CN102072899A - Catalytic light signal detection method for detecting hydrogen sulfide in gas and detector - Google Patents
Catalytic light signal detection method for detecting hydrogen sulfide in gas and detector Download PDFInfo
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- CN102072899A CN102072899A CN2010105818691A CN201010581869A CN102072899A CN 102072899 A CN102072899 A CN 102072899A CN 2010105818691 A CN2010105818691 A CN 2010105818691A CN 201010581869 A CN201010581869 A CN 201010581869A CN 102072899 A CN102072899 A CN 102072899A
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Abstract
The present invention discloses a catalytic light signal detection method for detecting hydrogen sulfide in gas and a detector. The detection method has high detection efficiency and accuracy and adopts a nano catalytic light detector for detection. A nano composite material of CeO2 and Al2O3 is adopted, wherein the mass of the CeO2 accounts for 5-20 percent of the total mass of the nano composite material, the detection wavelength is 400-460nm, the heating temperature range of the nano material is 280-400 DEG C, air is used as a carrier gas, and the flow rate of the carrier gas is 50-80ml/min. The detector comprises a quartz bottle, the upper end of the cylindrical quartz bottle is provided with an upper cover, the upper cover is provided with a sample feeding port and an emptying port, and a positive electrode and a negative electrode are fixed on the upper cover; a ceramic tube is arranged in the quartz bottle, a heating wire is arranged in the ceramic tube, and the two ends of the heating wire are respectively connected with the positive electrode and the negative electrode; and a plurality of small quartz tubes are filled between the quartz bottle and the ceramic tube; and the outer surfaces of the small quartz tubes are coated with the nano material.
Description
Technical field:
The present invention relates to a kind of method and detecting device thereof that detects hydrogen sulfide content in the rock gas, especially a kind of simple in structure, easy operating, is catalytic luminescence signal detecting method and the detecting device thereof that carrier gas, operating cost are low, have sulfuretted hydrogen in the high rock gas of good stable and reappearance, detection efficiency and precision with the air.
Background technology:
Original rock gas is that hydrocarbon is main combination gas, and the existing useful component of making fuel and raw material also has useless, poisonous component, as sulfuretted hydrogen (H
2Component such as S).The marketable natural gas gas quality index is then by gross calorific value, H
2S content, total sulfur content, CO
25 indexs such as content and water dew point constitute.H
2S is colourless inflammable gas with rotten-egg odour, and proportion 1.19 easily gathers low-lying place, is hypertoxic waste gas in the commercial production.It is a kind of never poison, be again asphyxiating and irritative gas, main injury nervous centralis and respiratory system, eyes and heart etc., irritations such as the lighter shows as and sheds tears, eye shouting pain, runny nose and bottleneck throat burning heat sensation, or with headache, dizzy, weak, nauseating etc.; Moderate intoxication person mucosa irritation sx cough, uncomfortable in chest, blurred vision, eye chemosis occur and symptoms such as obvious headache, dizziness is arranged, and the slight disturbance of consciousness occurs; Stupor, pulmonary edema, respiratory and circulatory failure then appear in severe intoxication; As suck H
2S concentration was called " lightning class death " with regard to the energy causing death in 2 minutes to 800ppm.Simultaneously, H
2S has the strong corrosion effect to the steel of drilling well apparatus and well head set-up; In gas production, gas transmission line, H
2S corrosion thing and sulphur precipitation easily cause pipe network to stop up and the gas-bearing formation infringement, so H
2S is regarded as the drugpusher in the rock gas.Along with rock gas is increased day by day by increasingly extensive use, environmental protection pressure, people are to the H in the rock gas
2S content is more paid close attention to, and requires at (usually below 1ppm) within the environmental protection standard.
Measure H in the rock gas at present
2The method of S is to utilize vapor-phase chromatography or American Society Testing and Materials's standard " ASTM 4810-06 tests the standard method of sulfuretted hydrogen in the rock gas with the painted length method of detector tube " etc. to measure.Gas chromatograph cost an arm and a leg and method of operating loaded down with trivial details, increased time of analyzing and testing; The poor accuracy of the painted length method of detector tube.
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 and high repeatability and other advantages.Up to now also not about detecting the method for sulfuretted hydrogen in the rock gas and the relevant report of detecting device 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 is provided, is catalytic luminescence signal detecting method and the detecting device thereof that carrier gas, operating cost are low, have sulfuretted hydrogen in the high rock gas of good stable and reappearance, detection efficiency and precision with the air.
Technical solution of the present invention is: the catalytic luminescence signal detecting method of sulfuretted hydrogen in a kind of rock gas, it is characterized in that it being to detect with the nano catalytic luminescence detecting device, and used nano material is CeO
2With Al
2O
3Nano composite material, CeO
2Account for 5～20% of nano composite material gross mass, the detection wavelength is 400～460nm, 280～400 ℃ of nano material heating-up temperature scopes, and air is as carrier gas, and flow rate of carrier gas is 50～80ml/min.
The catalytic luminescence signal detecting method detecting device of sulfuretted hydrogen in a kind of above-mentioned rock gas, it is characterized in that: the cylindrical quartz bottle is arranged, in cylindrical quartz bottle upper end loam cake is arranged, be provided with injection port and drain, be fixed with positive electrode and negative electrode last covering last covering; Described quartzy bottle is built-in with ceramic pipe, and heater strip is arranged in the ceramic pipe, and the heater strip two ends join with positive electrode and negative electrode respectively; Be filled with a plurality of little quartz ampoules between described quartzy bottle and the ceramic pipe, gravelstone English tube outer surface scribbles nano material.
The diameter of described cylindrical quartz bottle and highly be 15～30mm; Described ceramic pipe length is 5～10mm, and external diameter is 2～5mm; The length of described little quartz ampoule is 2～10mm, and external diameter is 1～3mm.
The present invention is set at cerium oxide and ferric oxide nano compound substance with the nano material in the nano catalytic luminescence detecting device, in quartzy bottle, be filled with a plurality of little quartz ampoule that outside surface scribbles nano material again simultaneously, increase the surface area of nano-material coating, further improved luminescence efficiency; The flow path dead volume of sample carrier gas reduces greatly simultaneously, 2 S component contacts more abundant in the rock gas with nano-material surface, response time on nano material shortens greatly, signal response time is rapid, signal to noise ratio (S/N ratio) strengthens, the signal bands of a spectrum narrow down (similar sharp-pointed chromatogram elution curve), and detection efficiency, resolution and detection sensitivity all improve greatly.The light signal that is detected becomes correlativity with the concentration of sulfuretted hydrogen in the rock gas, can realize the content of sulfuretted hydrogen in the rock gas is carried out fast, accurately detects, overcome with gas chromatograph and analyzed the shortcoming that existing instrument and equipment costs an arm and a leg, analysis time is long.Have (several ten thousand yuan) simple in structure, with low cost, easy operating, selectivity is strong, operating cost is few, have good stable and reappearance, detection efficiency and precision advantages of higher.
Description of drawings:
Fig. 1 is the structural representation of embodiment of the invention detecting device.
Embodiment:
The embodiment of the invention has been provided with cylindrical quartz bottle 1, in cylindrical quartz bottle 1 upper end loam cake 2 is arranged, and is provided with injection port 3 and drain 4 on loam cake 2, is fixed with positive electrode 5 and negative electrode 6 on loam cake 2; Described quartzy bottle 1 is built-in with ceramic pipe 7, and heater strip 8 is arranged in the ceramic pipe 7, and heater strip 8 two ends join with positive electrode 5 and negative electrode 6 respectively; Be filled with a plurality of little quartz ampoules 9 between described quartzy bottle 1 and the ceramic pipe 4, little quartz ampoule 9 outside surfaces scribble nano material, and nano material is by CeO
2With Al
2O
3The nano composite material that mixes, CeO
2Account for 10% of nano composite material gross mass; The diameter of cylindrical quartz bottle 1 and highly be 15～30mm; Described ceramic pipe 7 length are 5～10mm, and external diameter is 2～5mm; The length of described little quartz ampoule 9 is 2～10mm, and external diameter is 1～3mm.The detection wavelength is 425nm, and detected temperatures is under the normal temperature and pressure, 320 ℃ of the heating-up temperature scopes of nano material, and flow rate of carrier gas 20ml/min, sample size are 1ml, the operating voltage of photomultiplier is 1000kv, the range of linearity 0.05-500ppm that sulfuretted hydrogen detects.
Experimental example 1: with Australian inlet natural gas is laboratory sample, the content of the sulfuretted hydrogen of measuring with the method for embodiment 1 is 0.72ppm, and the detected value of " ASTM 4810-06 tests the standard method of sulfuretted hydrogen in the rock gas with the painted length method of detector tube " is 0.7ppm.
Experimental example 2: with the ring inlet natural gas is laboratory sample, the content of the sulfuretted hydrogen of measuring with the method for embodiment 1 is 0.83ppm, and the detected value of " ASTM 4810-06 tests the standard method of sulfuretted hydrogen in the rock gas with the painted length method of detector tube " is 0.8ppm.
Claims (4)
1. the catalytic luminescence signal detecting method of sulfuretted hydrogen in the rock gas is characterized in that it being to detect with the nano catalytic luminescence detecting device, and used nano material is CeO
2With Al
2O
3Nano composite material, CeO
2Account for 5～20% of nano composite material gross mass, the detection wavelength is 400～460nm, 280～400 ℃ of nano material heating-up temperature scopes, and air is as carrier gas, and flow rate of carrier gas is 50～80ml/min.
2. catalytic luminescence signal detecting method detecting device of sulfuretted hydrogen in the rock gas according to claim 1, it is characterized in that: cylindrical quartz bottle (1) is arranged, in cylindrical quartz bottle (1) upper end loam cake (2) is arranged, on loam cake (2), be provided with injection port (3) and drain (4), on loam cake (2), be fixed with positive electrode (5) and negative electrode (6); Described quartzy bottle (1) is built-in with ceramic pipe (7), and heater strip (8) is arranged in the ceramic pipe (7), and heater strip (8) two ends join with positive electrode (5) and negative electrode (6) respectively; Be filled with a plurality of little quartz ampoules (9) between described quartzy bottle (1) and the ceramic pipe (7), little quartz ampoule (9) outside surface scribbles nano material.
3. quartz ball filled type homonymy according to claim 2 turnover nano catalytic luminescence detecting device is characterized in that: the diameter of described cylindrical quartz bottle (1) and highly be 15～30mm; Described ceramic pipe (7) length is 5～10mm, and external diameter is 2～5mm; The length of described little quartz ampoule (9) is 2～10mm, and external diameter is 1～3mm.
4. the catalytic luminescence signal detecting method detecting device of sulfuretted hydrogen in the rock gas according to claim 2, it is characterized in that: described nano composite material is CeO
2With Al
2O
3, CeO
2Account for 5～20% of nano composite material gross mass.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010581869.1A CN102072899B (en) | 2010-12-10 | 2010-12-10 | Catalytic light signal detection method for detecting hydrogen sulfide in gas and detector |
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| CN201010581869.1A CN102072899B (en) | 2010-12-10 | 2010-12-10 | Catalytic light signal detection method for detecting hydrogen sulfide in gas and detector |
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| CN102072899B CN102072899B (en) | 2014-09-24 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105164516A (en) * | 2013-04-16 | 2015-12-16 | 德尔格安全股份两合公司 | Measuring device, reaction carrier and measuring method |
| CN108444987A (en) * | 2018-03-19 | 2018-08-24 | 广东华晟安全职业评价有限公司 | The detection method of hydrogen sulfide gas in a kind of detection workplace |
| CN113189952A (en) * | 2021-05-12 | 2021-07-30 | 中国石油天然气股份有限公司 | Product natural gas quality control interlocking system and control method for natural gas purification plant |
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| WO2007042081A1 (en) * | 2005-10-14 | 2007-04-19 | Alstom Technology Ltd | Optical sensor device for local analysis of a combustion process in a combustor of a thermal power plant |
| US20090068755A1 (en) * | 2007-09-11 | 2009-03-12 | Steeves Diane M | Optical biosensing platform utilizing nanocrystalline zinc oxide |
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2010
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| WO2007042081A1 (en) * | 2005-10-14 | 2007-04-19 | Alstom Technology Ltd | Optical sensor device for local analysis of a combustion process in a combustor of a thermal power plant |
| US20090068755A1 (en) * | 2007-09-11 | 2009-03-12 | Steeves Diane M | Optical biosensing platform utilizing nanocrystalline zinc oxide |
| CN101793835A (en) * | 2010-03-18 | 2010-08-04 | 中华人民共和国辽宁出入境检验检疫局 | Method for simultaneously detecting hydrogen sulfide and thiol in crude oil by using photoelectric double signals and detector thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105164516A (en) * | 2013-04-16 | 2015-12-16 | 德尔格安全股份两合公司 | Measuring device, reaction carrier and measuring method |
| CN105164516B (en) * | 2013-04-16 | 2018-12-18 | 德尔格安全股份两合公司 | Measuring device, reaction pedestal and measurement method |
| US11117126B2 (en) | 2013-04-16 | 2021-09-14 | Dräger Safety AG & Co. KGaA | Measuring device, reaction carrier and measuring method |
| CN108444987A (en) * | 2018-03-19 | 2018-08-24 | 广东华晟安全职业评价有限公司 | The detection method of hydrogen sulfide gas in a kind of detection workplace |
| CN108444987B (en) * | 2018-03-19 | 2021-02-12 | 广东华晟安全职业评价有限公司 | Detection method for detecting hydrogen sulfide gas in workplace |
| CN113189952A (en) * | 2021-05-12 | 2021-07-30 | 中国石油天然气股份有限公司 | Product natural gas quality control interlocking system and control method for natural gas purification plant |
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