylphosphine phosphorus and is stirred, be gradually warmed up to 300 DEG C, keeps 30min,
Obtain black colloidal solution.After being cooled to room temperature, ethanol washing is added, centrifuge separation is redispersed in after cleaning several times repeatedly
In 50mL ethanol solution.A certain amount of molecular sieve carrier is added, steeped overnight is stirred, is put into Muffle furnace 500 after solvent evaporated
DEG C calcining 3h.Obtain the Pd/ molecular sieve catalytic material of respective negative carrying capacity.
Embodiment 1: under different temperatures, Pd/ZSM-5 (50) molecular sieve catalytic material is urged for methane ethane mixed gas
Oxidation
Reaction evaluating device is continuously flowed using small fixed, the silica alumina ratio of micron-level molecular sieve carrier ZSM-5 is 50,
Pd load capacity is 0.5wt%.Tube inner diameter is 4mm, and reaction gas is the ethane and 21% oxygen of the methane of 508ppm, 515ppm
Mixed gas, air speed be 18 000gmlh-1.The conversion results of methane and ethane under different temperatures, condition of normal pressure
As shown in Figure 1, it can be seen that within the temperature range of 300~340 DEG C, ethane complete oxidation is carbon dioxide, and methane is kept
It is constant.
Under embodiment 2, different temperatures, Pd/ZSM-5-3 (25) molecular sieve catalytic material is for methane ethane mixed gas
Catalytic oxidation
Reaction evaluating device is continuously flowed using small fixed, the silica alumina ratio of nano-class molecular sieve carrier ZSM-5-3 is
25, Pd load capacity are 0.5wt%.Tube inner diameter is 4mm, and reaction gas is the ethane and 21% of the methane of 508ppm, 515ppm
The mixed gas of oxygen, air speed are 18 000gmlh-1.The conversion ratio of methane and ethane under different temperatures, condition of normal pressure
As a result as shown in fig. 2, it can be seen that within the temperature range of 260~360 DEG C, ethane complete oxidation is carbon dioxide, and methane
It remains unchanged.
Under embodiment 3, different temperatures, Pd/ZSM-5 (25) molecular sieve catalytic material is urged for methane ethane mixed gas
Oxidation
Reaction evaluating device is continuously flowed using small fixed, the silica alumina ratio of micron-level molecular sieve carrier ZSM-5 is 25,
Tube inner diameter is 4mm, and reaction gas is methane, the ethane of 515ppm and the mixed gas of 21% oxygen of 508ppm, and air speed is
18 000g·ml·h-1.The conversion results of methane and ethane under different temperatures, condition of normal pressure are as shown in figure 3, can see
Out, within the temperature range of 340~350 DEG C, ethane complete oxidation is carbon dioxide, and methane remains unchanged.
Under embodiment 4, different temperatures, Pd/MOR (25) molecular sieve catalytic material is used for the catalysis of methane ethane mixed gas
Oxidation reaction
Reaction evaluating device is continuously flowed using small fixed, the silica alumina ratio of micron-level molecular sieve carrier MOR is 25, instead
Answering bore is 4mm, and reaction gas is methane, the ethane of 515ppm and the mixed gas of 21% oxygen of 508ppm, air speed 18
000g·ml·h-1.The conversion results of methane and ethane are as shown in Figure 4 under different temperatures, condition of normal pressure, it can be seen that In
Within the temperature range of 340~360 DEG C, ethane complete oxidation is carbon dioxide, and methane remains unchanged.
Under comparative example 1, different temperatures, Pd/ZSM-5 (200) molecular sieve catalytic material is for methane ethane mixed gas
Catalytic oxidation
Reaction evaluating device is continuously flowed using small fixed, the silica alumina ratio of micron-level molecular sieve carrier ZSM-5 is
200, tube inner diameter 4mm, reaction gas is methane, the ethane of 515ppm and the mixed gas of 21% oxygen of 508ppm, empty
Speed is 18 000gmlh-1.The conversion results of methane and ethane under different temperatures, condition of normal pressure are as shown in figure 5, can be with
Find out, the catalysis material of the ZSM-5 (200) with weaker acid does not have the ability of selective oxidation non-methane total hydrocarbons.
The catalysis oxidation of comparative example 1-4 and comparative example 1 is results, it can be seen that due to different silica alumina ratios and difference
The surface nature of the molecular sieve of size has very big difference, especially has very big difference in nature in surface acidity, and
Surface acidity can play the role of during catalytic oxidation alkane it is very huge, therefore, excellent surface and suitable load
The synergistic effect of active metal is the key factor that the catalyst works.
