CN101614669B - Method and detector for detecting methanol and methyl tertiary butyl ether in gasoline by nano cataluminescence - Google Patents
Method and detector for detecting methanol and methyl tertiary butyl ether in gasoline by nano cataluminescence Download PDFInfo
- Publication number
- CN101614669B CN101614669B CN2009100129609A CN200910012960A CN101614669B CN 101614669 B CN101614669 B CN 101614669B CN 2009100129609 A CN2009100129609 A CN 2009100129609A CN 200910012960 A CN200910012960 A CN 200910012960A CN 101614669 B CN101614669 B CN 101614669B
- Authority
- CN
- China
- Prior art keywords
- butyl ether
- nano
- gasoline
- quartz capillary
- tertiary butyl
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a method and a detector for detecting methanol and methyl tertiary butyl ether in gasoline by nano cataluminescence, using a nano catalytic illuminator for detection. Stannic oxide is used as the nanomaterial, the detecting wavelength is 400-460 nm, the heating temperature ranges from 120 to 300 DEG C, and a flow rate of carrier gas is 1-40 ml/min. A detected optical signal and the concentration of the methanol and the methyl tertiary butyl ether form a linear relation, thereby the content of the methanol and the methyl tertiary butyl ether in the gasoline can be rapidly and precisely detected simultaneously, and the defects of high price of an apparatus, long time of analysis and poor accuracy caused by using a gas chromatograph for analysis are overcome. The invention has advantages of simple structure, easy operation, low cost (only thousands of RMB), strong selectivity, fewer transportation fees, long service life, high sensitivity, good reproducibility, and the like.
Description
Technical field:
The present invention relates to a kind of method and checkout equipment that detects methyl alcohol and methyl tert-butyl ether in the gasoline, especially a kind of simple in structure, easy operating is done carrier gas with air, does not need chemical reagent and H
2, high-purity gas carrier gas such as He, cost is low, highly sensitive, the nano catalytic luminescence of favorable reproducibility, long service life detects methyl alcohol and methyl tert-butyl ether in the gasoline method and detecting device.
Background technology:
Gasoline is formed very complicated, and it is individual that the component of having known reaches hundreds of, even thousands of.General ethanol petrol is in gasoline, to add ethanol (for example E10 gasoline promptly adds 9.5%～10.5% (V/V) ethanol) at present, because methyl alcohol is relatively cheap, therefore also often is added in the blended gasoline.Methyl alcohol toxicity is bigger, mainly acts on nervous system, has tangible anesthetic action.Main impaired organ is central nervous system, optic nerve and retina after the acute methanol poisoning, regular meeting occur dizziness, headache, dizzy, weak, lurch, have a sleepless night, phenomenons such as apathy, clouding of consciousness; The serious acute methanol poisoning eyesight can occur and sharply descend, even loses the sight of both eyes, at last can be dead because of respiratory failure.Therefore, the methanol content in the blended gasoline must satisfy standard-required, otherwise is judged to be non-conformity article.Because methyl tert-butyl ether (being MTBE) can significantly improve the octane value of unleaded gasoline; Therefore also often be added in the blended gasoline; But because methyl tert-butyl ether in the nature difficult degradation, have the hidden danger of polluted underground water, so its addition is limited by strictness also; Otherwise be regarded as violating environmental regulation, be judged to be non-conformity article.At present, when methyl alcohol is with the methyl tertbutyl ether content in check such as the U.S. ASTMD 6839-2002 standard gasoline, all be employing multidimensional gas chromatograph (like the M3 reformulated gasoline analyser of AC company).Not only instrument and equipment cost an arm and a leg (more than 120 ten thousand yuan), analysis time long (about 75 minutes); And separation process is complicated, influenced factor is many; Even under identical separation condition to also often there being unknown peak to occur in the gasoline sample analytic process of different process; The chromatographic peak broadening causes bigger quantitative error, the accuracy that influence is measured.
Existing nano-material surface-catalyzed luminescent detecting device is to be that to place diameter be that 12～20mm, length are in the quartz ampoule of 100～150mm to 4～7mm electric ceramic rod with the diameter that scribbles nano material; Diagonally opposing corner is provided with injection port, drain on quartz ampoule, corresponding optical filter or grating, the photosignal conversion equipment (near ultraviolet sensitive spectroscopy measurement type Weak-luminescence measuring instrument, photomultiplier etc.) of being provided with nano material outside quartz ampoule.During measurement; The electric ceramic rod heats nano material; Sampling systems such as pneumatic pump get into quartz ampoule with carrier gas from injection port with sample, and the nano-material surface of flowing through is discharged from drain, and the nano-material surface-catalyzed light that sends is behind optical filter or grating removal parasitic light; Become the electric signal that is adapted to data processing units such as microcomputer through the photosignal conversion equipment again, carry out check and analysis.Nano material in the existing nano-material surface-catalyzed luminescent detecting device adopts alundum (Al, zinc paste, iron oxide etc. usually; Be used for quantitative test ethanol, trimethylamine etc. and food hormone medicine residue detection etc., have simple in structure, easy operating, (several ten thousand yuan) cheap for manufacturing cost, selectivity is strong, operating cost is few, long service life, highly sensitive and high repeatability and other advantages.But up to now also not about detect methyl alcohol and the method for methyl tert-butyl ether and the relevant report of detecting device in the gasoline simultaneously with nano-material surface-catalyzed luminescent.
