CN110146609A - A kind of the qualitative and quantitative analysis analytical equipment and method of gas component - Google Patents
A kind of the qualitative and quantitative analysis analytical equipment and method of gas component Download PDFInfo
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- CN110146609A CN110146609A CN201910372997.6A CN201910372997A CN110146609A CN 110146609 A CN110146609 A CN 110146609A CN 201910372997 A CN201910372997 A CN 201910372997A CN 110146609 A CN110146609 A CN 110146609A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
Abstract
The present invention provides the qualitative and quantitative analysis analytical equipments and method of a kind of gas component.The quantitative of gas component, qualitative detection may be implemented in the device and method that test and analyze, the method is using system gas chromatography, different valves is opened by different time sections, into different chromatographic columns, it is different with the polarity of pillar according to retention time difference, to realize qualitative and quantitative analysis.The qualitative and quantitative analysis analysis for testing and analyzing device and method and preparing the gas component in the reaction of the tert-butyl alcohol especially suitable for oxidation of isobutane；And the qualitative and quantitative analysis analysis of the gas component in the reaction that the qualitative and quantitative analysis of the gas component suitable for the reaction that propylene oxidation prepares propylene oxide is analyzed and isobutene prepares the methyl tert-butyl alcohol.
Description
Technical field
The invention belongs to gas composition analysis method and apparatus technical fields, and in particular to a kind of gas component it is qualitative,
Quantitative detecting analysis device and method, in particular to a kind of oxidation of isobutane prepare determining for the gas component in the reaction of the tert-butyl alcohol
Property, quantitative detecting analysis device and method.
Background technique
In the preparation process of any one chemical products, require to the gas phase or liquid phase component progress in reaction mass
Qualitative or quantitative analysis realizes the regulation to reaction such as conversion ratio, activity, yield for the dynamic of monitoring reaction course.
Illustratively, in the reaction that oxidation of isobutane prepares the tert-butyl alcohol, to carry out in real time the qualitative of each component in reaction stream and
Quantitative detection.Especially for gaseous component, due to the complicated components in gas stream, it is not easy to realize institute using conventional method
There are the qualitative and quantitative analysis of component, especially accurate quantitative detection.
In the preparation process of conventional chemical products, the substance that may contain in gas phase system includes but is not limited to H2、O2、
N2、CO、CO2、C1-C4Hydrocarbons, oxygen carrier etc..Illustratively, the hydrocarbons oxidation or catalysis oxidation of C1-C4
The reaction for preparing alcohols, epoxide, organic peroxide usually carries out at high temperature under high pressure, and product composition is very multiple
It is miscellaneous, for example including unreacted raw material, oxidant；The initiator that reaction starting is added；There is principal product oxygenatedchemicals；There are also each
Kind by-product, entire reaction system is exactly a vapor liquid equilibrium system.OXO products are generally there are in liquid, but reaction system
Gas composition has C1-C4Hydro carbons, H2、O2、N2、CO、CO2, with oxygenatedchemicals etc. existing for gaseous state, these gaseous components
Boiling point from -196 DEG C~117 DEG C, 300 DEG C of span or so；And from nonpolar O2、N2To highly polar acetic acid, butyric acid, second two
Alcohol, propylene glycol, reaction system is qualitative, quantifies all troublesome time-consuming.The detection of one gas phase sample even needs to use 3-4 platform color
Spectrum could complete measurement, greatly reduce working efficiency.
Summary of the invention
In order to improve the deficiencies in the prior art, the object of the present invention is to provide a kind of qualitative and quantitative analyses of gas component
Analytical equipment and method.The quantitative of gas component, qualitative detection may be implemented in the device and method that test and analyze, in addition, institute
It states and tests and analyzes device and method suitable for containing C simultaneously1-C4Hydrocarbons (such as alkane, alkene or alkynes), H2、O2、N2、
CO、CO2, the gases such as oxygenatedchemicals steam detection.The oxygenatedchemicals for example can be methanol, ethyl alcohol, propyl alcohol, isopropyl
Alcohol, butanol, the tert-butyl alcohol, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, acetone, butanone, propylene oxide, ethylene oxide, formic acid, acetic acid, third
Acid, butyric acid, tert-butyl hydroperoxide, di-tert-butyl peroxide (DTBP), iso-butyl formate (TBF), iso-butyl formate (IBF)
At least one of Deng.The method is different valves to be opened by different time sections, into difference using gas chromatography
Chromatographic column, it is different according to the polarity of retention time difference and pillar, to realize qualitative and quantitative analysis.The detection and analysis
Device and method prepare the qualitative and quantitative analysis point of the gas component in the reaction of the tert-butyl alcohol especially suitable for oxidation of isobutane
Analysis；The qualitative and quantitative analysis of gas component suitable for the reaction that propylene oxidation prepares propylene oxide is analyzed, and is applied also for different
Butylene prepares the qualitative and quantitative analysis analysis of the gas component in the reaction of the methyl tert-butyl alcohol.