The catalysis material of the molecular sieve supported different noble metals of comparative example 2, ZSM-5 (50) is used for methane ethane gating catalytic oxidation
The activity performance of reaction compares
Reaction evaluating device is continuously flowed using small fixed, molecular sieve carrier is micron-sized ZSM-5, silica alumina ratio
It is 50, noble-metal-supported amount is 0.5wt%.Tube inner diameter is 4mm, and reaction gas is the second of the methane of 508ppm, 515ppm
The mixed gas of alkane and 21% oxygen, air speed are 18 000gmlh-1.In atmospheric conditions, the catalysis oxygen of methane and ethane
It is as shown in table 1 below to change result.Wherein, the selectivity of carbon dioxide is 98% or more.
By the data in table 1, it can be seen that only Pd has the energy of gating catalytic oxidation non-methane total hydrocarbons in noble metal
Power.
The catalysis oxidation result of the different catalysis materials of table 1
Embodiment 5, moisture and CO2Equal environmental gas are to the activity influence of Pd/ZSM-5 (50) catalysis material using small-sized solid
Fixed bed continuously flows reaction evaluating device, and molecular sieve carrier is micron order ZSM-5, silica alumina ratio 50, and Pd load capacity is
0.5wt%, tube inner diameter 4mm, one pack system concentrations of reactant gas are methane 508ppm and ethane 515ppm, the H of addition2O is dense
Degree is 50%RH, CO2Concentration is 2%, and air speed is 18 000gmlh-1.In atmospheric conditions, the catalysis oxygen of methane and ethane
The results are shown in Table 2 for change.Wherein, the selectivity of carbon dioxide is 98% or more.
By the data in table 2, it can be seen that common CO in ambiance2And H2O is not biggish to catalyst activity
It influences.
Table 2 adds moisture and CO2When catalysis oxidation result
Typical case's NMHC substance such as embodiment 6, propane, toluene, acetylene, ethyl acetate, dichloroethanes is to Pd/ZSM-5 (50)
The activity influence of catalysis material
Continuously flow reaction evaluating device using small fixed, molecular sieve carrier ZSM-5, silica alumina ratio 50, Pd is negative
Carrying capacity is 0.5wt%.Tube inner diameter is 4mm, and propane 200ppm, toluene is added in methane ethane combination gas respectively
The typical NMHC substance of 200ppm, acetylene 100ppm, ethyl acetate 200ppm and dichloroethanes 200ppm, air speed 26000h-1。
In atmospheric conditions, the results are shown in Table 3 for the catalysis oxidation of each non-methane total hydrocarbons single-component gas.Wherein, the choosing of carbon dioxide
Selecting property is 98% or more.
By the data in table 3, it can be seen that the catalyst all has other several typical non-methane total hydrocarbons very excellent
Different selective catalysis activity.
Table 3 adds catalysis oxidation result when different NMHC
Embodiment 7,
The flow chart using the method for non-linear infrared (NDIR) technology detection NMHC concentration is adopted as shown in fig. 6, tool
Body step are as follows:
(1) tested gas is controlled into its flow direction by triple valve, when passing through first via void column, be tested organic in gas
Object does not change, and then gas enters in NDIR detector, the CO measured2Concentration is the background CO of gas2Concentration, as sky
White value is deducted；
(2) by triple valve by the tangential third road medium temperature gating catalytic oxidation column of gas, catalyst is in catalysis oxidation column
Pd/ZSM-5 (50) catalysis material, within the temperature range of 300~340 DEG C, all NMHC can complete oxidation be carbon dioxide,
Methane is able to maintain constant, to measure by NDIR sensor CO2It can convert to obtain NMHC concentration after concentration background correction value
(in terms of C).
According to the above process to the dense of the NMHC in 100ppm methane, 100ppm ethane and 100ppm ethyl acetate gaseous mixture
Degree is detected.Catalyst uses micron order Pd/ZSM-5 (50), and it is 340 DEG C that NMHC, which is catalyzed column temperature,.Testing result such as 4 institute of table
Show:
The testing result of NMHC in 4 mixed gas of table
There is very high essence using the non-linear infrared method detection NMHC of catalysis oxidation-it can be seen from the above results
Degree, up to 99% or more.
