CN1831531A - Instrument for quantitative analysing micro-alkyne in C5 fraction and its analysing method - Google Patents
Instrument for quantitative analysing micro-alkyne in C5 fraction and its analysing method Download PDFInfo
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- CN1831531A CN1831531A CN 200510053814 CN200510053814A CN1831531A CN 1831531 A CN1831531 A CN 1831531A CN 200510053814 CN200510053814 CN 200510053814 CN 200510053814 A CN200510053814 A CN 200510053814A CN 1831531 A CN1831531 A CN 1831531A
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Abstract
A method for carrying out quantitative analysis on trace amount of alkyne in C5 fraction includes using polarity packed column to separate alkyne out from C5 fraction then cutting said alkyne into weak polarity or nonpolarity packed column for separating out each alkyne composition in packed column, finally applying external standard manner to carry out quantitative analysis on content of alkyne. The gas - phase chromatographic analyzer for realizing said method is also disclosed.
Description
Technical field
The present invention relates to a kind of instrument and method thereof, specifically, the present invention relates to a kind of instrument and method thereof that adopts the quantitative analysis by gas chromatography micro-alkyne with the quantitative analysis by gas chromatography trace impurity.
Background technology
Cracked C 5 fraction is the important by-products of petroleum cracking.Along with dwindling of the economic benefit room for promotion of the expansion of cracking ethylene device and ethylene unit, how to utilize cracked C 5 fraction more and more to attract much attention.With cracked C 5 fraction be separated into various products for example products such as chemical grade isoprene, polymerization grade isoprene, m-pentadiene, dicyclopentadiene be one of method of efficiently utilizing C5 fraction.Yet, no matter be carbon Wuyuan material, product, or the intermediate link of carbon five separation process, the alkynes that they contain all is critical controlling index.Owing in C5 fraction, contain components such as carbon four, carbon five, carbon six, not only contain alkane, mono-olefin, diolefin, alkynes, cyclic hydrocarbon etc., and each component also exists isomeride, the component complexity, the boiling range scope is big.At present, the analytical technology of each component in the existing C5 fraction generally adopts packed column to carry out macro-analysis; Alkynes in the material of carbon Wuyuan can only carry out macro-analysis, can not accurately analyze its content.Enter the intermediate material of first extraction cells of carbon five separation process, because its component is more, micro-alkyne is clipped in the middle of them, can not separate well, thereby can't analyze its accurate content.
Along with the development of chromatographic technique, people's capillary chromatographic column that begins one's study is analyzed C5 fraction.For example cold will light is at " the HP-1 micellar electrokinetic capillary chromatography of C5 fraction component " (analytical test journal, in May, 1999, the 18th rolls up the 43rd~46 page of the 3rd phase) and " application of capillary chromatography in the C 5 fraction control analysis " (petroleum refining and chemical industry, in April, 2000, the 64th~67 page of the 31st the 4th phase of volume) propose to adopt capillary chromatographic column to analyze the method for C5 fraction in, adopt in the literature chromatograph-mass spectrometer qualitative exactly each component, determined 65 components (not comprising dipolymer) in the C5 fraction substantially.But this method still is the macro-analysis method.Adopt capillary chromatographic column, its post footpath is very little, has determined its sample size few in the extreme, therefore can not quantitatively accurately analyze microcomponent thereon.
Domestic existing cracking c_5 tripping device, so far can only the quantitative test component less chemical grade and the micro-alkyne in the polymerization grade isoprene product, and gas circuit complexity need with four root chromatogram columns and two six-way valves.
In sum, providing a kind of analytical instrument and the analytical approach of quantitatively analyzing micro-alkyne in the C5 fraction accurately of simple possible is the unsolved always difficult problems of people.
Summary of the invention
The present invention is directed to the above-mentioned problems in the prior art,, provide a kind of analytical instrument that addresses the above problem and analytical approach thereof through a large amount of careful deep researchs.
The gas chromatographicanalyzer device of micro-alkyne in the quantitative test C5 fraction of the present invention, comprise and adopt a polarity packed column and a low pole or nonpolar packed column, with the polarity packed column alkynes in the C5 fraction is separated, then this part alkynes is cut into low pole or nonpolar packed column, in packed column, each alkynes component is separated, adopted external standard method quantitative test alkynes content.
