CN104569241B - C in gas Chromatographic Determination gasoline or micro-inverse product6the method of following oxygenatedchemicals - Google Patents
C in gas Chromatographic Determination gasoline or micro-inverse product6the method of following oxygenatedchemicals Download PDFInfo
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Abstract
A kind of with C in gas Chromatographic Determination gasoline or micro-inverse product6The method of following oxygenatedchemicals, including the injection port that sample is passed through gas chromatograph, nonpolar chromatographic column is entered after entering pre-cut post, when boiling point is not more than the component of n-undecane all after pre-cut post flows out, by changing chromatographic column pressure program, boiling point is gone out gas chromatogram more than the heavy constituent of n-undecane by shunting outlet blowback, adjust electromagnetic valve on-position, after the isolated component of nonpolar chromatographic column enters highly polar chromatographic column, detected by flame ionization detector again, when 2 hexanones are after nonpolar chromatographic column exits into highly polar chromatographic column, change the position of electromagnetic valve, the carrier gas flowing through nonpolar chromatographic column flows to damping column, the component making boiling point be higher than 2 hexanones is directly entered another flame ionization detector by damping column and detects.This method can reduce the Monitoring lower-cut of oxygenatedchemicals.
Description
Technical field
The present invention is a kind of method of oxygenates level in gas Chromatographic Determination hydrocarbon mixture, specifically, is C in one gas Chromatographic Determination gasoline or micro-inverse product6The method of following oxygenatedchemicals.
Background technology
Micro oxygen containing compound in gasoline fraction is a very important non-hydrocarbon impurities of class contained in gasoline, its content can produce material impact to technical study and product quality, particularly in the technical study of catalytic cracking producing more propylene, the demand measuring oxygenatedchemicals in product is the most urgent.Propylene is as basic industrial chemicals, and its demand constantly rises, and only by traditional steam cracking technique, its yield is difficult to meet the demand in market.The technique of catalytic pyrolysis producing more propylene, is the new way producing propylene, and owing to the raw material of Deep Catalytic Cracking process is complex, the quality of produced propylene is had a significant impact by the micro oxygen containing compound impurity in gained propylene product.For exploring oxygenatedchemicals in the generation of process products process and the regularity of distribution, in addition to the content of the oxygenatedchemicalss such as the methanol in gas-phase product, acetone is measured, meanwhile, the content of the oxygenatedchemicalss such as the Trace Methanol in corresponding gasoline fraction, acetone need to be measured.But the product that microreactor obtains contains substantial amounts of heavy constituent, and the amount generated is little, it is impossible to cut out gasoline fraction.Even and if medium-sized product can cut, but owing to the boiling point of the micro oxygen containing compounds such as methanol is relatively low, still-process exists the risk of loss and its real content and distribution cannot be obtained.A set of can be used for directly measuring the system of micro oxygen containing compound in the micro-inverse product containing heavy constituent, to coordinate the needs of technical study for this reason, it may be necessary to develop.
Owing to vapour oil composition is considerably complicated, the content of the oxygenatedchemicals that wherein may contain is the lowest, the most several μ g/g, and conventional chromatogram analysis method is difficult to separate the oxygenatedchemicals of trace with hydrocarbon component.The oxygenatedchemicalss such as the current methanol measured in gasoline, the twin columns methods using SH/T0663 or the gas chromatogram/oxygen selective detector assay method of SH/T0720, the Determination Limit of one pack system mass fraction may each be about 0.1%, it is impossible to meets the requirement of microanalysis more.
Summary of the invention
It is an object of the invention to provide C in a kind of gas Chromatographic Determination gasoline or micro-inverse product6The method of following oxygenatedchemicals, this method can measure C in micro-example6The content of following oxygenatedchemicals, significantly reduces the Monitoring lower-cut of oxygenatedchemicals.
C in the use gas Chromatographic Determination gasoline of present invention offer or micro-inverse product6The method of following oxygenatedchemicals, comprises the steps:
(1) micro-inverse product or gasoline sample are passed through gas chromatograph and have the injection port of shunting outlet, enter pre-cut post, carry out separating and enter the nonpolar chromatographic column being connected with pre-cut post according to sample component boiling point order, when boiling point is not more than the component of n-undecane all after pre-cut post flows out, reduce the inlet pressure of pre-cut post to less than the pressure being supplied to three-way valve by blowback carrier gas, boiling point is gone out gas chromatogram more than the heavy constituent of n-undecane by shunting outlet blowback by the blowback carrier gas being passed through by three-way valve
(2) electromagnetic valve is placed in open position, make the isolated component of nonpolar chromatographic column be carried along into highly polar chromatographic column by the carrier gas flowing through its outlet, wherein oxygenatedchemicals is separated with hydrocarbon, detect subsequently into flame ionization detector, obtain the chromatogram of oxygenatedchemicals
(3) when methyl-n-butyl ketone is after nonpolar chromatographic column exits into highly polar chromatographic column, change the position of electromagnetic valve, make the isolated boiling point of nonpolar chromatographic column be carried along into damping column higher than the component of methyl-n-butyl ketone by the carrier gas flowing through its outlet, enter back into the detection of another flame ionization detector.
The present invention utilizes containing blowback and the gas chromatography system of heartcut assembly, by controlling blowback time and the electromagnetic valve switching mode of heartcut assembly, eliminating the interference that micro oxygen containing compound is measured by hydrocarbon component, the method for foundation can measure C in gasoline fraction or micro-inverse product1～C4Alcohol, C2～C5Aldehyde, C3～C6Six carbon and the content of following oxygenatedchemicals such as ketone, methyl tertiary butyl ether(MTBE) (MTBE), ethyl tert-butyl oxide (ETBE), tert amyl methyl ether(TAME) (TAME), Monitoring lower-cut can as little as 1～2 μ g/g.Efficiently solve because micro-inverse product amount is few, be difficult to cut out gasoline component and problem that below six carbon that cause, little molecular oxygen-containing compounds content is difficult to measure.
Accompanying drawing explanation
Fig. 1 is the inventive method schematic flow sheet.
The standard curve of the different oxygenatedchemicalss that Fig. 2 is done by the present invention.
Fig. 3 is the oxygenatedchemicals chromatogram in the light FCC gasoline that present example 1 measures.
Fig. 4 is the oxygenatedchemicals chromatogram in the catalytic pyrolysis product of the producing more propylene that present example 2 measures.
Detailed description of the invention
The present invention is by controlling the blowback time of pre-cut post, boiling point is separated from testing sample more than the heavy constituent of n-undecane, remaining component enters nonpolar chromatographic column and separates, by the electromagnetic valve position of main dispatching centre cutting assembly, the oxygenatedchemicals that can be difficult to nonpolar chromatographic column separate sends into highly polar chromatographic column, separate oxygenatedchemicals further, and detect, after methyl-n-butyl ketone enters highly polar chromatographic column, the on-position of conversion electromagnetic valve, it is connected with damping column, the component making boiling point be higher than methyl-n-butyl ketone enters damping column and is directly detected by another flame ionization detector.The present invention removes heavy constituent by blowback, by electromagnetic valve switching nonpolar chromatographic column is difficult to isolate six unimodal carbon again and following oxygenatedchemicals chromatographic peak is cut in highly polar chromatographic column separate further, effectively eliminate the interference of other component, the Monitoring lower-cut of oxygenatedchemicals in sample is greatly reduced.
