CN1900711A - Method and device for detecting micro oxygen containing compound in low boiling point hydrocarbon - Google Patents
Method and device for detecting micro oxygen containing compound in low boiling point hydrocarbon Download PDFInfo
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- CN1900711A CN1900711A CN 200610042938 CN200610042938A CN1900711A CN 1900711 A CN1900711 A CN 1900711A CN 200610042938 CN200610042938 CN 200610042938 CN 200610042938 A CN200610042938 A CN 200610042938A CN 1900711 A CN1900711 A CN 1900711A
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Abstract
Liquid phase sampling, and sample injection of liquid phase are adopted in the disclosed method. Overcoming errors brought from sampling and injecting modes adopted in current analysis and mensuration method, the disclosed method makes sample of entering into chromatograph keep original composition so that detected result of chromatogram is capable of reflecting composition of analyzed materiel truly and accurately. The invention also discloses relevant measuring equipment. The equipment includes sampling steel cylinder, and gas chromatograph connected to the sampling steel cylinder through liquid valve. Through gas valve, injection port of sampling steel cylinder is connected to inert gases cylinder to fill inert gases into sampling steel cylinder in order to keep certain pressure for hydrocarbon in low boiling point inside steel cylinder so as to guarantee that sample in liquid phase can be taken out.
Description
Technical field
The present invention relates to a kind of assay method of micro substance, relate in particular to the assay method of micro oxygen containing compound in a kind of low boiling hydrocarbon.
Background technology
Low boiling point hydrocarbon is meant the hydro carbons that is gaseous state at normal temperatures and pressures, mainly is with C
3, C
4Component is main, contains the oxygenatedchemicals of trace simultaneously.The analysis determining method of micro oxygen containing compound in the existing low boiling hydrocarbon, usually adopt the analytical approach of gas chromatography: with sample process vessel extraction from turning round with bladders or steel cylinder, use syringe from bladders (perhaps steel cylinder), to get the sample of certain volume then, deliver into chromatograph, detect.But, in commercial production or experimental study, low boiling hydrocarbon presents liquid state in process pipe or equipment container, when containing boiling point in the hydro carbons and be higher than other component (impurity) of hydro carbons itself, adopt above-mentioned sampling and input mode, because the relative volatility of hydro carbons and other component is different, the hydrocarbon composition that enters in the chromatogram is many, and other components are few, cause the sample distortion easily.The unreasonable composition that makes analysis result can't accurately reflect the analytic sample of wanting on this input mode.
Summary of the invention
The object of the present invention is to provide the gas chromatographic analysis assay method of micro oxygen containing compound in a kind of low boiling point hydrocarbon.This method can overcome the error that sampling and input mode bring in the existing analysis determining method, makes to enter chromatographic sample and keep original composition, thereby makes the testing result of chromatogram can truly reflect the material composition that will analyze.
The present invention measures that the method for micro oxygen containing compound comprises following processing step in the low boiling point hydrocarbon:
1. liquid phase sampling: in the sampling steel cylinder, charge into inert gas, make the low boiling point hydrocarbon in the steel cylinder keep certain pressure, to guarantee to take out liquid phase sample;
2. chromatogram liquid phase sample introduction: make the low boiling point hydrocarbon sample in the sampling steel cylinder under pressure, enter gas chromatograph with liquid phase greater than the low boiling point hydrocarbon saturated vapour pressure;
3. vapor detection: after liquid phase sample enters the vaporizer gasification of gas chromatograph, adopt not that shunting mode enters the chromatographic column of filling with Macrogol 2000 0, detect;
4. component is measured: the chromatographic peak area of low boiling point hydrocarbon and oxygenatedchemicals in the working sample, and adopt external standard method to calculate the correction factor of each component; The correction factor of each component is calculated as follows:
In the formula: R
FiThe correction factor of-component i
C
Mark iThe concentration of-component i, mg/Kg
A
Mark i-stratographic analysis obtains the area of component i
I-low boiling point hydrocarbon or oxygenatedchemicals;
5. the mensuration of oxygenatedchemicals: the content that is calculated as follows impurity in the sample:
C
i＝A
iR
fi
In the formula: C
iThe content of oxygenatedchemicals in the-sample, mg/Kg;
A
iThe chromatographic peak area of oxygenatedchemicals in the-sample;
R
Fi-oxygenatedchemicals amount correction factor.