The gas chromatographicanalyzer device of micro-alkyne in the quantitative test C5 fraction of the present invention comprises two packed columns, connects with four-way valve between two packed columns; One end of first packed column is connected with injector 8, and the interface 1 of the other end and four-way valve 5 is connected; The interface 4 of interface 1 adjacency that is connected with first packed column of one end of second packed column and four-way valve connects, and the other end is connected with hydrogen flame detector; On two other interface of four-way valve, connect vapour lock 11,12 respectively; Wherein the interface 2 of the interface adjacency that is connected with first packed column of an end of vapour lock 11 and four-way valve connects, and the other end is connected with thermal conductivity detector (TCD); Last interface 3 of one end of vapour lock 12 and four-way valve is connected, and the other end is connected with carrier gas through pressure maintaining valve; The air resistance of the vapour lock 11 that is connected with thermal conductivity detector (TCD) and the air resistance of second packed column equate that the air resistance of the vapour lock 12 that is connected with hydrogen flame detector and the air resistance of first packed column equate.
The gas chromatographicanalyzer device of micro-alkyne in the another kind of quantitative test C5 fraction of the present invention comprises two packed columns and two four-way valves; Wherein the interface 2 ' of first four-way valve 14 is connected with injector 8, and the diagonal angle interface 4 ' of this interface is connected with interface 1 by blank pipe and second four-way valve 5; Two other diagonal angle interface 1 ' of first four-way valve, 3 ' is connected with first packed column; Second four-way valve be connected with second packed column with interface 4 interface 1 adjacency, the other end of second packed column is connected with hydrogen flame detector; Second four-way valve be connected with vapour lock 11 with interface 2 interface 1 adjacency, the other end of this vapour lock 11 is connected with thermal conductivity detector (TCD); Last interface 3 of second four-way valve is connected with vapour lock 12, and its other end is connected with carrier gas through pressure maintaining valve; The air resistance of the vapour lock 11 that is connected with thermal conductivity detector (TCD) and the air resistance of second packed column equate that the air resistance of the vapour lock 12 that is connected with hydrogen flame detector and the air resistance of first packed column equate.
In above-mentioned two schemes, the stationary phase of described first packed column is made up of polarity immobile liquid and diatomite support, and the weight percent content of polarity immobile liquid and diatomite support is respectively 5~30% and 70~95%; The stationary phase of described second packed column is made up of low pole immobile liquid and diatomite support, and the weight percent content of low pole immobile liquid and diatomite support is respectively 5~30% and 70~95%.
Preferably, wherein the used polarity immobile liquid of first packed column can be selected from β, a kind of in β-oxydipropionitrile, hexamethyl phosphoramide, dimethylsulfolane, 5-methyl-N-Methyl pyrrolidone and the Macrogol 2000 0;
Second used low pole immobile liquid of packed column can be selected from a kind of in ethylazelaate, dinonyl phthalate, di(2-ethylhexyl)phosphate cresols ester, xylenylphosphate, two-2-methoxyl hexane diacid ethyl ester, different thirty alkane and the last of the ten Heavenly stems dioctyl phthalate ester in two ninth of the ten Heavenly Stems;
The diatomite support that the stationary phase of first and second packed column uses, can be identical or inequality, wherein said diatomite support can be selected from a kind of in 101 pickling zeyssatite, 201 pickling zeyssatite, Anaprep A zeyssatite, Chromosorb P zeyssatite, Diasolid A zeyssatite, Diatomite P zeyssatite, DiatoportS zeyssatite, K zeyssatite and the KVA zeyssatite.
The grain size of described first packed column and the stationary phase of second packed column can be identical or inequality, is selected from 60~100 purpose particles.
The column length of described first packed column and second packed column can be identical or inequality with internal diameter, and their column length is selected from 4~10 meters, and internal diameter is selected from 2~5mm.
The carrier gas that described two packed columns use is nitrogen, hydrogen or argon gas.
Described air resistance is that gas passes through vapour lock 11 or 12 and the resistance during packed column, and the pressure when showing as gas by them falls. Vapour lock 11 or 12 is a standard vapour lock element, and its vapour lock size can be regulated as required.
The method of micro-alkyne is in the quantitative test C5 fraction that the present invention proposes, use above-mentioned gas chromatographicanalyzer device, first packed column is communicated with the vapour lock 11 that is connected with thermal conductivity detector (TCD) through four-way valve, second packed column is communicated with the vapour lock 12 that is connected with hydrogen flame detector, and be equal by the carrier gas flux of two packed columns; Injector is injected in C5 fraction, enter first packed column, C5 fraction is separated on first packed column through injector; When wherein alkynes flows to the tail end of first packed column, the rotary four-way valve partly is cut into second packed column with alkynes, after having cut four-way valve is rotated back to original position, each alkynes component is separated on second packed column, detects quantitatively with hydrogen flame detector.