Claims (9)
1. the method for non-methane total hydrocarbons concentration, includes the following steps: in a kind of detection gas
By under test gas by medium temperature selective catalytic oxidation column, catalysis oxidation is carried out under conditions of 260~380 DEG C, is used
The concentration of carbon dioxide in gas of the NDIR instrument detection after catalysis oxidation obtains the dense of NMHC under test gas through conversion
Degree；
The composition of the catalyst loaded in the medium temperature selective catalytic oxidation column is as follows:
Including carrier and the active metal being carried on the carrier；
The carrier is molecular sieve；
The active metal is palladium；
In the catalyst, the mass content of the active metal is 0.1~10%.
2. according to the method described in claim 1, it is characterized by: the molecular sieve is ZSM Series Molecules sieve, Beta molecule
Sieve, MOR molecular sieve, Y type molecular sieve, A type molecular sieve or X-type molecular sieve.
3. method according to claim 1 or 2, it is characterised in that: the catalyst further includes being carried on the molecular sieve
On promoter metal ingredient；
The promoter metal is at least one of potassium, sodium, manganese, iron, cobalt, nickel, cerium, lanthanum, chromium, vanadium and tin.
4. method according to any one of claim 1-3, it is characterised in that: the silica alumina ratio of the molecular sieve be 20~
80。
5. according to the method described in claim 4, it is characterized by: the molecular sieve is the nanoscale ZSM-5 that silica alumina ratio is 25
When molecular sieve, the temperature of the catalysis oxidation is 260~360 DEG C.
6. according to the method described in claim 4, it is characterized by: the molecular sieve is the micron order ZSM-5 that silica alumina ratio is 25
When molecular sieve, the temperature of the catalysis oxidation is 350~370 DEG C.
7. according to the method described in claim 4, it is characterized by: the molecular sieve is the micron order ZSM-5 that silica alumina ratio is 50
When molecular sieve, the temperature of the catalysis oxidation is 300~340 DEG C.
8. according to the method described in claim 4, it is characterized by: the molecular sieve is that the micron order MOR that silica alumina ratio is 25 divides
When son sieve, the catalysis oxidation temperature is 340~360 DEG C.
9. method according to claim 1 to 8, it is characterised in that: the quality of NMHC is dense in the under test gas
Degree is 1~1500mg/m3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910812908.5A CN110411973B (en) | 2019-08-30 | 2019-08-30 | Method for detecting concentration of non-methane total hydrocarbons in gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910812908.5A CN110411973B (en) | 2019-08-30 | 2019-08-30 | Method for detecting concentration of non-methane total hydrocarbons in gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110411973A true CN110411973A (en) | 2019-11-05 |
| CN110411973B CN110411973B (en) | 2021-12-17 |
Family
ID=68369425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910812908.5A Active CN110411973B (en) | 2019-08-30 | 2019-08-30 | Method for detecting concentration of non-methane total hydrocarbons in gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110411973B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114002343A (en) * | 2021-09-30 | 2022-02-01 | 深圳市普瑞美泰环保科技有限公司 | VOCs concentration determination method, equipment and readable storage medium |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370815A (en) * | 2001-02-12 | 2002-09-25 | 普莱克斯技术有限公司 | Method and apparatus for purifying CO2 material flow |
| CN101143282A (en) * | 2006-09-15 | 2008-03-19 | 中国石油化工股份有限公司 | Organic waste gas purifying method |
| EP1989533A1 (en) * | 2006-02-28 | 2008-11-12 | Panalytique Inc. | System and method of eliminating interference for impurities measurement in noble gases |
| KR20140088291A (en) * | 2012-12-31 | 2014-07-10 | 주식회사 씨이티이노텍 | Solar ray generation device using gas filter |
| CN104678062A (en) * | 2015-03-03 | 2015-06-03 | 重庆创图环境检测有限公司 | VOC (volatile organic compound) gas and non-methane total hydrocarbon gas sampling and detecting system |