Wherein vapourizing temperature is 100～110 ℃ in the step vapor detection 3., and the chromatographic column column temperature is 65～70 ℃.
For the ease of measuring the content of micro oxygen containing compound in the low boiling point hydrocarbon, the present invention provides the device of micro oxygen containing compound in a kind of specific determination low boiling point hydrocarbon simultaneously, this device comprise the sampling steel cylinder with the gas chromatograph that is connected by liquid valve of sampling steel cylinder, the injection port of described sampling steel cylinder is connected with the inert gas bottle by air valve, so that in the sampling steel cylinder, charge into inert gas, make the low boiling point hydrocarbon in the steel cylinder keep certain pressure, to guarantee to take out liquid phase sample;
Simultaneously in order to ensure the pressure of the low boiling point hydrocarbon sample in the sampling steel cylinder greater than the low boiling point hydrocarbon saturated vapour pressure, between sampling steel cylinder and inert gas bottle, be provided with tensimeter.
In order to improve the accuracy of sample detection, between sampling steel cylinder and gas chromatograph, be provided with filtrator, with the floating outstanding material in the filtering sample.
The present invention is owing to adopt liquid phase sampling, liquid phase sample injection method, overcome in the existing analysis determining method error that sampling and input mode bring, make to enter chromatographic sample and keep original composition, thereby make the testing result of chromatogram can reflect the composition of the material of analyzing really and accurately.
Description of drawings
The synoptic diagram of oxygenatedchemicals determinator in Fig. 1 low boiling liquid hydrocarbon
Embodiment
(1) sensing equipment
Comprise sampling steel cylinder 1, inert gas bottle 4 and gas chromatograph 3, the admission valve of the steel cylinder 1 of wherein taking a sample is connected with inert gas bottle 4, and is provided with tensimeter 5 between the admission valve of the outlet valve of inert gas bottle 4 and the steel cylinder 1 of taking a sample; The outlet valve of sampling steel cylinder 1 is connected with gas chromatograph 3 by filtrator 6, and is provided with liquid valve 2 at the inlet of gas chromatograph 3, guarantees that sample enters gas chromatograph 3 with liquid phase.
(2) assay method
1. liquid phase sampling: with the mixed c 4 is base-material, and preparation contains the standard model of sec-butyl alcohol, the tert-butyl alcohol, MEK 10mg/Kg.Open the outlet valve of inert gas bottle, in the sampling steel cylinder, charge into inert gas, regulate the pressure in the sample steel cylinder, make the interior low boiling point hydrocarbon sample of sampling steel cylinder, keep liquid phase to guarantee the low boiling point hydrocarbon sample in the steel cylinder at pressure greater than the low boiling point hydrocarbon saturated vapour pressure;
2. chromatogram liquid phase sample introduction: open the steel cylinder outlet valve, the cleaning of off-gas quantity tube of flowing through under certain pressure flows out from blow-down pipe.In order to guarantee in the pipeline all fulls of liquid, connect a stainless steel capillary to increase resistance at the drain of valve, treat operation sampling valve sample introduction after blow-down pipe steady flow a quarter of an hour, sample enters the gasification of chromatograph vaporizer with liquid state;
3. vapor detection: liquid phase sample all enters chromatographic column after entering the vaporizer gasification of gas chromatograph under situation about not shunting, detect.Checkout equipment and condition: GC-4000A gas chromatograph, hydrogen flame detector, improved Macrogol 2000 0 chromatographic column, 68 ℃ of column temperatures, 100 ℃ of vapourizing temperatures, 150 ℃ of detecting devices.
4. the correction factor of each component is measured and calculated to component
The chromatographic peak area of low boiling point hydrocarbon and oxygenatedchemicals in the working sample, and adopt external standard method to calculate the correction factor of each component; The correction factor of each component is calculated as follows:
In the formula: R
FiThe correction factor of-component i
C
Mark IThe concentration of-component i, mg/Kg
A
Mark I-stratographic analysis obtains the area of component i
I-sec-butyl alcohol (TBA), the tert-butyl alcohol (MEK), MEK (SBA)
After measured, the correction factor of each component is as follows
R
SBA＝0.000001259；R
TBA＝0.000001028；R
MEK＝0.000001197。
5. sample analysis
With the mixed c 4 is base-material, and preparation contains the sample a (10mg/Kg) and the b (100mg/Kg) of micro-MEK, sec-butyl alcohol, the tert-butyl alcohol.Sample under 0.06MPa pressure, from the sampling steel cylinder through six-way valve, under liquid state with the sample size direct injected of 5～10 μ L.Each sample repeats to do 10 times, carries out the checking of method repeatability, the results are shown in Table 1.
Be calculated as follows each component concentration:
C
i＝A
iR
fi
In the formula: C
iThe content of oxygenatedchemicals in the-sample, mg/Kg;
A
iThe chromatographic peak area of component I in the-sample;
R
Fi-certain constituent mass correction factor.
Table 1 sample detection result
| Sample | Analysis times | Component | ||
| TBA | MEK | SBA | ||
| a | 1 | 10.61 | 9.70 | 8.42 |
| 2 | 9.47 | 9.77 | 10.41 | |
| 3 | 9.20 | 9.98 | 7.85 | |
| 4 | 10.50 | 10.23 | 10.70 | |
| 5 | 12.50 | 10.54 | 11.22 | |
| 6 | 9.31 | 9.51 | 9.35 | |
| 7 | 9.16 | 8.79 | 9.78 | |
| 8 | 10.80 | 11.32 | 10.22 | |
| 9 | 9.65 | 9.84 | 9.06 | |
| 10 | 10.50 | 10.05 | 9.94 | |
| Mean value | 10.17 | 9.97 | 9.70 | |
| Variance | 1.08 | 0.44 | 1.08 | |
| Standard deviation | 1.04 | 0.66 | 1.04 | |
| b | 1 | 98.81 | 100.30 | 92.70 |
| 2 | 101.09 | 99.50 | 98.36 | |
| 3 | 103.61 | 102.60 | 99.50 | |
| 4 | 95.10 | 92.40 | 95.40 | |
| 5 | 95.51 | 95.80 | 103.10 | |
| 6 | 94.56 | 92.60 | 94.10 | |
| 7 | 94.11 | 96.20 | 93.00 | |
| 8 | 101.10 | 97.80 | 98.61 | |
| 9 | 98.40 | 98.50 | 97.40 | |
| 10 | 98.80 | 97.40 | 99.65 | |
| Mean value | 98.11 | 97.31 | 97.18 | |
| Variance | 10.39 | 10.35 | 11.13 | |
| Standard deviation | 3.22 | 3.22 | 3.34 | |
As can be seen from Table 1, this method can be measured the oxygenates level in the mixed c 4 more accurately.
Claims (5)
1, the assay method of micro oxygen containing compound in a kind of low boiling point hydrocarbon comprises following processing step:
1. liquid phase sampling: in the sampling steel cylinder, charge into inert gas, make the low boiling point hydrocarbon in the steel cylinder keep certain pressure, to guarantee to take out liquid phase sample;
2. chromatogram liquid phase sample introduction: make the low boiling point hydrocarbon sample in the sampling steel cylinder under pressure, enter gas chromatograph with liquid phase greater than the low boiling point hydrocarbon saturated vapour pressure;
3. vapor detection: after liquid phase sample enters the vaporizer gasification of gas chromatograph, adopt not that shunting mode enters the chromatographic column of filling with Macrogol 2000 0, detect;
4. component is measured: the chromatographic peak area of low boiling point hydrocarbon and oxygenatedchemicals in the working sample, and adopt external standard method to calculate the correction factor of each component; The correction factor of each component is calculated as follows:
In the formula:
R
FiThe correction factor of-component i
C
Mark iThe concentration of-component i
A
Mark i-stratographic analysis obtains the area of component i
I-low boiling point hydrocarbon or oxygenatedchemicals;
5. the mensuration of oxygenatedchemicals: the content that is calculated as follows oxygenatedchemicals in the sample:
C
i＝A
iR
fi
In the formula:
G
iThe content of oxygenatedchemicals in the-sample
A
iThe chromatographic peak face of oxygenatedchemicals in the-sample
R
Fi-oxygenatedchemicals amount correction factor.
2, the assay method of micro oxygen containing compound in the low boiling point hydrocarbon according to claim 1, it is characterized in that: vapourizing temperature is 100～110 ℃ in the described vapor detection 3., the chromatographic column column temperature is 65～70 ℃.
3, the sensing equipment of micro oxygen containing compound in a kind of low boiling point hydrocarbon, comprise the sampling steel cylinder (1) with the sampling steel cylinder by the gas chromatograph (3) that sampling valve (2) is connected, it is characterized in that: the injection port of described sampling steel cylinder is connected with inert gas bottle (4) by air valve; Described sampling valve (2) is a liquid valve.
4, as the sensing equipment of micro oxygen containing compound in the low boiling point hydrocarbon as described in the claim 3, it is characterized in that: be provided with tensimeter (5) between described sampling steel cylinder (1) and the inert gas bottle (4).
5, as the sensing equipment of micro oxygen containing compound in the low boiling point hydrocarbon as described in claim 3 or 4, it is characterized in that: be provided with filtrator (6) between described sampling steel cylinder (1) and gas chromatograph (3).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100429385A CN100552451C (en) | 2006-06-02 | 2006-06-02 | The assay method of micro oxygen containing compound and equipment in a kind of low boiling point hydrocarbon |
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|---|---|---|---|
| CNB2006100429385A CN100552451C (en) | 2006-06-02 | 2006-06-02 | The assay method of micro oxygen containing compound and equipment in a kind of low boiling point hydrocarbon |
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|---|---|
| CN1900711A true CN1900711A (en) | 2007-01-24 |
| CN100552451C CN100552451C (en) | 2009-10-21 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103235069A (en) * | 2013-04-27 | 2013-08-07 | 昆明冶研新材料股份有限公司 | Liquid sample introduction device and method for gas chromatograph |
| CN104764819A (en) * | 2015-04-03 | 2015-07-08 | 大连理工大学 | Method for rapidly measuring halogenated semi-volatile organic pollutant sub-cooled vapor pressure in environment |
| CN114910572A (en) * | 2021-02-10 | 2022-08-16 | 上海中化科技有限公司 | Sample introduction device and method, and quantitative analysis device and method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4289029A (en) * | 1979-11-02 | 1981-09-15 | Uop Inc. | High temperature injection and vaporization system for gas chromatography |
| CN2384220Y (en) * | 1999-06-25 | 2000-06-21 | 吉林省电力科学研究院 | Chromatographic analysis direct filling device for gas solved in oil |
| CN2412218Y (en) * | 1999-11-05 | 2000-12-27 | 段景峰 | Flashing gasified sampling-fetching device for liquid hydrocarbon |
| CN2431565Y (en) * | 2000-07-21 | 2001-05-23 | 中国石化集团扬子石油化工有限责任公司 | Industrial gas phase chromatography sampler |
| WO2004092711A1 (en) * | 2003-04-14 | 2004-10-28 | Perkinelmer Las, Inc. | System and method for extracting headspace vapor |
-
2006
- 2006-06-02 CN CNB2006100429385A patent/CN100552451C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103235069A (en) * | 2013-04-27 | 2013-08-07 | 昆明冶研新材料股份有限公司 | Liquid sample introduction device and method for gas chromatograph |
| CN103235069B (en) * | 2013-04-27 | 2016-06-22 | 昆明冶研新材料股份有限公司 | Liquid sampling device and method for gas chromatograph |
| CN104764819A (en) * | 2015-04-03 | 2015-07-08 | 大连理工大学 | Method for rapidly measuring halogenated semi-volatile organic pollutant sub-cooled vapor pressure in environment |
| CN114910572A (en) * | 2021-02-10 | 2022-08-16 | 上海中化科技有限公司 | Sample introduction device and method, and quantitative analysis device and method |
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| Publication number | Publication date |
|---|---|
| CN100552451C (en) | 2009-10-21 |
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