Summary of the invention:
The present invention is in order to solve the above-mentioned technical matters of existing in prior technology, a kind of simple in structure, easy operating to be provided, do carrier gas with air, not needing chemical reagent and H
2, high-purity gas carrier gas such as He, cost is low, highly sensitive, the nano catalytic luminescence of favorable reproducibility, long service life detects methyl alcohol and methyl tert-butyl ether in the gasoline method and detecting device.
Technical solution of the present invention is: the method for methyl alcohol and methyl tert-butyl ether in a kind of nano catalytic luminescence detection gasoline; It is characterized in that it being to detect with the nano catalytic luminescence reactor; Used nano material is a tin ash; The detection wavelength is 400～460nm, 120～300 ℃ of heating-up temperature scopes, flow rate of carrier gas 1～40ml/min.
The method of methyl alcohol and methyl tert-butyl ether is used detecting device in a kind of detection of nano catalytic luminescence according to claim 1 gasoline; Optical filter or grating 1, photosignal conversion equipment 2 and nano material 3 are arranged; Said nano material 3 is a tin ash, and the wavelength of said optical filter or grating is 400～460nm.
Be provided with housing 4, be built-in with heating element 5 and quartz capillary 6 at housing 4, said nano material 3 is coated in the inwall of quartz capillary 6 and leaves transparent surface 7; Transparent surface 7 is oppositely arranged with optical filter or grating 1, and the two ends of quartz capillary 6 join with sample introduction pipe 8, blow-down pipe 9 respectively.
Be equipped with photo-conduction cell 10 between said transparent surface 7 and optical filter or the grating 1.
The diameter of the middle part of said quartz capillary 6 has rounding off face 11 less than two ends between middle part and the two ends, said nano material 3 is coated in the middle part.
Said sample introduction pipe 8, blow-down pipe 9 are kapillary, are plugged in the two ends of quartz capillary 6.
Described photo-conduction cell 10 is an optical fiber.
The diameter of the middle part of said quartz capillary 6 is 0.1～0.75mm.
The present invention is set at tin ash with the nano material in the nano catalytic luminescence detecting device; The concentration of light signal that is detected and methyl alcohol and methyl tert-butyl ether is linear; Can realize that content to methyl alcohol in the gasoline and methyl tert-butyl ether carries out the while fast, accurately detect, overcome and analyzed with gas chromatograph that existing instrument and equipment costs an arm and a leg, analysis time long and the shortcoming of poor accuracy.Have simple in structure, easy operating, (several ten thousand yuan) with low cost, selectivity is strong, operating cost is few, long service life, highly sensitive and high repeatability and other advantages.
Description of drawings:
Fig. 1 is the structural representation of the embodiment of the invention 2.
Fig. 2 is the structural representation of the embodiment of the invention 3.
Embodiment:
Embodiment 1:
Select existing nano-material surface-catalyzed luminescent detecting device for use; But detecting device uses nano material to be tin ash, and it is 400～460nm that detecting device uses the wavelength of optical filter or grating, and it is 440～460nm that methyl alcohol detects wavelength; The detection wavelength of methyl tert-butyl ether is 400～425; The heating-up temperature scope is 120～300 ℃ during detection, and flow rate of carrier gas is 1～40ml/min, range of linearity 100ug～300mg/mL.
Experimental example 1: with 93
#Unleaded gasoline is a sample, and the content of the methyl alcohol that the method for use embodiment 1 is measured is 0.09% (V/V), and the detected value of multidimensional gas chromatographic is 0.08% (V/V); The content of the methyl tert-butyl ether of measuring is 0.65% (V/V), the detected value 0.62% (V/V) of multidimensional gas chromatographic.
Embodiment 2:
As shown in Figure 1: as material and fixed form to be arranged all with the optical filter or the grating 1 of prior art; Photosignal conversion equipment 2 is 400～460nm with the wavelength of prior art different is optical filter or grating 1, is provided with housing 4; Be built-in with heating element 5 and quartz capillary 6 at housing 4; Heating element 5 and quartz capillary 6 can be used any of prior art, and heating element 5 can join with temperature-control circuit, make the temperature factor that influences catalytic luminescence accurately controlled.Scribble nano material 3 at quartz capillary 6 inwalls, nano material 3 adopts tin ash.Must reserve the part blank when being coated with nano material 3, promptly transparent surface 7, leave some space like on the downside that 3 of nano materials is coated in quartz capillary 6 inwalls or the part on upper side.Transparent surface 7 is oppositely arranged with optical filter or grating 1, and the two ends of quartz capillary 6 join with sample introduction pipe 8, blow-down pipe 9 respectively.
Detection method is with embodiment 1.
Embodiment 3:
As shown in Figure 2:
Basic structure is with embodiment 1, and different with embodiment 1 is for fear of the loss of light signal and the interference of parasitic light, between said transparent surface 7 and optical filter or grating 1, to be equipped with photo-conduction cell 10.The diameter of the middle part of said quartz capillary 6 is less than two ends, and the diameter of middle part is 0.1～0.75mm, and rounding off face 11 is arranged between middle part and the two ends, and said nano material 3 is coated in the middle part.For ease of being connected of quartz capillary 6 and sample introduction pipe 8, blow-down pipe 9, dismounting; Said sample introduction pipe 8, blow-down pipe 9 preferably are kapillary; The polyimide coating of kapillary outside just can guarantee closely to be plugged in the two ends of quartz capillary 5, and said photo-conduction cell 10 is an optical fiber.
Detection method is with embodiment 1.
Experimental example 2: with 97
#Unleaded gasoline is a sample, and the content of the methyl alcohol that present embodiment 2,3 is measured is 0.04% (V/V), and the detected value of multidimensional gas chromatographic is 0.03% (V/V); The content of the methyl tert-butyl ether of measuring is 5.28% (V/V), the detected value 5.01% (V/V) of multidimensional gas chromatographic.
Claims (4)
1. a nano catalytic luminescence detects the detecting device that methyl alcohol and methyl tert-butyl ether are used in the gasoline; It is characterized in that: be provided with housing (4); Be built-in with heating element (5) and quartz capillary (6) at housing (4), nano material (3) is coated in the inwall of quartz capillary (6) and leaves transparent surface (7); Transparent surface (7) is oppositely arranged with optical filter or grating (1); The two ends of quartz capillary (6) join with sample introduction pipe (8), blow-down pipe (9) respectively; Said nano material (3) is a tin ash; The wavelength of said optical filter or grating is 400～460nm, 120～300 ℃ of heating-up temperature scopes, flow rate of carrier gas 1～40ml/min; The diameter of the middle part of said quartz capillary (6) has rounding off face (11) less than two ends between middle part and the two ends, said nano material (3) is coated in the middle part; Said sample introduction pipe (8), blow-down pipe (9) are kapillary, are plugged in the two ends of quartz capillary (6).
2. the detecting device that methyl alcohol and methyl tert-butyl ether are used in the nano catalytic luminescence detection gasoline according to claim 1 is characterized in that: be equipped with photo-conduction cell (10) between said transparent surface (7) and optical filter or the grating (1).
3. the detecting device that methyl alcohol and methyl tert-butyl ether are used in the nano catalytic luminescence detection gasoline according to claim 2, it is characterized in that: described photo-conduction cell (10) is an optical fiber.
4. the detecting device that methyl alcohol and methyl tert-butyl ether are used in the nano catalytic luminescence detection gasoline according to claim 1, it is characterized in that: the diameter of the middle part of said quartz capillary (6) is 0.1～0.75mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100129609A CN101614669B (en) | 2009-08-06 | 2009-08-06 | Method and detector for detecting methanol and methyl tertiary butyl ether in gasoline by nano cataluminescence |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100129609A CN101614669B (en) | 2009-08-06 | 2009-08-06 | Method and detector for detecting methanol and methyl tertiary butyl ether in gasoline by nano cataluminescence |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101614669A CN101614669A (en) | 2009-12-30 |
| CN101614669B true CN101614669B (en) | 2012-06-27 |
Family
ID=41494431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100129609A Expired - Fee Related CN101614669B (en) | 2009-08-06 | 2009-08-06 | Method and detector for detecting methanol and methyl tertiary butyl ether in gasoline by nano cataluminescence |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101614669B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101793836B (en) * | 2010-03-18 | 2011-09-21 | 中华人民共和国辽宁出入境检验检疫局 | Method for simultaneously detecting methanol and ethanol in gasoline by using photoelectric double signals and detector thereof |
| CN101799424B (en) * | 2010-03-18 | 2011-09-21 | 中华人民共和国辽宁出入境检验检疫局 | Method for simultaneously detecting ethanol and MTBE (methyl tert-butyl ether) in gasoline by photoelectric double-signal and detector |
| CN102127433B (en) * | 2010-12-31 | 2013-12-25 | 中华人民共和国辽宁出入境检验检疫局 | Tin dioxide nano-rod material for nanocatalysis luminescent sensor and preparation method thereof |
| CN103163123B (en) * | 2013-02-22 | 2015-05-20 | 北京联合大学生物化学工程学院 | Catalysis sensitive material for methanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435685A (en) * | 2002-01-29 | 2003-08-13 | 清华大学 | Luminous gas-sensitive sensor based on nanomaterial and process for film-forming of nanomaterial |
| CN1554939A (en) * | 2003-12-23 | 2004-12-15 | 清华大学 | Method for detecting organic molecule in solution by nano material catalytic light emitting and detector |
-
2009
- 2009-08-06 CN CN2009100129609A patent/CN101614669B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435685A (en) * | 2002-01-29 | 2003-08-13 | 清华大学 | Luminous gas-sensitive sensor based on nanomaterial and process for film-forming of nanomaterial |
| CN1554939A (en) * | 2003-12-23 | 2004-12-15 | 清华大学 | Method for detecting organic molecule in solution by nano material catalytic light emitting and detector |
Non-Patent Citations (3)
| Title |
|---|
| JP特开平9-145621A 1997.06.06 |
| 徐旸.纳米SnO2/萘酞菁铜及其杂化薄膜的制备与气敏性质研究.《黑龙江大学硕士学位论文》.2003,第1-8页. * |
| 饶志明 等.基于TiO2-Y2O3粉体催化发光甲醇气体传感器的研究.《化学学报》.2007,第65卷(第6期),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101614669A (en) | 2009-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Petruci et al. | Online analysis of H2S and SO2 via advanced mid-infrared gas sensors | |
| CN101614669B (en) | Method and detector for detecting methanol and methyl tertiary butyl ether in gasoline by nano cataluminescence | |
| CN103336070A (en) | Detection device and method for quantitatively detecting composition of sulfur-containing fault gas in sulfur hexafluoride electrical equipment | |
| CN101793835B (en) | Method for simultaneously detecting hydrogen sulfide and thiol in crude oil by using photoelectric double signals and detector thereof | |
| CN203870077U (en) | Secondary cold trap enrichment device and GC-FID (Gas Chromatography-Flame Ionization Detector) combined device for detecting trace phosphine | |
| CN110702639A (en) | Method for measuring furfural content in wool aldehyde | |
| CN108181407B (en) | Method for detecting impurity F in ibuprofen raw material | |
| CN104007196A (en) | Secondary cold trap enrichment and GC-FID (Gas Chromatography-Flame Ionization Detector) combining device and method for detecting trace hydrogen phosphide | |
| CN101571484B (en) | Nano-material surface-catalyzed luminescent micro-sensor | |
| CN102262082B (en) | Optical fiber sensor-molecular imprinting online detection method for detecting propofol in biological samples and optical fiber sensor-molecular imprinting online detection device. | |
| CN102072899B (en) | Catalytic light signal detection method for detecting hydrogen sulfide in gas and detector | |
| CN203203928U (en) | On-line detection instrument for total lead | |
| CN102854267B (en) | Measuring method of trace oxy-compound in liquid-phase propylene | |
| CN201417254Y (en) | Nano material surface catalytic luminescence miniature sensor | |
| CN101799424B (en) | Method for simultaneously detecting ethanol and MTBE (methyl tert-butyl ether) in gasoline by photoelectric double-signal and detector | |
| CN103776931A (en) | Measuring method of ethylamine in workplace air | |
| CN110895266B (en) | Analysis device and method for measuring content of hydrogen sulfide and phosphine | |
| CN101793836B (en) | Method for simultaneously detecting methanol and ethanol in gasoline by using photoelectric double signals and detector thereof | |
| CN102305835B (en) | Method for detecting formic acid by using hydrogen flame ionization detector based on catalytic reduction technology | |
| CN103257117A (en) | Rapid gasoline component measurement system | |
| CN202947998U (en) | Chromatographic instrument | |
| CN102128824B (en) | Method for detecting optical signals of H2S in natural gas and detector thereof | |
| CN2553374Y (en) | Double-beam ultraviolet detector | |
| CN201945556U (en) | Nano catalytic luminescent sensor with reflection layer | |
| CN201955307U (en) | Nanometer catalyzed luminous spiral sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120627 Termination date: 20130806 |