CN104614477A - Method for determining trace methanol content of 1-butylene - Google Patents
Method for determining trace methanol content of 1-butylene Download PDFInfo
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- CN104614477A CN104614477A CN201410606740.XA CN201410606740A CN104614477A CN 104614477 A CN104614477 A CN 104614477A CN 201410606740 A CN201410606740 A CN 201410606740A CN 104614477 A CN104614477 A CN 104614477A
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Abstract
The invention relates to a method for determining trace methanol content of 1-butylene. The determination steps include: setting the carrier gas, fuel gas and combustion-supporting gas as the chromatographic conditions of a gas chromatograph, conducting drying and purification by silica gel and a 5A molecular sieve; adopting a capillary chromatographic column to determine the hydrogen flow, air flow, carrier gas initial pressure and split ratio; conducting sample determination: connecting a 1-butylene sample filled sampling steel cylinder to a liquid hydrocarbon flash vaporization sample injector, pre-heating the liquid hydrocarbon flash vaporization sample injector to a stable temperature of 100DEG C, connecting the liquid hydrocarbon flash vaporization sample injector to the gas chromatograph, opening a sample injector valve, carrying out exhaust replacement for about 3min, starting a chromatograph sample injection button, conducting sample injection by a quantitative tube, recording the methanol peak area in the sample by a chromatographic work station, and finally calculating the methanol content of the sample. According to the invention, by means of the liquid hydrocarbon flash vaporization sample injector, the sample vaporization can be more uniform and stable, then the chromatographic column is employed to perform analytical detection, and the method has good effects in the aspects of simplifying operation, reducing the detection limit, eliminating error and the like.
Description
Technical field
The present invention relates to petrochemicals detection technique field, is a kind of assay method detecting Trace Methanol content in the 1-butylene of methanol content in 1-butylene product specifically.
Background technology
1-butylene produces poly primary raw material, in 1-butylene, methanol content exceeds standard and causes polymerization reaction system electrostatic high, device heavy-duty service, operate restive, even jeopardize device to stop, conclusive effect is played to production and quality monitoring all the time, therefore accurately detect Trace Methanol content in 1-butylene and seem extremely important.At present, in 1-butylene sample, the assay method of Trace Methanol performs the SH/T 1547 mensuration vapor-phase chromatography of Trace Methanol and tertbutyl ether " in the 1-butylene ", the poor operability of discover method in practice: 1-butylene and the hangover of other carbon four peak, sometimes part covers methyl alcohol peak, cause methyl alcohol detection limit higher, result reliability is poor.
Summary of the invention
The object of this invention is to provide a kind of assay method detecting Trace Methanol content in the 1-butylene of methanol content in 1-butylene product.
The object of the invention is to be achieved by the following technical solution: the assay method of Trace Methanol content in 1-butylene, is characterized in that: test determination step comprises:
The chromatographic condition of gas chromatograph is set: carrier gas is nitrogen, and purity is greater than 99.99%(V/V); Combustion gas is hydrogen, and purity is greater than 99.99%(V/V); Combustion-supporting gas is air, through silica gel and 5A molecular sieve drying, purification; Gas is methanol content 0.00102%(V/V);
Vapourizing temperature: 248 ~ 252 DEG C;
Detector temperature: 300 DEG C;
Capillary chromatographic column post case: equilibration time is 1 minute, post case program, for opening, keeps 2 minutes at 50 DEG C, and then 10 DEG C/min keeps 2 minutes to 200 DEG C; Working time is 19 minutes;
Hydrogen flowing quantity: 30ml/min;
Air mass flow: 400ml/min;
Carrier gas original pressure: 1.42 psi;
Split ratio: 10:1;
Calibration: accurately enter calibrating gas 1ml by chromatographic gasometry pipe, methyl alcohol peak area A in chromatographic work station record gas
s;
Specimen Determination: take 1-butylene sample, the sampling steel cylinder being full of 1-butylene sample is connected on the flash vaporized injector of liquid hydrocarbon, the flash vaporized injector of liquid hydrocarbon in advance thermal-stable at 100 DEG C, the flash vaporized injector of liquid hydrocarbon is connected with gas chromatograph, open injector valve, exhaust displacement about 3 minutes, start chromatograph sample introduction button, quantity tube sample introduction 1ml, methyl alcohol peak area A in chromatographic work station record sample
i;
Result calculates: as follows with the methanol content that ppm (V/V) represents:
X
i= S * A
i/A
s
In formula: X
i----methanol content in sample, ppm (V/V);
Methanol content in S---Standard Gases, ppm (V/V);
A
i---the peak area of methyl alcohol in sample;
A
s---the peak area of methyl alcohol in gas standard specimen.
