CN102788851A - One-injection single-column sampling chromatographic analysis method for gas in transformer oil - Google Patents

One-injection single-column sampling chromatographic analysis method for gas in transformer oil Download PDF

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CN102788851A
CN102788851A CN2012102921420A CN201210292142A CN102788851A CN 102788851 A CN102788851 A CN 102788851A CN 2012102921420 A CN2012102921420 A CN 2012102921420A CN 201210292142 A CN201210292142 A CN 201210292142A CN 102788851 A CN102788851 A CN 102788851A
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chromatographic column
column
gas
sample introduction
methane conversion
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CN102788851B (en
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章金谋
张政
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Abstract

The invention relates to a method for gas chromatographic analysis. A one-injection single-column sampling chromatographic analysis method for gas in transformer oil in comprises separation of a chromatographic column, detection of a thermal conductivity cell and detection of an FID (Flame Ionization Detector), wherein before the detection of the FID, methane conversion needs to be carried out on gas by a methane conversion device. The method is characterized in that the methane conversion device is provided with a bypass regulation pipe and a bypass adjusting valve; the packing materials of the chromatographic column comprise about 56% of Porapak N-type packing material, about 14% of Porapak Q-type packing material, about 25% of Hayesep N-type packing material, and about 5% of Hayesep Q-type packing material according to the mass percentage. The method has the beneficial effects that one-injection sampling with a single column can be effectively realized, the cost is lower, the process is simple and convenient, and simultaneously the influence of unstable factors such as high-content CO and CO2 in the complex process on detection and separation of CH4 and C2H4 are overcome.

