CN101793836B - Method for simultaneously detecting methanol and ethanol in gasoline by using photoelectric double signals and detector thereof - Google Patents
Method for simultaneously detecting methanol and ethanol in gasoline by using photoelectric double signals and detector thereof Download PDFInfo
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- CN101793836B CN101793836B CN2010101265232A CN201010126523A CN101793836B CN 101793836 B CN101793836 B CN 101793836B CN 2010101265232 A CN2010101265232 A CN 2010101265232A CN 201010126523 A CN201010126523 A CN 201010126523A CN 101793836 B CN101793836 B CN 101793836B
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Abstract
The invention discloses a method for simultaneously detecting methanol and ethanol in gasoline by using photoelectric double signals and a detector thereof. The invention has the advantages of simple structure, easy operation, low operating cost (using air as the carrier gas), favorable stability and reproducibility, and high detection efficiency and precision. The nano catalysis luminescent detector is used for detection; the nano material is titanium oxide/tin oxide composite material, and tin oxide accounts for 35-55% of the total mass of the composite material; the detection wavelength is 400-460 nm; the heating temperature range for the nano material is 200-300 DEG C; the flow rate of the carrier gas is 20-200 ml/min; a voltage is applied to both ends of the nano material; and the current value is taken as the detection signal. Compared with the prior art, the detector is characterized in that both ends of the nano semiconductor metal oxide are respectively provided with a positive electrode and a negative electrode, and a current output and photoelectric signal conversion device between the positive electrode and the negative electrode is connected with an electric signal detection circuit.
Description
Technical field:
The present invention relates to a kind of method and checkout equipment that detects methyl alcohol and ethanol in the gasoline, especially a kind of simple in structure, easy operating, operating cost low (is carrier gas with the air), have method and detecting device that good stable and the high photoelectricity dual signal of reappearance, detection efficiency and precision detect methyl alcohol and ethanol in the gasoline simultaneously.
Background technology:
Gasoline is formed very complicated, and it is individual that the component of having known reaches hundreds of, even thousands of.General in the market ethanol petrol is a kind of blended gasoline, promptly adds ethanol (for example E10 gasoline promptly adds 9.5%～10.5% (V/V) ethanol) in gasoline, and the ethanol content that is added belongs to the index that must check; Because methyl alcohol is relatively cheap, therefore also often be 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.
At present, according in check such as U.S. ASTMD 6839-02 (2007) the standard gasoline when methyl alcohol, ethanol content, be to adopt multidimensional gas chromatograph (as 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 complexity, influenced factor are 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 that the diameter that will scribble nano material is that to place diameter be that 12～20mm, length are in the quartz ampoule of 100～150mm to 4～7mm electric ceramic rod, 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 enter quartz ampoule with carrier gas from injection port with sample, the nano-material surface of flowing through is discharged from drain, 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, because the catalytic luminescence signal of methyl alcohol and ethanol is approaching, make the catalytic luminescence signal on the nano catalytic material surface of flowing through be difficult to differentiate, sometimes need to rely on the change analysis condition to come separate signal, not only complex operation, prolonged the time of analyzing and testing, main is the accuracy that has directly influenced quantitative test.Up to now also not about detect methyl alcohol and the method for ethanol and the relevant report of detecting device in the gasoline simultaneously with nano-material surface-catalyzed luminescent and electrochemical signals.
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, operating cost low (is carrier gas with the air) is provided, has method and detecting device that good stable and the high photoelectricity dual signal of reappearance, detection efficiency and precision detect methyl alcohol and ethanol in the gasoline simultaneously.
Technical solution of the present invention is: a kind of photoelectricity dual signal detects the method for methyl alcohol and ethanol in the gasoline simultaneously, it is characterized in that detecting with the nano catalytic luminescence detecting device, used nano material is the compound substance of titanium dioxide and tin oxide, tin oxide is 35～55% of compound substance gross mass, the detection wavelength is 400～460nm, 200～300 ℃ of the heating-up temperature scopes of nano material, flow rate of carrier gas 20～200ml/min; Applying voltage and get the electric current that is produced at the two ends of described nano material is detection signal.