The present invention adopts the flash vaporized injector direct injected of liquid hydrocarbon, and capillary gas chromatographic column is separated, and flame ionization ditector detects, and quantified by external standard method measures Trace Methanol content in 1-butylene, is applicable to methanol content and is not less than 0.0002%.
Improve with test through repeatedly inquiring into, the present invention is by increasing the flash vaporized injector of sample vaporization device-liquid hydrocarbon, sample is gasified evenly stable, then adopts a kind of New GC column to carry out analysiss to detect, simplifying the operation, reduce in detection limit, elimination error etc. and achieve good effect.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described.
Fig. 1 is the present invention typical case chromatogram simplified schematic diagram;
Fig. 2 is that Fig. 1 amplifies typical chromatogram simplified schematic diagram.
The present invention to be described in further detail by example below in conjunction with accompanying drawing; but following example is only the present invention's example wherein; do not represent the rights protection scope that the present invention limits, the scope of the present invention is as the criterion with claims.
Embodiment
example 1
1) reagent and material:
Carrier gas: nitrogen, purity is greater than 99.99%(V/V)
Combustion gas: hydrogen, purity is greater than 99.99%(V/V)
Combustion-supporting gas: air, through silica gel and 5A molecular sieve drying, purification.
Gas: methanol content 0.00102%(V/V), provided by Dalian Chemical Physics Research Institute.
2) instrument
Gas chromatograph: the gas chromatograph being furnished with flame ionization ditector, this chromatograph at least should be greater than the twice of noise to the peak height that methyl alcohol produces under least concentration.
Chromatographic column: ga-oxyplot, 10m*350um*10um capillary chromatographic column
Sampling device: the flash vaporized injector of liquid hydrocarbon
3) test procedure
Chromatographic condition sets: vapourizing temperature: 250 DEG C (guarantee that in sample, each component is vaporized completely, or select the temperature with suitable vaporization effect, such as 248 ~ 252 DEG C, data are in table 2)
Detector temperature: 300 DEG C
Post case: equilibration time 1 minute,
Post case program is opened
50 DEG C keep 2 minutes, and then 10 DEG C/min keeps 2 minutes to 200 DEG C
19 minutes working times (ensureing that in sample, each component is separated completely and flows out chromatographic column completely)
Hydrogen flowing quantity: 30ml/min;
Air mass flow: 400ml/min;
Carrier gas original pressure: 1.42 psi;
Split ratio: 10:1;
Calibration:
Calibrating gas 1ml is accurately entered, methyl alcohol peak area A in chromatographic work station record gas by chromatographic gasometry pipe
s.
Specimen Determination:
1-butylene sample is taked according to GB/T 13290-91 regulation.The sampling steel cylinder being full of 1-butylene sample is connected on the flash vaporized injector of liquid hydrocarbon, the flash vaporized injector of liquid hydrocarbon in advance thermal-stable at 100 DEG C.The flash vaporized injector of liquid hydrocarbon is connected with gas chromatograph, opens injector valve, exhaust displacement about 3 minutes, starts chromatograph sample introduction button, quantity tube sample introduction 1ml, methyl alcohol peak area A in chromatographic work station record sample
i.
Result calculates: as follows with the methanol content that ppm (V/V) represents: X
i=S * A
i/ A
s
In formula: X
i---methanol content in sample, ppm (V/V);
Methanol content in S---Standard Gases, ppm (V/V);
A
i---the peak area of methyl alcohol in sample;
A
s---the peak area of methyl alcohol in gas standard specimen;
Analysis result: represent its analysis result with the arithmetic mean of twice replication.
Conclusion: this method is applied to Trace Methanol assay in MTBE device technique process and product sample 1-butylene, and sample introduction is easy to operate and safe, fully, be separated completely, detection limit is low, and measurement result is reproducible, and accuracy is high in vaporization.
Shown in accompanying drawing 1-2,1). butylene and other hydro carbons (0.760min); 2). methyl alcohol (13.059min).
Example related data: measure methanol content in MTBE device 1-butylene sample, data see the following form 1.