| CN104772038A (en) * | 2015-03-25 | 2015-07-15 | 中国石油天然气股份有限公司 | Method for purifying acrylonitrile apparatus absorbing tower tail gas by using Pd-CeO2/Me-beta molecular sieve |
| CN105344213A (en) * | 2015-11-23 | 2016-02-24 | 中国科学院生态环境研究中心 | Method for long-time stable low-temperature catalysis complete oxidation removal of ethylene |
| CN105806899A (en) * | 2016-05-25 | 2016-07-27 | 吉林大学 | Production and application of Pt-SnO2 oxide semiconductor carbon monoxide sensor |
| CN106053652A (en) * | 2016-06-20 | 2016-10-26 | 上海市计算技术研究所 | Method and device for monitoring methane or non-methane hydrocarbon |
| CN205719955U (en) * | 2016-04-07 | 2016-11-23 | 南京波腾科技工程有限公司 | The continuous monitoring device of NMHC |
| US20170088487A1 (en) * | 2015-09-25 | 2017-03-30 | Exxonmobil Chemical Patents Inc. | Hydrocarbon Conversion |
| CN106732576A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of catalyst for catalytic oxidation and its preparation method and application |
| CN107907486A (en) * | 2017-11-29 | 2018-04-13 | 中国科学院生态环境研究中心 | A kind of method using oxidized form sensor detection low-concentration ethane |
| US20180111084A1 (en) * | 2016-01-12 | 2018-04-26 | Beijing University Of Chemical Technology | INTEGRATED PURIFICATION METHOD AND SYSTEM FOR THE INDUSTRIAL EXHAUST GAS CONTAINING CYANIDES, HYDROCARBONS AND NOx |
| CN108333284A (en) * | 2018-02-08 | 2018-07-27 | 北京雪迪龙科技股份有限公司 | The method and its system of carbon compound are detected based on catalytic conversion technique |
| CN207805342U (en) * | 2017-12-26 | 2018-09-04 | 北京华钛高科科技有限公司 | A kind of industry VOCs exhaust treatment systems |
| CN109225316A (en) * | 2018-10-08 | 2019-01-18 | 中自环保科技股份有限公司 | A kind of exhaust gas treatment catalyst and its preparation method and application |
| CN109870532A (en) * | 2019-03-13 | 2019-06-11 | 翼捷安全设备（昆山）有限公司 | Online non-methane total hydrocarbons analysis system |
-
2019
- 2019-08-30 CN CN201910812908.5A patent/CN110411973B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370815A (en) * | 2001-02-12 | 2002-09-25 | 普莱克斯技术有限公司 | Method and apparatus for purifying CO2 material flow |
| EP1989533A1 (en) * | 2006-02-28 | 2008-11-12 | Panalytique Inc. | System and method of eliminating interference for impurities measurement in noble gases |
| CN101410710A (en) * | 2006-02-28 | 2009-04-15 | 巴拿利提科有限公司 | System and method of eliminating interference for impuritiesmeasurement in noble gases |
| US20090132206A1 (en) * | 2006-02-28 | 2009-05-21 | Panalytique Inc. | System and method of eliminating interference for impurities measurement in noble gases |
| CN101143282A (en) * | 2006-09-15 | 2008-03-19 | 中国石油化工股份有限公司 | Organic waste gas purifying method |
| KR20140088291A (en) * | 2012-12-31 | 2014-07-10 | 주식회사 씨이티이노텍 | Solar ray generation device using gas filter |
| CN104678062A (en) * | 2015-03-03 | 2015-06-03 | 重庆创图环境检测有限公司 | VOC (volatile organic compound) gas and non-methane total hydrocarbon gas sampling and detecting system |
| CN104772038A (en) * | 2015-03-25 | 2015-07-15 | 中国石油天然气股份有限公司 | Method for purifying acrylonitrile apparatus absorbing tower tail gas by using Pd-CeO2/Me-beta molecular sieve |
| US20170088487A1 (en) * | 2015-09-25 | 2017-03-30 | Exxonmobil Chemical Patents Inc. | Hydrocarbon Conversion |
| CN106732576A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of catalyst for catalytic oxidation and its preparation method and application |
| CN105344213A (en) * | 2015-11-23 | 2016-02-24 | 中国科学院生态环境研究中心 | Method for long-time stable low-temperature catalysis complete oxidation removal of ethylene |
| US20180111084A1 (en) * | 2016-01-12 | 2018-04-26 | Beijing University Of Chemical Technology | INTEGRATED PURIFICATION METHOD AND SYSTEM FOR THE INDUSTRIAL EXHAUST GAS CONTAINING CYANIDES, HYDROCARBONS AND NOx |
| CN205719955U (en) * | 2016-04-07 | 2016-11-23 | 南京波腾科技工程有限公司 | The continuous monitoring device of NMHC |
| CN105806899A (en) * | 2016-05-25 | 2016-07-27 | 吉林大学 | Production and application of Pt-SnO2 oxide semiconductor carbon monoxide sensor |
| CN106053652A (en) * | 2016-06-20 | 2016-10-26 | 上海市计算技术研究所 | Method and device for monitoring methane or non-methane hydrocarbon |
| CN107907486A (en) * | 2017-11-29 | 2018-04-13 | 中国科学院生态环境研究中心 | A kind of method using oxidized form sensor detection low-concentration ethane |