In the inventive method, described pre-cut post is nonpolar or low pole capillary chromatographic column, and the fixing of its filling is preferably the methyl phenyl silicone containing 5% phenyl, the preferred 2m of column length, the preferred 0.32mm of internal diameter mutually.Pre-cut post for being more than the separation of the heavy constituent of n-undecane by sample mid-boiling point.Pre-cut post one end is connected with chromatographic injection port, and the other end and a three-way valve are connected, and the another two interface of three-way valve is connected with blowback carrier gas inlet pipeline and nonpolar chromatographic column respectively.Sample is entered pre-cut post by chromatography column feed materials mouth, and required component enters nonpolar chromatographic column, and heavy constituent is carried by blowback carrier gas and discharged chromatographic analysis system by chromatograph shunting outlet.
The fixing of described nonpolar chromatographic column is preferably methyl polysiloxane mutually, and the preferred 30m of column length, internal diameter is preferably 0.32mm.
In the present invention, flowed through the flow direction of the nonpolar chromatography column effluent of carrier gas traffic organising of nonpolar column outlet by control.Described carrier gas flows to be controlled by heartcut assembly, and described heartcut assembly is the gas flow path pipeline controlled by electromagnetic valve, including electromagnetic valve, one section of damping and micro-fluidic threeway.One end of nonpolar chromatographic column is connected with the entrance of the micro-fluidic threeway of heartcut assembly, and two interfaces of micro-fluidic threeway are connected with highly polar chromatographic column and damping column respectively, and is connected with the electromagnetic valve in heartcut assembly by pipeline.When electromagnetic valve is set to " opening (ON) " position, the carrier gas entering electromagnetic valve flows through the nonpolar column outlet highly polar chromatographic column of entrance, when electromagnetic valve is set to " cutting out (OFF) " position, the carrier gas entering electromagnetic valve flows to change, and enters damping column through nonpolar column outlet.
Described highly polar chromatographic column is preferably OxyPLOT chromatographic column, and the preferred 10m of column length, internal diameter is preferably 0.53mm.
Described damping column is preferably elastic quartz column jecket, and its chromatographic column resistance is equal with highly polar chromatographic column.
Described highly polar chromatographic column and the outlet of damping column connect two flame ionization detectors (FID) respectively, are used for detecting effluent.
In the present invention (1) step, preferably controlling injection port of chromatograph temperature is 250～280 DEG C, and pressure is 70～75kPa, and controlling split ratio under voltage regulation way is 10～15:1, and sampling volume is 0.5～1.5 μ L；Nitrogen is carrier gas, enters pre-cut post at micro-inverse product or gasoline sample and reaches certain time, when preferably 0.5～1.0min, three-way valve is passed through carrier gas and carries out blowback removing heavy constituent.
The present invention (2) step is cutting detection carbon six and following little molecular oxygen-containing compound, and (3) step is the component removing sample mid-boiling point higher than methyl-n-butyl ketone, removes its interference to tested component.
Chromatographic column in the inventive method, operating condition including pre-cut post, nonpolar chromatographic column, highly polar chromatographic column and damping column is: initial temperature preferably 80～120 DEG C, keeps 3～5min, heating rate preferably 5～10 DEG C/min, final temperature preferably 200～220 DEG C, keeps 5～10min.
The operating condition of described FID is: temperature is 250～280 DEG C, hydrogen flowing quantity preferably 30～35mL/min, air mass flow preferably 350～400mL/min, nitrogen (compensation gas) flow preferably 25～30mL/min.
After sample introduction certain time, when being preferably 0.1min, electromagnetic valve is set to " ON ", the isolated component of nonpolar chromatographic column is made to be carried along into highly polar chromatographic column by carrier gas, when sample introduction 4.0～4.5min, the position of change electromagnetic valve, to " OFF ", makes nonpolar chromatographic column connect with damping column, make the nonpolar chromatographic column isolated boiling point component higher than methyl-n-butyl ketone by damping column, after FID detects, flow out chromatograph.
The oxygenatedchemicals chromatogram that (2) step is obtained by the present invention, in oxygenatedchemicals standard sample according to preparation, the retention time of each component is qualitative, set up quantitation curves further according to each constituent content in standard specimen and chromatographic peak area, use external standard method that the Oxygen-containing Components measured is carried out quantitatively.
External standard method is used to carry out quantitative to component method particularly includes: the C of precise 80mg1～C4Alcohol, C2～C5Aldehyde, C3～C6Ketone, MTBE, DIPE and TAME, add 10g normal heptane, and being configured to above-mentioned each constituent content is the alcohol of 8000 μ g/g, aldehyde, ketone, the mixed standard solution of ether.The standard specimen solution that each constituent content is respectively the oxygenatedchemicals of 2,10,20,80,200 μ g/g is made according to weighing method normal heptane stepwise dilution.According to selected highly polar chromatographic column operating condition measure each standard specimen solution, to each component with content as abscissa, chromatographic peak area as vertical coordinate, be depicted as the quantitation curves of each component.The standard curve of some of which component is shown in Fig. 2.
The quantitation curves equation of a certain component can use formula (1) to represent:
Aj=ajCj+bj(1)
In formula (1),
AjThe chromatographic peak area of component j；
CjThe content of component j, μ g/g;
aj、bjThe standard curve equation coefficient of component j.
The present invention is surveyed each Oxygen-containing Components all can set up the standard curve equation shown in formula (1) as stated above.
After setting up the standard curve equation of each component, according to the content of each Oxygen-containing Components in formula (2) calculating sample:
In formula (2),
CiThe content of tested Oxygen-containing Components i, μ g/g;
AiThe chromatographic peak area of tested Oxygen-containing Components i；
ai、biThe coefficient of the standard curve equation of component i；
ρ0The density of normal heptane, 0.684g/cm used by preparation standard specimen3;
ρsThe density of sample.
The method that the present invention is described below in conjunction with the accompanying drawings.
In Fig. 1, the gas chromatograph used by the present invention is provided with split sampling mouth, three root chromatogram columns, a damping column and heartcut assembly (Deans Switch) 17, and described heartcut assembly 17 includes micro-fluidic threeway, one section of damping 18 and electromagnetic valve 16.One end of pre-cut post 1 is connected with split sampling mouth 5, the other end is connected with the entrance of three-way valve 7, the outlet of three-way valve 7 is connected with blowback lines 11 and nonpolar chromatographic column 2 respectively, the other end of nonpolar chromatographic column 2 is connected with the entrance 8 of the micro-fluidic threeway in heartcut assembly (Deans Switch) 17, micro-fluidic three are connected with two interfaces (12, 13), one of them interface 13 is connected with highly polar chromatographic column 4, another interface 12 is connected with the damping column 3 matched with highly polar post 4 chromatographic column resistance, highly polar chromatographic column 4 is connected with two flame ionization detectors 9 and 10 respectively with the outlet of damping column 3.
When measuring sample, by sample by split sampling mouth 5 injecting chromatograph, during in sample, component initially enters the pre-cut post 1 being connected with injection port 5.In pre-cut post 1, component separates according to the order of boiling point, after the component of boiling point no more than n-undecane all exits into, from pre-cut post, the nonpolar chromatographic column 2 being attached thereto, change the pressure of injection port, being less than the pressure of the blowback carrier gas entered by pipeline 11, pre-cut post 1 mid-boiling point is i.e. carried by blowback carrier gas more than the heavy constituent of n-undecane and goes out chromatograph by shunting outlet 6 blowbacks.
Under sample introduction state, set the position of the electromagnetic valve 16 being connected with heartcut (Deans switch) assembly as opening (ON), the carrier gas (flow2) entering electromagnetic valve is flowed along the marked direction of electromagnetic valve solid line, it is supplied to the pressure that micro-fluidic three-way interface 12 is certain through connecting pipeline 14, after analysis is started, the pressure of micro-fluidic three-way interface 12 is more than the pressure of nonpolar chromatographic column 2 outlet, entered the component outflow of nonpolar chromatographic column 2 by pre-cut post after, the highly polar chromatographic column 4 that oxygenatedchemicals is had special reserve capability flowing to be attached thereto i.e. is carried by carrier gas, carry out Oxygen-containing Components to separate with hydrocarbon component, oxygenatedchemicals after chromatographic isolation enters flame ionization detector 9 and detects.When methyl-n-butyl ketone is after nonpolar chromatographic column 2 exits into highly polar chromatographic column 4, change the position (being set to OFF) of electromagnetic valve 16, carrier gas (flow2) flows to change, flow along the marked direction of electromagnetic valve dotted line, it is supplied to the pressure that micro-fluidic three-way interface 13 is certain through connecting pipeline 15, make its pressure pressure more than the outlet of nonpolar chromatographic column 2, make the boiling point flowed out from nonpolar chromatographic column not enter highly polar chromatographic column 4 higher than remaining component of 2-ketone, but flow to damping column 3 and enter flame ionization detector 10 and detect.
The inventive method is the mensuration of single component content carbon less than six oxygenatedchemicals more than 0.5 μ g/g be applicable to the micro-inverse product measuring initial boiling point to 500 DEG C, including C1～C4Alcohol, C2～C5Aldehyde, C3～C6Ketone, methyl tertiary butyl ether(MTBE), ethyl tert-butyl oxide, the assay of tert amyl methyl ether(TAME).The inventive method is also applied for measuring the mensuration of the little molecular oxygen-containing compounds content of the different process gasoline fraction product such as above-mentioned carbon less than six in straight-run naphtha, reformed oil, catalytically cracked gasoline.
Further illustrate the present invention below by example, but the present invention is not limited to this.
Example 1
The retention time of each oxygenatedchemicals is determined by the inventive method.
Using the Agilent7890 gas chromatograph of Agilent company, connect chromatographic column as shown in Figure 1, set injector temperature as 250 DEG C, under voltage regulation way, inlet pressure is 72.26kPa, split ratio 10:1, and sampling volume is 1 μ L；Nitrogen is carrier gas, and the two-way pressure controlling flow1 and flow2 is respectively 68.95kPa and 29.51kPa；The initial temperature of chromatographic column used is 100 DEG C, keeps 5min, and heating rate is 5 DEG C/min, and final temperature is 210 DEG C, keeps 8min；Electromagnetic valve 16 is set as ON state；Detector uses double FID, and temperature is 280 DEG C, and hydrogen flowing quantity is 30mL/min, and air mass flow is 350mL/min, and nitrogen (compensation gas) flow is 25mL/min.Pre-cut post 1 is HP-5(2m × 0.32mm × 0.25 μm)；Nonpolar chromatographic column 2 is DB-1(30m × 0.32mm × 1.0 μm)；Highly polar chromatographic column 4 is OxyPLOT(10m × 0.53mm × 40 μm), damping column is elastic quartz column jecket.
For blowback heavy constituent, injection port initial pressure keeps 0.7min, with the speed of 700kPa/min, pre-cut column inlet pressure is reduced to 56kPa.Owing to pre-cut column outlet pressure is more than the pressure of injection port, blowback carrier gas is i.e. entered pre-cut post by pipeline 11, flows out from shunting outlet 6 after reversely flowing through pre-cut post 1.Thus the heavy constituent blowback being retained on pre-cut post is gone out chromatograph.
With this understanding, determining that methyl-n-butyl ketone all flows out the time needed for chromatographic column is 4.2min, between at this moment, point arranges electromagnetic valve 16 is OFF state, makes the component flowing out nonpolar chromatographic column 2 after methyl-n-butyl ketone not enter in highly polar chromatographic column 4, and enters detector by damping column 3 and detect.
Under above-mentioned chromatograph imposes a condition, analyze each constituent content and be respectively oxygenatedchemicals mixing qualitative criteria's solution of 100 μ g/g, record the retention time of each component.The each component retention time and the boiling point that measure are shown in Table 1.
Example 2
Prepare the standard sample that each constituent mass mark is 2.0 μ g/g, analyze mensuration under the same conditions as in example 1, with normal heptane gradually dilution standard sample concentration, and sample introduction analysis, determine the detection limit of each compound mensuration.When signal to noise ratio is 3, the detection limit of each component determined is shown in Table 2.
As shown in Table 2, due to C1～C3Alcohol polarity is relatively strong, there is certain adsorption, and its detection limit is higher, is 1.0 μ g/g～2.0 μ g/g, and the detection limit of acetaldehyde and propionic aldehyde is respectively 2.0 μ g/g and 1.0 μ g/g, and the detection limit of other Oxygen-containing Components is 0.5 μ g/g.
Table 1
Table 2
Example 3
Use the Agilent7890 gas chromatograph of Agilent company, be furnished with automatic sampler, heartcut assembly, blowback assembly, double fid detector.According to connecting chromatographic column shown in Fig. 1.Chromatographic column includes: pre-cut post 1, for HP-5(2m × 0.32mm × 0.25 μm), nonpolar chromatographic column 2, for DB-1(30m × 0.32mm × 1.0 μm), highly polar chromatographic column 4, for OxyPLOT(10m × 0.53mm × 40 μm), damping column, for elastic quartz column jecket.Chromatographic condition is: injector temperature 250 DEG C, and under voltage regulation way, inlet pressure is 72.26kPa, split ratio 10:1, and sampling volume is 1 μ L；Nitrogen is carrier gas, keeps 0.7min, terminates to analysis to 56kPa, holding with the rate reduction of 700kPa/min；The pressure of flow1 and flow2 two-way carrier gas is respectively 68.95kPa and 29.51kPa, and the initial temperature of chromatographic column used is 100 DEG C, keeps 5min, and heating rate is 5 DEG C/min, and final temperature is 210 DEG C, keeps 8min；It is OFF that electromagnetic valve 16 arranges state, is set to ON, is set to OFF during sample introduction 4.2min during sample introduction 0.1min；Detector uses double FID, and temperature is 280 DEG C, and hydrogen flowing quantity is 30mL/min, and air mass flow is 350mL/min, and nitrogen (compensation gas) flow is 25mL/min.
After instrument condition is stable, being injected the light FCC gasoline sample of 1.0 μ L high-acid crude oil processing by automatic sampler to the injection port 5 of instrument, and start chromatograph collection signal and record integral result, chromatogram is shown in Fig. 3.After analysis completes, the retention time according to chromatographic peak is qualitative to component, according to the chromatographic peak area of the component peaks determined, calculates the content of each component according to formula (2), and it the results are shown in Table 3.
Table 3
Example 4
Chromatographic system connected mode as described in example 3 connects the chromatograph operating parameter needed for chromatographic column, and setting.After instrument condition is stable, inject, to the injection port of instrument, the most cleaved Product samples that the end point of distillation is 500 DEG C that the medium-sized reactor of Deep Catalytic Cracking process of 1.0 μ L producing more propylenes obtains by automatic sampler.Starting chromatograph gather signal and record integral result, the chromatogram of sample is shown in Fig. 4.As shown in Figure 4, boiling point exceedes the heavy constituent of gasoline fraction and does not disturb the mensuration of little molecular oxygen-containing compound.
Claims (9)
1. one kind with C in gas Chromatographic Determination gasoline or micro-inverse product6The method of following oxygenatedchemicals, bag
Include following steps:
(1) micro-inverse product or gasoline sample are passed through gas chromatograph and have the injection port of shunting outlet, enter
Pre-cut post (1), carries out separating and enter non-with what pre-cut post (1) was connected according to sample component boiling point order
Polarity chromatographic column (2), when boiling point is not more than the component of n-undecane all after pre-cut post (1) flows out,
The inlet pressure reducing pre-cut post (1) is extremely less than the pressure being supplied to three-way valve (7) by blowback carrier gas, by
The blowback carrier gas that three-way valve (7) is passed through is anti-by shunting outlet (6) more than the heavy constituent of n-undecane by boiling point
Blowout gas chromatogram,
(2) electromagnetic valve (16) is placed in open position, makes nonpolar chromatographic column (2) isolated component
It is carried along into highly polar chromatographic column (4) by the carrier gas flowing through its outlet, wherein oxygenatedchemicals is divided with hydrocarbon
From, detect subsequently into flame ionization detector (9), obtain the chromatogram of oxygenatedchemicals,
(3) when methyl-n-butyl ketone is after nonpolar chromatographic column (2) exits into highly polar chromatographic column (4), change
The position of power transformation magnet valve (16), makes nonpolar chromatographic column (2) the isolated boiling point group higher than methyl-n-butyl ketone
Divide the carrier gas by flowing through its outlet to be carried along into damping column (3), enter back into another flame ionization detector
(10) detection,
Described pre-cut post (1) is nonpolar or low pole capillary chromatographic column, fixing of pre-cut post (1)
Being the methyl phenyl silicone containing 5% phenyl mutually, described highly polar chromatographic column (4) is OxyPLOT
Chromatographic column,
The operating condition of chromatographic column used is: initial temperature is 80～120 DEG C, keeps 3～5min, and heating rate is
5～10 DEG C/min, final temperature is 200～220 DEG C, keeps 5～10min.
The most in accordance with the method for claim 1, it is characterised in that the chromatographic column of described pre-cut post (1)
Long 2m, internal diameter is 0.32mm.
The most in accordance with the method for claim 1, it is characterised in that described nonpolar chromatographic column (2)
Fixing is methyl polysiloxane mutually, and column length 30m, internal diameter is 0.32mm.
The most in accordance with the method for claim 1, it is characterised in that the color of described highly polar chromatographic column (4)
Spectrum column length 10m, internal diameter is 0.53mm.
The most in accordance with the method for claim 1, it is characterised in that described damping column (3) is elastic stone
English column jecket.
The most in accordance with the method for claim 1, it is characterised in that (1) injection port of chromatograph temperature in step
250～280 DEG C, pressure is 70～75kPa, and controlling split ratio under voltage regulation way is 10～15:1, sample introduction body
Amassing is 0.5～1.5 μ L；Nitrogen is carrier gas, micro-inverse product or gasoline sample enter pre-cut post (1) 0.5～
During 1.0min, reduce the inlet pressure of pre-cut post (1), three-way valve (7) the blowback carrier gas being passed through is carried out
Blowback.
The most in accordance with the method for claim 1, it is characterised in that flame ionization detector (9,10)
Temperature be 250～280 DEG C, hydrogen flowing quantity is 30～35mL/min, and air mass flow is 350～400mL/min,
Nitrogen make-up gas flow is 25～30mL/min.
8. according to the method described in claim 1 or 7, it is characterised in that when sample introduction 0.1min, by electricity
Magnet valve (16) is placed in open position, makes nonpolar chromatographic column (2) isolated component enter highly polar chromatograph
Post (4), when sample introduction 4.0～4.5min, changes the position of electromagnetic valve (16), makes nonpolar chromatographic column
(2) isolated boiling point enters damping column (3) higher than the component of methyl-n-butyl ketone.
The most in accordance with the method for claim 1, it is characterised in that the oxygenatedchemicals that (2) step is obtained
Chromatogram, qualitative, further according to mark according to the retention time of each component in the oxygenatedchemicals standard sample of preparation
Each constituent content and chromatographic peak area in sample set up quantitation curves, use external standard method oxygen-containing to measure
Compound component is carried out quantitatively.
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| CN107315051A (en) * | 2016-06-12 | 2017-11-03 | 中国石油化工股份有限公司 | The detection method of methyl tertiary butyl ether(MTBE) in gas station, POL storage operation place air |
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