A kind of above-mentioned photoelectricity dual signal detects the method detecting device of methyl alcohol and ethanol in the gasoline simultaneously, quartz ampoule is arranged, quartz ampoule is provided with injection port and drain, quartz ampoule is built-in with the ceramic heat rod, at ceramic heat rod internal fixation heating element is arranged, outside the ceramic heat rod, scribble nano semi-conductor metal oxide, corresponding optical filter or grating and the photosignal conversion equipment of being provided with nano semi-conductor metal oxide, described nano semi-conductor metal oxide is the compound substance of titanium dioxide and tin oxide, tin oxide is 35～55% of compound substance gross mass, two ends at described nano semi-conductor metal oxide are respectively equipped with positive electrode, negative electrode, positive electrode, electric current output between the negative electrode and photosignal conversion equipment and electrical signal detection circuit join.
The center of described injection port and drain all is positioned on the axis of quartz ampoule.
The present invention is set at titanium dioxide and tin oxide nano compound substance with the nano material in the nano catalytic luminescence detecting device, the light signal that is detected all becomes correlativity with methyl alcohol with electrochemical signals with concentration of ethanol, can be simultaneously the content of methyl alcohol in the gasoline and ethanol be carried out fast, accurately detects, 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; Solved that prior art only gets that nano-material surface-catalyzed light signal detects and the luminous signal that exists is difficult to differentiate, complex operation, the problem that prolonged the analyzing and testing time, the present invention also has (several ten thousand yuan) simple in structure, with low cost, easy operating, selectivity is strong, operating cost is few, long service life, stability and reappearance is good, detection efficiency and precision advantages of higher.
Description of drawings:
Fig. 1 is the structural representation of the embodiment of the invention.
Embodiment:
Below in conjunction with description of drawings the specific embodiment of the present invention.
The embodiment of the invention is to detect with the nano catalytic luminescence detecting device, used nano material is the compound substance of titanium dioxide and tin oxide, tin oxide is 35～55% of compound substance gross mass, the detection wavelength is 400～460nm, 200～300 ℃ of the heating-up temperature scopes of nano material, flow rate of carrier gas 20～200ml/min, the atomizer temperature is 210 ℃ makes the sample atomizing, two ends in described nano material apply voltage, the electric current that makes intensity 1～15mA during by zero load nano material and to get the current value that is produced be detection signal.
Used detecting device is as shown in Figure 1: quartz ampoule 1 is arranged, quartz ampoule 1 is provided with injection port 2 and drain 3, quartz ampoule 1 is built-in with ceramic heat rod 4, at ceramic heat rod 4 internal fixation heating element 5 is arranged, outside ceramic heat rod 4, scribble nano semi-conductor metal oxide 6, with nano semi-conductor metal oxide 6 corresponding optical filter or grating 7 and the photosignal conversion equipments 8 of being provided with, described nano semi-conductor metal oxide 6 is the compound substance of titanium dioxide and tin oxide, tin oxide is 35～55% of compound substance gross mass, be respectively equipped with positive electrode 9 at the two ends of described nano semi-conductor metal oxide 6, negative electrode 10, can be at positive electrode 9, reometer (electrical signal detection circuit 11) joins between the negative electrode 10, also electric current can be drawn, current output terminal and mould/number conversion circuit 12 joins, and described photosignal conversion equipment 8 and mould/number conversion circuit 12 joins with microprocessor (electrical signal detection circuit 11) simultaneously.For fear of the big problem of dead volume that causes because of injection port 2 and drain 3 diagonal angle settings, the center of described injection port 2 and drain 3 all is positioned on the axis of quartz ampoule 1.
According to the method for prior art heating element 5 and power supply are joined during detection, simultaneously positive and negative electrode 9,10 and power supply are joined, the nano material of the electric current that makes intensity 1～15mA during by zero load.Gasoline atomized according to art methods and be carrier gas with the air, enter from injection port 2, flow out from drain 3, promptly the flow through composite layer of titanium dioxide and tin oxide of sample, generation and methyl alcohol become the light signal and the electric signal of correlativity with concentration of ethanol.By light signal and electric signal are handled and detected, can measure methyl alcohol and ethanol content separately in the gasoline, the range of linearity 0.002%～30.00% (V/V) that methyl alcohol detects, the range of linearity 0.005%～20.00% (V/V) that ethanol detects.
Experimental example 1: with the E10 ethanol petrol is laboratory sample, and the content of the ethanol of measuring with the method for the embodiment of the invention is 9.97% (V/V), and the detected value of multidimensional gas chromatographic is 10.23% (V/V); The content of the methyl alcohol of measuring with the method for embodiment is 0.02% (V/V), the detected value 0.02% (V/V) of multidimensional gas chromatographic.
Experimental example 2: with 93
#Unleaded gasoline is a laboratory sample, and the content of the ethanol of measuring with the method for embodiment is 0.00% (V/V), and the detected value of multidimensional gas chromatographic is 0.00% (V/V); The content of the methyl alcohol of measuring with the method for embodiment is 0.00% (V/V), the detected value 0.00% (V/V) of multidimensional gas chromatographic.
Experimental example 3: with the blended gasoline is laboratory sample, and the content of the ethanol of measuring with the method for embodiment is 10.05% (V/V), and the detected value of multidimensional gas chromatographic is 10.27% (V/V); The content of the methyl alcohol of measuring with the method for embodiment is 0.12% (V/V), the detected value 0.13% (V/V) of multidimensional gas chromatographic.
Claims (3)
1. a photoelectricity dual signal detects the method for methyl alcohol and ethanol in the gasoline simultaneously, it is characterized in that detecting with the nano catalytic luminescence detecting device, used nano material is the compound substance of titanium dioxide and tin oxide, tin oxide is 35～55% of compound substance gross mass, the detection wavelength is 400～460nm, 200～300 ℃ of the heating-up temperature scopes of nano material, flow rate of carrier gas 20～200ml/min; Applying voltage and get the electric current that is produced at the two ends of described nano material is detection signal.
One kind according to claim 1 the photoelectricity dual signal detect the method detecting device of methyl alcohol and ethanol in the gasoline simultaneously, quartz ampoule (1) is arranged, quartz ampoule (1) is provided with injection port (2) and drain (3), quartz ampoule (1) is built-in with ceramic heat rod (4), at ceramic heat rod (4) internal fixation heating element (5) is arranged, outside ceramic heat rod (4), scribble nano semi-conductor metal oxide (6), corresponding optical filter or grating (7) and the photosignal conversion equipment (8) of being provided with nano semi-conductor metal oxide (6), it is characterized in that: described nano semi-conductor metal oxide (6) is the compound substance of titanium dioxide and tin oxide, tin oxide is 35～55% of compound substance gross mass, be respectively equipped with positive electrode (9) at the two ends of described nano semi-conductor metal oxide (6), negative electrode (10), positive electrode (9), electric current output and photosignal conversion equipment (8) between the negative electrode (10) join with electrical signal detection circuit (11).
3. photoelectricity dual signal according to claim 2 detects the method detecting device of methyl alcohol and ethanol in the gasoline simultaneously, and it is characterized in that: the center of described injection port (2) and drain (3) all is positioned on the axis of quartz ampoule (1).
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| CN2010101265232A CN101793836B (en) | 2010-03-18 | 2010-03-18 | Method for simultaneously detecting methanol and ethanol in gasoline by using photoelectric double signals and detector thereof |
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| CN2010101265232A CN101793836B (en) | 2010-03-18 | 2010-03-18 | Method for simultaneously detecting methanol and ethanol in gasoline by using photoelectric double signals and detector thereof |
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| CN101793836B true CN101793836B (en) | 2011-09-21 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1527051A (en) * | 2003-09-23 | 2004-09-08 | 清华大学 | Organic gas testing nano material method and sensor |
| CN101614669A (en) * | 2009-08-06 | 2009-12-30 | 中华人民共和国辽宁出入境检验检疫局 | The method and the detecting device of methyl alcohol and methyl tert-butyl ether in the nano catalytic luminescence detection gasoline |
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| US8114679B2 (en) * | 2007-09-11 | 2012-02-14 | The United States Of America As Represented By The Secretary Of The Army | Optical biosensing platform utilizing nanocrystalline zinc oxide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1527051A (en) * | 2003-09-23 | 2004-09-08 | 清华大学 | Organic gas testing nano material method and sensor |
| CN101614669A (en) * | 2009-08-06 | 2009-12-30 | 中华人民共和国辽宁出入境检验检疫局 | The method and the detecting device of methyl alcohol and methyl tert-butyl ether in the nano catalytic luminescence detection gasoline |
Non-Patent Citations (2)
| Title |
|---|
| Jinjun Shi et al..Nanosized SrCO3-based chemiluminescence sensor for ethanol.《Analytica Chimica Acta》.2002,第466卷(第1期),第69–78页. * |
| 叶青等.纳米Ce1-xMnxO2催化剂上乙醇催化氧化发光研究.《化学学报》.2006,第64卷(第8期),第751-755页. * |
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