| CN207805342U (en) * | 2017-12-26 | 2018-09-04 | 北京华钛高科科技有限公司 | A kind of industry VOCs exhaust treatment systems |
| CN108333284A (en) * | 2018-02-08 | 2018-07-27 | 北京雪迪龙科技股份有限公司 | The method and its system of carbon compound are detected based on catalytic conversion technique |
| CN109225316A (en) * | 2018-10-08 | 2019-01-18 | 中自环保科技股份有限公司 | A kind of exhaust gas treatment catalyst and its preparation method and application |
| CN109870532A (en) * | 2019-03-13 | 2019-06-11 | 翼捷安全设备（昆山）有限公司 | Online non-methane total hydrocarbons analysis system |
Non-Patent Citations (4)
| Title |
|---|
| GANG WANG ET: "Adsorption of benzene, cyclohexane and hexane on ordered mesoporous carbon", 《J O U R N A L O F E N V I R O N M E N T A L S C I E N C E S》 * |
| JUNG-NAM PARK ET: "A highly dispersed Pd–Mg/SiO2 catalyst active for methanation of CO2", 《JOURNAL OF CATALYSIS》 * |
| 刘欢 等: "新型载体对 VOCs 催化氧化反应性能的影响", 《应用化工》 * |
| 郝正平 等: "我国工业VOCs减排控制与管理对策研究", 《环境科学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114002343A (en) * | 2021-09-30 | 2022-02-01 | 深圳市普瑞美泰环保科技有限公司 | VOCs concentration determination method, equipment and readable storage medium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110411973B (en) | 2021-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110411972A (en) | A kind of method of general volatile organic pollutant and non-methane total hydrocarbons concentration in while detection gas | |
| Zhao et al. | Effects of different mixing ratios on emissions from passenger cars fueled with methanol/gasoline blends | |
| Berezkin | Analytical reaction gas chromatography | |
| CN206974972U (en) | A kind of NMHC gas analyzer | |
| Wei et al. | Direct measurement of formaldehyde and methanol emissions from gasohol engine via pulsed discharge helium ionization detector | |
| Chuang et al. | Transient in situ infrared methods for investigation of adsorbates in catalysis | |
| Nakagawa et al. | Detection of organic molecules dissolved in water using a γ-Al2O3 chemiluminescence-based sensor | |
| US20030166294A1 (en) | Method for improved detection of carbon monoxide by infrared absorption spectroscopy | |
| Possanzini et al. | Determination of low boiling aldehydes in air and exhaust gases by using annular denuders combined with HPLC techniques | |
| Wardencki et al. | Gas chromatographic sulphur-sensitive detectors in environmental analysis | |
| CN110411973A (en) | A kind of method of non-methane total hydrocarbons concentration in detection gas | |
| CN111551643A (en) | Method and system for detecting carbon-containing compound based on catalytic conversion technology | |
| US4717675A (en) | Method for selective conversion of organic compounds and detecting same by gas chromotography and chemiluminescence detection | |
| CN110412190A (en) | The analysis system and its analysis method of methane and non-methane total hydrocarbons | |
| Beroza et al. | Carbon Skeleton Chromatography Using Hot-Wire Thermal-Conductivity Detection. | |
| Jia et al. | A new cataluminescence sensor for carbon tetrachloride using its catalytic reduction by hydrogen on palladium/carbon surface | |
| Jonsson et al. | Formation of methyl nitrite in engines fueled with gasoline/methanol and methanol/diesel | |
| Zheng et al. | Development of trichloroethylene gaseous sensor utilizing ZnO–Y 2 O 3 as nanocatalyst based on thermal desorption/cataluminescence | |
| CN109870532A (en) | Online non-methane total hydrocarbons analysis system | |
| WO2023050825A1 (en) | Vocs concentration measurement method and device, and readable storage medium | |
| Wen et al. | Development of a sensitive gas sensor by trapping the analytes on nanomaterials and in situ cataluminescence detection | |
| CN102305835B (en) | Method for detecting formic acid by using hydrogen flame ionization detector based on catalytic reduction technology | |
| CN1412553A (en) | Detection method of hydroxyl free radical | |
| Hung | Development of a copper–lanthanum oxide catalyst for the removal of gaseous ammonia by catalytic oxidation: Physicochemical and electrochemical characterization of catalyst materials | |
| Gaffney et al. | Gas chromatographic detection of reduced sulfur compounds using ozone chemiluminescence |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |