CN102788851B - Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method - Google Patents
Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method Download PDFInfo
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- CN102788851B CN102788851B CN201210292142.0A CN201210292142A CN102788851B CN 102788851 B CN102788851 B CN 102788851B CN 201210292142 A CN201210292142 A CN 201210292142A CN 102788851 B CN102788851 B CN 102788851B
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Abstract
The present invention relates to a kind of gas chromatography analysis method.Described Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method, comprise chromatographic column separation, conductance cell detects and FID detects, need gas to carry out methane conversion by methane reformers before FID detects, it is characterized in that, described methane reformers is provided with bypass adjustable pipe and bypass valve; Described chromatographic column filler is as follows: Porapak N-type filler about 56%; Porapak Q type filler about 14%; Hayesep N-type filler about 25%; Hayesep Q type filler about 5%; Described number percent is mass percent.Beneficial effect of the present invention is: effectively can realize single-column one pin sample introduction, cost is lower, simple flow, overcomes the labile factor in Complicated Flow simultaneously, as high-load CO, CO
2to CH
4, C
2h
4detect the impact etc. be separated.
Description
[technical field]
The present invention relates to a kind of gas chromatography analysis method.
[background technology]
Mainly utilize dissolved gas in vapor-phase chromatography Transformer Oil Analysis in prior art, general adopt a pin sampling system, its advantage is to reduce analytical error, meets the few crude oil sample analysis of amount of gas evolved, simple to operate.A conventional pin sampling system mainly comprises twin columns parallel shunt method and a pin sample introduction six-way valve switches method two kinds.
The defect of one pin sample introduction twin columns parallel shunt method is as follows: the first, and split ratio is in operation and can changes; The second, TCD reference must emptying and make thermal conductivity cell detector unstability of base line fixed; 3rd, the molecular sieve column of use can make CO
2go out peak-to-peak molded breadth, time length, easily lost efficacy; Four, O
2interference make CO before there is shoulder peak, CH
4front appearance heavy burden peak, interference measurement.
The defect that one pin sample introduction six-way valve switches method is as follows: the first, and the switching of valve causes baseline to suddenly change, impact analysis; The second, use 13X molecular sieve column, serviceable life is short, easily because of adsorption moisture and CO
2and lost efficacy; 3rd, there is CO, CO of high-load
2to CH
4, C
2h
4the impact be separated; Four, C
2h
2detection sensitivity is low.Above-mentioned defect mainly chromatographic column separating property and analysis process causes.
For this reason, people start the research that single-column is separated.At present, single-column is separated CO, CO of there is high-load
2to CH
4, C
2h
4the impact be separated, this is CO and CO due to Gas in Oil of Transformer
2content is often higher, common at hundreds of extremely thousands of ppm, and hydrocarbon gas content is general lower, belongs to micro-rank.So the sensitivity of GB GB/T7252-2001 regulation hydrocarbon indication is 0.1ppm, and CO, CO
2for 25ppm.
[summary of the invention]
The object of the present invention is to provide a kind of can the Gas in Oil of Transformer analytical approach of single-column sample introduction, weaken single-column simultaneously and be separated high-load CO, CO of existing
2to CH
4, C
2h
4detect the impact be separated.
The present invention is achieved through the following technical solutions:
Described Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method, comprise chromatographic column separation, conductance cell detects and FID detects, need gas to carry out methane conversion by methane reformers before FID detects, described methane reformers is provided with bypass adjustable pipe and bypass valve; Described chromatographic column filler is as follows:
Porapak N-type filler about 56%
Porapak Q type filler about 14%
Hayesep N-type filler about 25%
Hayesep Q type filler about 5%
Described number percent is mass percent.
Further, described chromatographic column manufacture method is as follows:
(1) chromatographic column that internal diameter is about 2mm is chosen;
(2) insert about 1cm silica wool in described chromatographic column one end, then insert 1cm stainless (steel) wire or 1cm close-fitting tubule, and the described chromatographic column other end is connected with mixing steel cylinder;
(3) chromatographic column filler prepared is placed in described steel cylinder, and passes into gas in steel cylinder, utilize air pressure that described chromatographic column filler is filled with described chromatographic column;
(4) stop ventilation returning to normal pressure to post internal gas pressure, unload chromatographic column, insert about 1cm silica wool in described chromatographic column and the tank connected one end of steel cylinder, then insert 1cm stainless (steel) wire or 1cm close-fitting tubule;
(5) burin-in process is carried out to populated chromatographic column.
Further, the throughput of described bypass adjustable pipe is about 90% of total throughput.
Further, the described volatilizable solvent of step (4) can be the acetone or alcohol of 2 milliliters to 8 milliliters.
Further, the gas that step (3) passes into is nitrogen, and the air pressure passed into maintains between 0.4mPa to 0.5mPa, duration of ventilation about 15 minutes.
Further, can also comprise the steps: that tank connected one end is not immersed in the water about 2mm with steel cylinder by described chromatographic column after step (3), see if there is bubble and carry out test column internal gas pressure by looking into and whether return to normal pressure.
Further, described in step (5), burin-in process process is as follows:
(1) by chromatographic column one termination gas chromatograph injection port, other end emptying;
(2) pass into nitrogen from injection port, post case temperature is set to about 130 degrees Celsius, and nitrogen flow is about 30mL/min, and digestion time is about 8 hours.
Beneficial effect of the present invention is: effectively can realize single-column one pin sample introduction, cost is lower, simple flow, overcomes the labile factor in Complicated Flow simultaneously, as high-load CO, CO
2to CH
4, C
2h
4detect the impact be separated.
[accompanying drawing explanation]
Fig. 1 is analysis process schematic diagram of the present invention;
Fig. 2 is stratographic analysis total result schematic diagram of the present invention;
Fig. 3 is stratographic analysis local result schematic diagram of the present invention;
Reference numeral: 1, injection port; 2, chromatographic column; 3, thermal conductivity cell detector; 4, methane reformers; 5, fid detector; 6, bypass adjustable pipe; 7, bypass valve.
[embodiment]
Below in conjunction with the drawings and the specific embodiments, the present invention is described further:
A kind of Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method, comprise chromatographic column separation, conductance cell detects and FID detects, need gas to carry out methane conversion by methane reformers 4 before FID detects, it is characterized in that, described methane reformers 4 is provided with bypass adjustable pipe 6 and bypass valve 7;
Described chromatographic column 2 filler is as follows:
Porapak N-type filler about 56%
Porapak Q type filler about 14%
Hayesep N-type filler about 25%
Hayesep Q type filler about 5%
Described number percent is mass percent.
Preferably, described chromatographic column 2 manufacture method is as follows:
(1) chromatographic column that internal diameter is about 2mm is chosen;
(2) insert about 1cm silica wool in described chromatographic column one end, then insert 1cm stainless (steel) wire or 1cm close-fitting tubule, and the described chromatographic column other end is connected with mixing steel cylinder;
(3) chromatographic column filler prepared is placed in described steel cylinder, and passes into gas in steel cylinder, utilize air pressure that described chromatographic column filler is filled with described chromatographic column;
(4) stop ventilation returning to normal pressure to post internal gas pressure, unload chromatographic column, insert about 1cm silica wool in described chromatographic column and the tank connected one end of steel cylinder, then insert 1cm stainless (steel) wire or 1cm close-fitting tubule;
(5) burin-in process is carried out to populated chromatographic column.
Preferably, the throughput of described bypass adjustable pipe 6 is about 90% of total throughput.
Preferably, the described volatilizable solvent of step (4) can be the acetone or alcohol of 2 milliliters to 8 milliliters.
Preferably, the gas that step (3) passes into is nitrogen, and the air pressure passed into maintains between 0.4mPa to 0.5mPa, duration of ventilation about 15 minutes.
Preferably, can also comprise the steps: that tank connected one end is not immersed in the water about 2mm with steel cylinder by described chromatographic column after step (3), see if there is bubble and carry out test column internal gas pressure by looking into and whether return to normal pressure.
Preferably, described in step (5), burin-in process process is as follows:
(1) by chromatographic column one termination gas chromatograph injection port, other end emptying;
(2) pass into nitrogen from injection port, post case temperature is set to about 130 degrees Celsius, and nitrogen flow is about 30mL/min, and digestion time is about 8 hours.
In the present embodiment, test parameters is as follows:
Use N
2as sample introduction carrier gas, flow is 22-25mL/min;
Use H
2as the reducing gas that methane reformers 4 transforms, flow is 22-25mL/min;
Use H
2as the burning gas for fid detector 5, flow is 0-15mL/min;
Air mass flow for fid detector 5 is 300-400mL/min;
Methane reformers 4 temperature 330-370 DEG C take Ni as catalyzer;
Chromatographic column 2 length adopted is about 4m, stainless steel, external diameter 3mm, temperature 65-70 DEG C;
Thermal conductivity cell detector 3 temperature 80-200 DEG C, bridge stream 70-100mA;
Injection port 1 temperature controls at 80-200 DEG C;
By regulating the bypass valve 7 entering the gas flow of methane reformers 4, make collateral ventilation flow account for 90% of total flow, bypass adjustable pipe 6 length is 1m-2m, stainless steel, external diameter 3mm.
In the present embodiment, chromatographic resolution result is as follows:
This single-column and analysis process, single injected sampling, can be separated H completely in 8 minutes
2, O
2, CO, CO
2, CH
4, C
2h
6, C
2h
4, C
2h
2etc. component.And significantly reduce CO, CO of high-load
2to CH
4, C
2h
4the impact be separated.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also carry out suitable change and amendment to above-mentioned embodiment.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although employ some specific terms in this instructions, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (5)
1. a Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method, comprise chromatographic column separation, conductance cell detects and FID detects, need gas to carry out methane conversion by methane reformers before FID detects, it is characterized in that, described methane reformers is provided with bypass adjustable pipe and bypass valve;
Described chromatographic column filler is as follows:
Porapak N-type filler about 56%
Porapak Q type filler about 14%
Hayesep N-type filler about 25%
Hayesep Q type filler about 5%
Described number percent is mass percent; Described chromatographic column manufacture method is as follows:
(1) chromatographic column that internal diameter is about 2mm is chosen;
(2) insert about 1cm silica wool in described chromatographic column one end, then insert 1cm stainless (steel) wire or 1cm close-fitting tubule, and the described chromatographic column other end is connected with mixing steel cylinder;
(3) chromatographic column filler prepared is placed in described steel cylinder, and passes into gas in steel cylinder, utilize air pressure that described chromatographic column filler is filled with described chromatographic column;
(4) stop ventilation returning to normal pressure to post internal gas pressure, unload chromatographic column, insert about 1cm silica wool in described chromatographic column and the tank connected one end of steel cylinder, then insert 1cm stainless (steel) wire or 1cm close-fitting tubule;
(5) burin-in process is carried out to populated chromatographic column.
2. single-column one pin sample introduction chromatogram analysis method according to claim 1, is characterized in that: the throughput of described bypass adjustable pipe is about 90% of total throughput.
3. single-column one pin sample introduction chromatogram analysis method according to claim 1, is characterized in that: the gas that step (3) passes into is nitrogen, and the air pressure passed into maintains between 0.4mPa to 0.5mPa, duration of ventilation about 15 minutes.
4. single-column one pin sample introduction chromatogram analysis method according to claim 1, it is characterized in that comprising the steps: that tank connected one end is not immersed in the water about 2mm with steel cylinder by described chromatographic column after step (3), see if there is bubble and carry out test column internal gas pressure by looking into and whether return to normal pressure.
5. single-column one pin sample introduction chromatogram analysis method according to claim 1, is characterized in that described in step (5), burin-in process process is as follows:
(1) by chromatographic column one termination gas chromatograph injection port, other end emptying;
(2) pass into nitrogen from injection port, post case temperature is set to about 130 degrees Celsius, and nitrogen flow is about 30mL/min, and digestion time is about 8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210292142.0A CN102788851B (en) | 2012-08-16 | 2012-08-16 | Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210292142.0A CN102788851B (en) | 2012-08-16 | 2012-08-16 | Gas in Oil of Transformer single-column one pin sample introduction chromatogram analysis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102788851A CN102788851A (en) | 2012-11-21 |
| CN102788851B true CN102788851B (en) | 2015-09-16 |
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Families Citing this family (3)
| 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 |
| EP3848703B1 (en) * | 2020-01-10 | 2024-01-03 | Inficon GmbH | Method for adapting the concentration of a sample gas in a gas mixture to be analysed by a gas chromatograph assembly, and chromatograph assembly therefor |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1224839C (en) * | 2003-07-31 | 2005-10-26 | 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 |
| US8442775B2 (en) * | 2010-04-02 | 2013-05-14 | Eduardo Pedrosa Santos | System and method for monitoring dissolved gases in insulating oil of high voltage equipment |
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