Usually, when the rotary four-way valve cuts by retention time is judged.Promptly at first do not cut, only use first packed column, make retention time; When finishing to last alkynes peak before first alkynes peak begun, during this period of time as clipping time.When analyzing next sample, use cut the clipping time that obtains.
Described C5 fraction is mixed pyrolysis C5 fraction, chemical grade isoprene, polymerization grade isoprene or the C5 fraction that removes carbon four components, m-pentadiene and cyclopentadiene component.
In analytical approach of the present invention, preferred, the carrier gas flux in two packed columns is 25-60ml/min, and post oven temperature, degree is 25-70 ℃.
Preferably, the flow of auxiliary gas is 25-60ml/min, and the flow of air-breathing gas is 25-60ml/min, and the temperature of thermal conductivity detector (TCD) is 150-200 ℃, and the temperature of hydrogen flame detector is 200-270 ℃, and the vapourizing temperature of injector is 120-200 ℃.
The preparation method of packed column used in the present invention is a conventional method, and concrete grammar is as follows, but is not limited to following method.
(1) first packed column: with immobile liquid use with carrier with the acetone solution of volume in double dish, pour into carrier in the double dish uniformly again, the consumption of carrier is the vehicle weight with pillar volume equal volume, wave and culture ware slowly, and wherein the weight ratio of immobile liquid and carrier is 30: 100.After solvent acetone volatilization, carrier becomes moistening when loose, uses the infrared lamp dry for standby.
(2) second packed columns: use to be dissolved in immobile liquid in the double dish uniformly with the methenyl choloride of volume with carrier, pour into carrier in the double dish equably again, the consumption of carrier is the vehicle weight with pillar volume equal volume, wave and culture ware slowly, wherein the weight ratio of immobile liquid and carrier is 30: 100.After solvent methenyl choloride volatilization, carrier becomes moistening when loose, uses the infrared lamp dry for standby.
(3) dress post: an end of pillar is stifled tight with copper mesh, to receive on the vacuum filtration device, the other end is received on the glass funnel, opens the suction filtration device, and the carrier for preparing is slowly poured in the funnel, beats pillar gently with rod wooden or made of paper.When the volume of carrier of packing into and calculating is some more slightly when no longer advancing pillar, that pillar two is stifled good standby with glass wool.
(4) aging: carrier gas is N
2, on pillar one termination carrier gas inlet, other end emptying in the post case.Measurement flow rate wore out 10 hours at 30ml/min.Cutting aging of column temperature is 60 ℃, and the analytical column aging temperature is 100 ℃.
The n-pentane solution of the micro-valylene (pentone) by measuring variable concentrations calculates the error and the deviation of analytical approach of the present invention.The error at measurment of the n-pentane solution of the valylene of table 1 expression variable concentrations; The measurement deviation of the n-pentane solution of the valylene of a certain concentration of table 2 expression.
When listed gravimetric value is represented to dispose solution in table 1 and the table 2, the concentration value that weighs with scale and calculate; Measured value is represented the concentration value that obtains with gas chromatography analysis method analysis of the present invention.
The deviation data listed by table 2 calculates:
Mean deviation=3.03/5=0.61
Relative deviation=0.61/19.40 * 100%=3.14%
Standard deviation s=[2.15/ (5-1)]
1/2=0.73
Relative standard deviation=0.73/19.40 * 100%=3.76%
Above-mentioned relative error and standard deviation meet the requirement of microanalysis, illustrate that analytical approach of the present invention is accurate and stable.
Table 1 errors table
Gravimetric value ppm | Measured value ppm | Absolute error | Relative error |
2.99 | 2.85 | -0.14 | -4.82% |
6.20 | 6.47 | +0.27 | +4.35% |
11.50 | 11.29 | -0.21 | -1.83% |
15.90 | 15.57 | -0.33 | -2.18% |
22.90 | 23.53 | +0.63 | +2.97% |
Table 2 deviation chart
Measure number of times | Measured value ppm | Gravimetric value ppm | Deviation | Absolute deviation d | d 2 |
1 | 19.28 | 19.40 | -0.12 | 0.12 | 0.01 |
2 | 20.24 | +0.84 | 0.84 | 0.71 | |
3 | 18.73 | -0.67 | 0.67 | 0.45 | |
4 | 18.68 | -0.72 | 0.72 | 0.52 | |
5 | 20.08 | +0.68 | 0.68 | 0.46 | |
Summation | 3.03 | 2.15 |
The gas chromatographicanalyzer device and the analytical approach thereof of micro-alkyne have the following advantages in the quantitative test C5 fraction of the present invention:
1. use analytical instrument of the present invention and analytical approach thereof, the quantitative test micro-alkyne accurately and reliably, simple easy operating.