Trace Methanol content in table 1 MTBE device 1-butylene
The different vapourizing temperature of table 2 is on the impact of measurement result
Claims (2)
- The assay method of Trace Methanol content in 1.1-butylene, is characterized in that: test determination step comprises:The chromatographic condition of gas chromatograph is set: carrier gas is nitrogen, and purity is greater than 99.99%(V/V); Combustion gas is hydrogen, and purity is greater than 99.99%(V/V); Combustion-supporting gas is air, through silica gel and 5A molecular sieve drying, purification; Gas is methanol content 0.00102%(V/V);Vapourizing temperature: 248 ~ 252 DEG C;Detector temperature: 300 DEG C;Capillary chromatographic column post case: equilibration time is 1 minute, post case program, for opening, keeps 2 minutes at 50 DEG C, and then 10 DEG C/min keeps 2 minutes to 200 DEG C; Working time is 19 minutes;Hydrogen flowing quantity: 30ml/min;Air mass flow: 400ml/min;Carrier gas original pressure: 1.42 psi;Split ratio: 10:1;Calibration: accurately enter calibrating gas 1ml by chromatographic gasometry pipe, methyl alcohol peak area A in chromatographic work station record gas s;Specimen Determination: take 1-butylene sample, the sampling steel cylinder being full of 1-butylene sample is connected on the flash vaporized injector of liquid hydrocarbon, the flash vaporized injector of liquid hydrocarbon in advance thermal-stable at 100 DEG C, the flash vaporized injector of liquid hydrocarbon is connected with gas chromatograph, open injector valve, exhaust displacement about 3 minutes, start chromatograph sample introduction button, quantity tube sample introduction 1ml, methyl alcohol peak area A in chromatographic work station record sample i;Result calculates: as follows with the methanol content that ppm (V/V) represents: X i=S * A i/ A sIn formula: X i---methanol content in sample, ppm (V/V);Methanol content in S---Standard Gases, ppm (V/V);A i---the peak area of methyl alcohol in sample;A s---the peak area of methyl alcohol in gas standard specimen.
- 2. the assay method of Trace Methanol content in 1-butylene according to claim 1, is characterized in that: selected gas chromatograph is the gas chromatograph being furnished with flame ionization ditector.
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| CN201410606740.XA CN104614477A (en) | 2014-11-03 | 2014-11-03 | Method for determining trace methanol content of 1-butylene |
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| CN201410606740.XA CN104614477A (en) | 2014-11-03 | 2014-11-03 | Method for determining trace methanol content of 1-butylene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107529620A (en) * | 2017-06-08 | 2018-01-02 | 内蒙古中煤蒙大新能源化工有限公司 | The analysis method of carbonyls in a kind of product of methanol-to-olefins device carbon four |
| CN108507901A (en) * | 2018-06-21 | 2018-09-07 | 河南省煤气(集团)有限责任公司义马气化厂 | The analysis method of trace carbinol in a kind of purified gas |
| CN113484448A (en) * | 2021-08-13 | 2021-10-08 | 中国航发沈阳黎明航空发动机有限责任公司 | Method for detecting content of methanol and ethanol in engine bleed air |
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| CN2034279U (en) * | 1988-06-25 | 1989-03-15 | 廖焕然 | Thermodesorption flash feeder |
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2014
- 2014-11-03 CN CN201410606740.XA patent/CN104614477A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN2034279U (en) * | 1988-06-25 | 1989-03-15 | 廖焕然 | Thermodesorption flash feeder |
Non-Patent Citations (5)
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| 中华人民共和国国家发展和改革委员会: "《中华人民共和国石油化工行业标准SH/T1547-2004》", 9 April 2004 * |
| 吴维成 等: "利用卡尔费休法测定二甲醚中微量水分", 《河南化工》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107529620A (en) * | 2017-06-08 | 2018-01-02 | 内蒙古中煤蒙大新能源化工有限公司 | The analysis method of carbonyls in a kind of product of methanol-to-olefins device carbon four |
| CN108507901A (en) * | 2018-06-21 | 2018-09-07 | 河南省煤气(集团)有限责任公司义马气化厂 | The analysis method of trace carbinol in a kind of purified gas |
| CN113484448A (en) * | 2021-08-13 | 2021-10-08 | 中国航发沈阳黎明航空发动机有限责任公司 | Method for detecting content of methanol and ethanol in engine bleed air |
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Application publication date: 20150513 |