Description

Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method
[technical field]
The present invention relates to a kind of gas chromatography analysis method.
[background technology]
Mainly utilize gc analysis transformer oil dissolved gas in the prior art, generally adopt a pin sampling system, its advantage is to reduce analytical error, satisfies the few crude oil sample analysis of amount of gas evolved, simple to operate.A conventional pin sampling system comprises that mainly a twin columns parallel connection shunting and a pin sample introduction six-way valve switch two kinds of methods.
The defective of one pin sample introduction twin columns parallel connection shunting is following: the first, and split ratio is in operation and can changes; The second, the TCD reference must emptying and make the thermal conductivity cell detector unstability of base line fixed; The 3rd, the molecular sieve column of use can make CO 2Go out peak-to-peak molded breadth, long, the easy inefficacy of time; The 4th, O 2Interference shoulder peak, CH appear before making CO 4Before the heavy burden peak appears, interference measurement.
The defective that one pin sample introduction six-way valve switches method is following: the first, and the switching of valve causes baseline sudden change, impact analysis; The second, use the 13X molecular sieve column, serviceable life is short, is prone to because of adsorption moisture and CO 2And lost efficacy; The 3rd, there are CO, the CO of high-load 2To CH 4, C 2H 4The influence that separates; The 4th, C 2H 2Detection sensitivity is low.Above-mentioned defective mainly is that chromatographic column separating property and analysis process cause.
For this reason, people begin the single-column Study on Separation.At present, single-column separates CO, the CO that has high-load 2To CH 4, C 2H 4The influence that separates, this is because the CO and the CO of Gas in Oil of Transformer 2Content is often higher, and is common at hundreds of extremely thousands of ppm, and hydrocarbon gas content is generally lower, belongs to micro-rank.So GB GB/T7252-2001 regulation hydro carbons detection sensitivity is 0.1ppm, and CO, CO 2Be 25ppm.
[summary of the invention]
The object of the present invention is to provide a kind of Gas in Oil of Transformer analytical approach that can the single-column sample introduction, weaken single-column simultaneously and separate high-load CO, the CO that exists 2To CH 4, C 2H 4Detect the influence that separates.
The present invention realizes through following technical scheme:
Said Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method; Comprise that chromatographic column is separated, conductance cell detects and FID detects; Before FID detects, need gas is carried out methane conversion through the methane conversion device, said methane conversion device is provided with bypass adjustable pipe and bypass valve; Said chromatographic column filler is following:
Porapak N type filler about 56%
Porapak Q type filler about 14%
Hayesep N type filler about 25%
Hayesep Q type filler about 5%
Said number percent is mass percent.
Further, said chromatographic column manufacturing approach is following:
(1) chooses the chromatographic column that internal diameter is about 2mm;
(2) insert about 1cm silica wool at said chromatographic column one end, insert 1cm stainless (steel) wire or 1cm close-fitting tubule again, and the said chromatographic column other end is connected with steel cylinder with mixing;
(3) chromatographic column filler for preparing is placed said steel cylinder, and in steel cylinder, feed gas, utilize air pressure that said chromatographic column filler is charged into said chromatographic column;
(4) stop to ventilate to the post internal gas pressure and return to normal pressure, unload chromatographic column, insert about 1cm silica wool, insert 1cm stainless (steel) wire or 1cm close-fitting tubule again in said chromatographic column and the tank connected end of steel cylinder;
(5) populated chromatographic column is carried out burin-in process.
Further, the throughput of said bypass adjustable pipe is about 90% of total throughput.
Further, the said volatilizable solvent of step (4) can be 2 milliliters to 8 milliliters a acetone or alcohol.
Further, the gas that step (3) feeds is nitrogen, and the air pressure of feeding maintains between the 0.4mPa to 0.5mPa, about 15 minutes of duration of ventilation.
Further, can also comprise the steps: afterwards said chromatographic column not to be immersed in the water about 2mm with the tank connected end of steel cylinder, whether have bubble to come the test column internal gas pressure whether to return to normal pressure through checking in step (3).
Further, the burin-in process process is following described in the step (5):
(1) with chromatographic column one termination gas chromatograph injection port, other end emptying;
(2) feed nitrogen from injection port, post oven temperature, degree is made as about 130 degrees centigrade, and nitrogen flow is about 30mL/min, and digestion time is about 8 hours.
Beneficial effect of the present invention is: can effectively realize single-column one pin sample introduction, cost is lower, and simple flow has overcome the labile factor in the complicated flow process simultaneously, like high-load CO, CO 2To CH 4, C 2H 4Detect the influence that separates.
[description of drawings]
Fig. 1 is an analysis process synoptic diagram of the present invention;
Fig. 2 is a stratographic analysis total result synoptic diagram of the present invention;
Fig. 3 is a stratographic analysis local result synoptic diagram of the present invention;
Reference numeral: 1, injection port; 2, chromatographic column; 3, thermal conductivity cell detector; 4, methane conversion device; 5, fid detector; 6, bypass adjustable pipe; 7, bypass valve.
[embodiment]
Below in conjunction with accompanying drawing and embodiment the present invention is done and to further describe:
A kind of Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method; Comprise that chromatographic column is separated, conductance cell detects and FID detects;, FID needs gas is carried out methane conversion through methane conversion device 4 before detecting; It is characterized in that said methane conversion device 4 is provided with bypass adjustable pipe 6 and bypass valve 7;
Said chromatographic column 2 fillers are following:
Porapak N type filler about 56%
Porapak Q type filler about 14%
Hayesep N type filler about 25%
Hayesep Q type filler about 5%
Said number percent is mass percent.
Preferably, said chromatographic column 2 manufacturing approaches are following:
(1) chooses the chromatographic column that internal diameter is about 2mm;
(2) insert about 1cm silica wool at said chromatographic column one end, insert 1cm stainless (steel) wire or 1cm close-fitting tubule again, and the said chromatographic column other end is connected with steel cylinder with mixing;
(3) chromatographic column filler for preparing is placed said steel cylinder, and in steel cylinder, feed gas, utilize air pressure that said chromatographic column filler is charged into said chromatographic column;
(4) stop to ventilate to the post internal gas pressure and return to normal pressure, unload chromatographic column, insert about 1cm silica wool, insert 1cm stainless (steel) wire or 1cm close-fitting tubule again in said chromatographic column and the tank connected end of steel cylinder;
(5) populated chromatographic column is carried out burin-in process.
Preferably, the throughput of said bypass adjustable pipe 6 is about 90% of total throughput.
Preferably, the said volatilizable solvent of step (4) can be 2 milliliters to 8 milliliters a acetone or alcohol.
Preferably, the gas that step (3) feeds is nitrogen, and the air pressure of feeding maintains between the 0.4mPa to 0.5mPa, about 15 minutes of duration of ventilation.
Preferably, can also comprise the steps: afterwards said chromatographic column not to be immersed in the water about 2mm with the tank connected end of steel cylinder, whether have bubble to come the test column internal gas pressure whether to return to normal pressure through checking in step (3).
Preferably, the burin-in process process is following described in the step (5):
(1) with chromatographic column one termination gas chromatograph injection port, other end emptying;
(2) feed nitrogen from injection port, post oven temperature, degree is made as about 130 degrees centigrade, and nitrogen flow is about 30mL/min, and digestion time is about 8 hours.
Test parameters is following in the present embodiment:
Use N 2As the sample introduction carrier gas, flow is 22-25mL/min;
Use H 2As the reducing gas of methane conversion device 4 conversion usefulness, flow is 22-25mL/min;
Use H 2As the burning gas that supplies fid detector 5 usefulness, flow is 0-15mL/min;
Supplying the air mass flow of fid detector 5 is 300-400mL/min;
Methane conversion device 4 temperature 330-370 ℃ is catalyzer with Ni;
Chromatographic column 2 length that adopt are about 4m, stainless steel, external diameter 3mm, temperature 65-70 ℃;
Thermal conductivity cell detector 3 temperature 80-200 ℃, bridge stream 70-100mA;
Injection port 1 temperature is controlled at 80-200 ℃;
Through regulating the bypass valve 7 of the gas flow that gets into methane conversion device 4, make the collateral ventilation flow account for 90% of total flow, bypass adjustable pipe 6 length are 1m-2m, stainless steel, external diameter 3mm.
The chromatographic resolution result is following in the present embodiment:
Figure 1
This single-column and analysis process, single injected sampling can separate H fully in 8 minutes 2, O 2, CO, CO 2, CH 4, C 2H 6, C 2H 4, C 2H 2Etc. component.And CO, the CO of high-load have significantly been reduced 2To CH 4, C 2H 4The influence that separates.
According to the announcement and the instruction of above-mentioned instructions, those skilled in the art in the invention can also carry out suitable change and modification to above-mentioned embodiment.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection domain of claim of the present invention modifications more of the present invention and change.In addition, although used some specific terms in this instructions, these terms are explanation for ease just, the present invention is not constituted any restriction.

Claims (7)

1. Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method; Comprise that chromatographic column is separated, conductance cell detects and FID detects;, FID needs gas is carried out methane conversion through the methane conversion device before detecting; It is characterized in that said methane conversion device is provided with bypass adjustable pipe and bypass valve;
Said chromatographic column filler is following:
Porapak N type filler about 56%
Porapak Q type filler about 14%
Hayesep N type filler about 25%
Hayesep Q type filler about 5%
Said number percent is mass percent.
2. single-column one pin sample introduction stratographic analysis flow process according to claim 1 is characterized in that:
Said chromatographic column manufacturing approach is following:
(1) chooses the chromatographic column that internal diameter is about 2mm;
(2) insert about 1cm silica wool at said chromatographic column one end, insert 1cm stainless (steel) wire or 1cm close-fitting tubule again, and the said chromatographic column other end is connected with steel cylinder with mixing;
(3) chromatographic column filler for preparing is placed said steel cylinder, and in steel cylinder, feed gas, utilize air pressure that said chromatographic column filler is charged into said chromatographic column;
(4) stop to ventilate to the post internal gas pressure and return to normal pressure, unload chromatographic column, insert about 1cm silica wool, insert 1cm stainless (steel) wire or 1cm close-fitting tubule again in said chromatographic column and the tank connected end of steel cylinder;
(5) populated chromatographic column is carried out burin-in process.
3. single-column one pin sample introduction stratographic analysis flow process according to claim 1, it is characterized in that: the throughput of said bypass adjustable pipe is about 90% of total throughput.
4. single-column one pin sample introduction stratographic analysis flow process according to claim 2, it is characterized in that: the said volatilizable solvent of step (4) can be 2 milliliters to 8 milliliters a acetone or alcohol.
5. single-column one pin sample introduction stratographic analysis flow process according to claim 2 is characterized in that: the gas that step (3) feeds is nitrogen, and the air pressure of feeding maintains between the 0.4mPa to 0.5mPa, about 15 minutes of duration of ventilation.
6. single-column one pin sample introduction stratographic analysis flow process according to claim 2; It is characterized in that to comprise the steps: afterwards said chromatographic column not being immersed in the water about 2mm with the tank connected end of steel cylinder, whether have bubble to come the test column internal gas pressure whether to return to normal pressure through checking in step (3).
7. single-column one pin sample introduction stratographic analysis flow process according to claim 2 is characterized in that the burin-in process process is following described in the step (5):
(1) with chromatographic column one termination gas chromatograph injection port, other end emptying;
(2) feed nitrogen from injection port, post oven temperature, degree is made as about 130 degrees centigrade, and nitrogen flow is about 30mL/min, and digestion time is about 8 hours.
CN201210292142.0A 2012-08-16 2012-08-16 Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method Active CN102788851B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103675142A (en) * 2013-12-16 2014-03-26 北京华电云通电力技术有限公司 Single-column chromatographic column for electric insulation oil gas separation and preparation method
CN108181412A (en) * 2016-12-08 2018-06-19 北京国网富达科技发展有限责任公司 A kind of movable type oil chromatography detecting system
CN115038962A (en) * 2020-01-10 2022-09-09 英福康有限责任公司 Method for adjusting concentration of sample gas in gas mixture to be analyzed through gas chromatograph assembly and chromatograph assembly thereof

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JPS5759162A (en) * 1980-09-26 1982-04-09 Mitsubishi Electric Corp Gas chromatograph analyser
JP2000275150A (en) * 1999-03-24 2000-10-06 Hitachi Ltd Device for analyzing gas dissolved in oil
CN1487295A (en) * 2003-07-31 2004-04-07 上海交通大学 Prepn of compound chromatographic column for separating mixed gas dissolved in transformer oil
CN200944098Y (en) * 2006-07-12 2007-09-05 徐明远 Transformer oil chromatogram analytical equipment
US20110246088A1 (en) * 2010-04-02 2011-10-06 Eduardo Pedrosa Santos System and method for monitoring dissolved gases in insulating oil of power transformers, reactors, on-load tap changers, current transformers, potential transformers, condensive bushings as well as similar high voltage equipments immersed in oil

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JPS5759162A (en) * 1980-09-26 1982-04-09 Mitsubishi Electric Corp Gas chromatograph analyser
JP2000275150A (en) * 1999-03-24 2000-10-06 Hitachi Ltd Device for analyzing gas dissolved in oil
CN1487295A (en) * 2003-07-31 2004-04-07 上海交通大学 Prepn of compound chromatographic column for separating mixed gas dissolved in transformer oil
CN200944098Y (en) * 2006-07-12 2007-09-05 徐明远 Transformer oil chromatogram analytical equipment
US20110246088A1 (en) * 2010-04-02 2011-10-06 Eduardo Pedrosa Santos System and method for monitoring dissolved gases in insulating oil of power transformers, reactors, on-load tap changers, current transformers, potential transformers, condensive bushings as well as similar high voltage equipments immersed in oil

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103675142A (en) * 2013-12-16 2014-03-26 北京华电云通电力技术有限公司 Single-column chromatographic column for electric insulation oil gas separation and preparation method
CN108181412A (en) * 2016-12-08 2018-06-19 北京国网富达科技发展有限责任公司 A kind of movable type oil chromatography detecting system
CN115038962A (en) * 2020-01-10 2022-09-09 英福康有限责任公司 Method for adjusting concentration of sample gas in gas mixture to be analyzed through gas chromatograph assembly and chromatograph assembly thereof
CN115038962B (en) * 2020-01-10 2023-11-10 英福康有限责任公司 Method for adjusting concentration of sample gas in gas mixture to be analyzed by gas chromatograph assembly and chromatograph assembly thereof

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