2. use analytical instrument of the present invention can only use a cutting four-way valve, simplified gas circuit, saved the cost of repacking gas chromatographicanalyzer device, and simplified operation.
3. analytical approach of the present invention has solved people's open question always, not only can analyze the micro-alkyne content in mixed pyrolysis C5 fraction, carbon five products, but also micro-alkyne content that can analytical pyrolysis C5 fraction tripping device intermediate material, can provide foundation for control and the adjusted parameter of optimizing each carbon five separative elements, and then can further improve the economic benefit of carbon five tripping devices.
Description of drawings
Fig. 1 is the pneumatic diagram of gas chromatographicanalyzer device of the quantitative test micro-alkyne of an expression use of the present invention four-way valve.
Fig. 2 is the pneumatic diagram of gas chromatographicanalyzer device of the quantitative test micro-alkyne of expression use of the present invention two four-way valves.
The analysis of spectra that Fig. 3 is to use embodiments of the invention 3 described analytical instrument to obtain.
Embodiment
Mode with embodiment further specifies the present invention below, but the present invention is not limited to these embodiment.
Embodiment 1
Further explain gas chromatographicanalyzer device of the present invention below in conjunction with Fig. 1.
Divide the gas circuit of 3420 gas chromatographs to transform in north, obtain analytical instrument of the present invention.
As shown in Figure 1, analytical instrument of the present invention comprises pressure maintaining valve 7, injector 8, post case 6, first packed column 9 of injector 8, second packed column 10, four-way valve 5, vapour lock 11, vapour lock 12, pressure maintaining valve 13, hydrogen flame detector and thermal conductivity detector (TCD), has four interfaces 1,2,3 and 4 on the four-way valve 5.
The stationary phase of packed column 9 is by β, and β-oxydipropionitrile immobile liquid and 101 Diasolid As are formed, and the weight percent content of immobile liquid and diatomite support is respectively 10% and 90%.
The stationary phase union two diethyl phthalate immobile liquids of packed column 10 and 201 Diasolid As are formed, and the weight percent content of immobile liquid and diatomite support is respectively 10% and 90%.
The grain size of the stationary phase of packed column 9 and packed column 10 is 60~120 orders.
The column length of packed column 9 is 6 meters, and internal diameter is 3mm.The column length of packed column 10 is 8 meters, and internal diameter is 3mm.
The carrier gas that packed column 9 and 10 uses is nitrogen.
Embodiment 2
Further explain analytical instrument of the present invention below in conjunction with Fig. 2.
Divide the gas circuit of 3420 gas chromatographs to transform in north, obtain analytical instrument of the present invention.
As shown in Figure 2, analytical instrument of the present invention comprises pressure maintaining valve 7, injector 8, post case 6, first packed column 9 of injector 8, second packed column 10, four-way valve 5, four-way valve 14, vapour lock 11, vapour lock 12, pressure maintaining valve 13, hydrogen flame detector and thermal conductivity detector (TCD), have four interfaces 1,2,3 and 4 on the four-way valve 5, have four interfaces 1 ', 2 ', 3 ' and 4 ' on the four-way valve 14.
The stationary phase of packed column 9 is made up of dimethylsulfolane immobile liquid and 201 Diasolid As, and the weight percent content of immobile liquid and diatomite support is respectively 15% and 85%.
The stationary phase of packed column 10 is made up of dinonyl phthalate immobile liquid and Chromosorb P diatomite support, and the weight percent content of low pole immobile liquid and diatomite support is respectively 25% and 75%.
The grain size of the stationary phase of packed column 9 and packed column 10 is 60~120 orders.
The column length of packed column 9 and packed column 10 is 6 meters, and internal diameter is 3mm.
The carrier gas that packed column 9 and packed column 10 use is hydrogen.
Adopt gas circuit shown in Figure 1, the internal diameter of first packed column is 3mm, and column length is 6 meters, and its stationary phase is by β, and β-oxydipropionitrile immobile liquid and 101 Diasolid As are formed, and the weight percent content of immobile liquid is 10%; The internal diameter of second packed column is 3mm, and column length is 6 meters, and its stationary phase union two diethyl phthalate immobile liquids and 201 diatomite supports are formed, and the weight percent content of immobile liquid is 10%; Carrier gas is a hydrogen, and the carrier gas flux of two packed columns is 45ml/min, and the flow of auxiliary gas is 45ml/min, and the temperature of injector is 200 ℃, and the temperature of thermal conductivity detector (TCD) and hydrogen flame detector is 200 ℃.
For analytical approach of the present invention is described, be that sample is analyzed with the C5 fraction material shown in the table 3, wherein contain the alkynes of trace.Sampling volume is 2 microlitres.
The main composition of table 3 C 5 fraction analytic sample and quality percentage composition
Component | Content (%) | Component | Content (%) |
Isoprene | 43.22 | 2-methyl-1-butene alkene | 7.79 |
1,4 pentadiene | 0.41 | The 2-methyl-2-butene | 8.54 |
Suitable+anti--1,3 pentadiene | 7.25 | Suitable+anti-2-amylene | 11.79 |
Isopentane | 0.28 | N-pentane | 10.90 |
Cyclopentadiene | 1.42 | Other | Surplus |
Do not cut when analyzing for the first time, make analytic sample only by first pillar, entering detecting device then detects, from the spectrogram that obtains, alkynes wherein coincides together, retention time is 10.64 minutes, will be defined as 10.00 minutes to 11.80 minutes clipping time according to time of rising and falling at this peak.
When analyzing for the second time,, obtain analysis of spectra shown in Figure 3 according to cutting above-mentioned clipping time.Analysis of spectra has been represented to have isolated micro-2-butine, pentone and 1-pentyne from this C5 fraction material sample, adopts the quantitatively content of these three alkynes of external standard method.Wherein, 30.11 minutes peak of retention time is a pentone, and 31.88 minutes peak of retention time is the 2-butine, and 35.78 minutes peak of retention time is the 1-pentyne.
The concentration that adopts external standard method to calculate pentone in the C5 fraction material is 15.10ppm, and the concentration of 2-butine is 2.57ppm, and the concentration of 1-pentyne is 6.86ppm.
Claims (10)
1. the gas chromatographicanalyzer device of micro-alkyne in the quantitative test C5 fraction, it is characterized in that: it comprises two packed columns, connects with four-way valve between two packed columns; One end of first packed column (9) is connected with injector (8), and the interface (1) of the other end and four-way valve (5) is connected; The interface (4) of interface (1) adjacency that is connected with first packed column of one end of second packed column (10) and four-way valve (5) connects, and the other end is connected with hydrogen flame detector; On two other interface (2,3) of four-way valve (5), connect vapour lock (11,12) respectively; Wherein the interface (2) of the interface adjacency that is connected with first packed column of an end of vapour lock (11) and four-way valve connects, and the other end is connected with thermal conductivity detector (TCD); The interface (3) of one end of vapour lock (12) and four-way valve is connected, and the other end is connected with carrier gas through pressure maintaining valve; The air resistance of the vapour lock that is connected with thermal conductivity detector (TCD) (11) and the air resistance of second packed column equate that the air resistance of the vapour lock that is connected with hydrogen flame detector (12) and the air resistance of first packed column equate.
2. the gas chromatographicanalyzer device of micro-alkyne in the quantitative test C5 fraction, it is characterized in that: it comprises two packed columns and two four-way valves; Wherein the interface (2 ') of first four-way valve (14) is connected with injector (8), and the interface (1) of the diagonal angle interface (4 ') of this interface (2 ') and second four-way valve (5) is connected; Two other diagonal angle interface (1 ', 3 ') of first four-way valve (14) is connected with first packed column (9); Second four-way valve (5) be connected with second packed column with interface (4) interface (1) adjacency, the other end of second packed column is connected with hydrogen flame detector; Second four-way valve (5) be connected with vapour lock (11) with interface (2) interface (1) adjacency, the other end of this vapour lock (11) is connected with thermal conductivity detector (TCD); The interface (3) of second four-way valve (5) is connected with vapour lock (12), and its other end is connected with carrier gas through pressure maintaining valve; The air resistance of the vapour lock that is connected with thermal conductivity detector (TCD) (11) and the air resistance of second packed column equate that the air resistance of the vapour lock that is connected with hydrogen flame detector (12) and the air resistance of first packed column equate.
3. instrument according to claim 1 and 2 is characterized in that:
The stationary phase of described first packed column is made up of polarity immobile liquid and diatomite support, and the weight percent content of polarity immobile liquid and diatomite support is respectively 5~30% and 70~95%;
The stationary phase of described second packed column is made up of low pole immobile liquid and diatomite support, and the weight percent content of low pole immobile liquid and diatomite support is respectively 5~30% and 70~95%.
4. instrument according to claim 3 is characterized in that:
Described polarity immobile liquid is β, β-oxydipropionitrile, hexamethyl phosphoramide, dimethylsulfolane, 5-methyl-N-Methyl pyrrolidone or Macrogol 2000 0;
Described low pole immobile liquid be ethylazelaate, dinonyl phthalate, di(2-ethylhexyl)phosphate cresols ester, xylenylphosphate, two-2-methoxyl hexane diacid ethyl ester, different thirty alkane or the last of the ten Heavenly stems dioctyl phthalate ester in two ninth of the ten Heavenly Stems;
Described diatomite support is 101 pickling zeyssatite, 201 pickling zeyssatite, Anaprep A zeyssatite, Chromosorb P zeyssatite, Diasolid A zeyssatite, Diatomite P zeyssatite, Diatoport S zeyssatite, K zeyssatite or KVA zeyssatite;
The diatomite support that the stationary phase of described two packed columns uses can be identical or inequality.
5. instrument according to claim 1 and 2 is characterized in that: the grain size of described first packed column and the stationary phase of second packed column can be identical or inequality, is selected from 60~100 purpose particles.
6. instrument according to claim 1 and 2 is characterized in that: the column length of described first packed column and second packed column can be identical or inequality with internal diameter, and their column length is selected from 4~10 meters, and internal diameter is selected from 2~5mm.
7. instrument according to claim 1 and 2 is characterized in that: the carrier gas that described two packed columns use is nitrogen, hydrogen or argon gas.
8. the method for micro-alkyne in the quantitative test C5 fraction, it is characterized in that: use one of claim 1-7 described gas chromatographicanalyzer device, wherein, first packed column is communicated with the vapour lock that is connected with thermal conductivity detector (TCD) (11) through four-way valve, second packed column is communicated with the vapour lock that is connected with hydrogen flame detector (12), and be equal by the carrier gas flux of two packed columns; C5 fraction enters first packed column through injector, and C5 fraction is separated on first packed column; When wherein alkynes flows to the tail end of first packed column, the rotary four-way valve partly is cut into second packed column with alkynes, after having cut four-way valve is rotated back to original position, each alkynes component is separated on second packed column, detects quantitatively with hydrogen flame detector.
9. method according to claim 8 is characterized in that: described C5 fraction is mixed pyrolysis C5 fraction, chemical grade isoprene, polymerization grade isoprene or the C5 fraction that removes carbon four components, m-pentadiene and cyclopentadiene component.
10. method according to claim 8, it is characterized in that: the analysis condition of described chromatography instrument is as follows: the carrier gas flux in described two packed columns is 25-60ml/min, post oven temperature, degree is 25-70 ℃, the flow of auxiliary gas is 25-60ml/min, the flow of air-breathing gas is 25-60ml/min, the temperature of thermal conductivity detector (TCD) is 150-200 ℃, and the temperature of hydrogen flame detector is 200-270 ℃, and the vapourizing temperature of injector is 120-200 ℃.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101354384B (en) * | 2007-07-27 | 2012-07-25 | 中国石油化工股份有限公司 | Method and instrument for quantitatively analyzing trace amount acetylene hydrocarbon in carbon four fractions |
CN109580816A (en) * | 2018-12-11 | 2019-04-05 | 兰州中科安泰分析科技有限责任公司 | It is a kind of for analyzing the gas chromatographic column of benzene homologues |
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CA2431615A1 (en) * | 2000-01-25 | 2001-08-02 | The State Of Oregon Acting By And Through The State Board Of Higher Educ Ation On Behalf Of Portland State University | Method and apparatus for concentrating samples for analysis |
CN2585232Y (en) * | 2002-12-11 | 2003-11-05 | 中国石油化工股份有限公司上海石油化工研究院 | On-line analysing device for propylene ammonia oxidation resultant |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101354384B (en) * | 2007-07-27 | 2012-07-25 | 中国石油化工股份有限公司 | Method and instrument for quantitatively analyzing trace amount acetylene hydrocarbon in carbon four fractions |
CN109580816A (en) * | 2018-12-11 | 2019-04-05 | 兰州中科安泰分析科技有限责任公司 | It is a kind of for analyzing the gas chromatographic column of benzene homologues |
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