Object of the present invention is to what is be achieved through the following technical solutions:
A kind of qualitative and quantitative analysis analytical equipment of gas component, described device include the first gas import to be measured, gas to be measured
Outlet, the first carrier gas inlet, the second carrier gas inlet, third carrier gas inlet, the first quantitative loop, the second quantitative loop, the first six-way valve,
Second six-way valve, ten-way valve, fid detector, TCD detector, the first damper tube, the second empty chromatographic column, the first pre-separation column, the
Pipeline between two pre-separation columns, the first chromatographic column, the second chromatographic column and connecting components；
The first gas import to be measured is connect by the first six-way valve with the first end of the first quantitative loop, the first quantitative loop
Second end is connect by the first six-way valve and ten-way valve with the first end of the second quantitative loop, and the second end of the second quantitative loop passes through ten
Port valve and gas to be measured outlet connect；
First carrier gas inlet is connect by the first six-way valve with the first end of the first quantitative loop, and the of the first quantitative loop
Two one end are connect by the first six-way valve with the first end of the first chromatographic column, and the second end and FID of first chromatographic column detect
Device connection；
Second carrier gas inlet is connect by ten-way valve with the second end of the second quantitative loop, the first end of the second quantitative loop
It is connect by ten-way valve with the first end of the first pre-separation column, the second end of the first pre-separation column passes through ten-way valve and second
The connection of pre-separation column first end；
The third carrier gas inlet is connect by the first damper tube with ten-way valve, the ten-way valve and the second pre-separation column
First end connection；
The second end of second pre-separation column is connect by the second six-way valve with the second chromatographic column or the second empty chromatographic column, described
Second chromatographic column or the second empty chromatographic column are connect by the second six-way valve with TCD detector.
According to the present invention, described device further includes that the first empty chromatographic column and drain, second carrier gas inlet pass through ten
Port valve is connect with the second end of the first pre-separation column, and the first end of the first pre-separation column passes through ten-way valve and the first empty chromatography
The first end of column connects, and the second end of the described first empty chromatographic column is connect with drain.
According to the present invention, first chromatographic column is for separating C1-C4At least one in hydrocarbons and oxygenatedchemicals
Kind；The first pre-separation column, the second pre-separation column and the second chromatographic column are for separating CH4、H2、O2、N2, CO and CO2In extremely
Few one kind.
According to the present invention, first six-way valve remember in the direction of the clock including port 1A, port 2A, port 3A ...,
Port 6A, the ten-way valve remember in the direction of the clock including port 1B, port 2B, port 3B ..., port 10B.
According to the present invention, the described first gas import to be measured is quantitative by port 6A, the port 1A and first of the first six-way valve
The first end of ring connects, and the second end of the first quantitative loop passes sequentially through port 4A, the port 5A and ten-way valve of the first six-way valve
The port 10B of port 10B connection, ten-way valve is connect by the port 1B of ten-way valve with the first end of the second quantitative loop, and second is fixed
The second end of amount ring passes sequentially through the port 8B of ten-way valve, port 9B and gas to be measured outlet connects.Under this state, fixed using first
The loading process of gas to be measured may be implemented in amount ring and the second quantitative loop.It specifically can be in the first six-way valve and ten-way valve as shown in figure 1
Solid line representated by valve connection relationship.
According to the present invention, it is fixed to pass sequentially through the port 2A of the first six-way valve, port 1A and first for first carrier gas inlet
The first end connection of ring is measured, the second end of the first quantitative loop passes sequentially through the port 4A, port 3A and the first color of the first six-way valve
The first end connection of column is composed, the second end of first chromatographic column is connect with fid detector.Under this state, first carrier gas
The carrier gas that import is passed through for example can be nitrogen, be used to purge the under test gas in the first quantitative loop, and carry it into first
Separation detection is carried out in chromatographic column.
According to the present invention, described device further includes automatic flow controller, the automatic flow controller and the first carrier gas
Import connection, for controlling the carrier gas flux for passing through the first carrier gas inlet.
According to the present invention, second carrier gas inlet pass through port 7B, the port 8B of ten-way valve and the second quantitative loop the
The first end of the connection of two ends, the second quantitative loop is connected by port 1B, the port 2B of ten-way valve and the first end of the first pre-separation column
It connects, the second end of the first pre-separation column passes sequentially through the first of the port 6B of ten-way valve, port 5B and the second pre-separation column
End connection, the second end of the second pre-separation column are connect with the second six-way valve.Under this state, the load that second carrier gas inlet is passed through
Gas for example can be nitrogen, be used to purge the under test gas in the second quantitative loop, and carry it into the first pre-separation column and
Pre-separation is carried out in two pre-separation columns, i.e. realization CH4、H2、O2、N2、CO、CO2、C1-C4Point of hydrocarbons and oxygenatedchemicals
From specifically can be C2-C4Hydrocarbons and oxygenatedchemicals stay in the first pre-separation column, by CH4、H2、O2、N2、CO、
CO2It is sent into the second pre-separation column and is separated again.
According to the present invention, second carrier gas inlet passes through port 7B, the port 6B of ten-way valve and the first pre-separation column
Second end connection, port 2B, the port 3B and the first sky chromatographic column that the first end of the first pre-separation column passes through ten-way valve
The other end of one end connection, the described first empty chromatographic column is connect with drain.
Under this state, the carrier gas that second carrier gas inlet is passed through for example can be nitrogen, be used to purge first pre- point
From C remaining in column1-C4Hydrocarbons and oxygenatedchemicals.
According to the present invention, the third carrier gas inlet passes through port 4B, the port 5B of the first damper tube and ten-way valve and the
The first end of two pre-separation columns connects, and the second end of the second pre-separation column is connect with the second six-way valve.
Under this state, the carrier gas that the third carrier gas inlet is passed through for example can be nitrogen, be used to purge second pre- point
From the CH in column4、H2、O2、N2、CO、CO2, and be sent in the second chromatographic column and then detected to obtain by TCD detector.
According to the present invention, described device further includes automatic pressure controller, the automatic pressure controller and the second carrier gas
Import is connected with third carrier gas inlet, for controlling the carrier gas flux for passing through the second carrier gas inlet and third carrier gas inlet.It is described
The quantity of automatic pressure controller is, for example, two, is connect respectively with the second carrier gas inlet and third carrier gas inlet, each control
The carrier gas flux of corresponding carrier gas inlet.
According to the present invention, second six-way valve be denoted as in the direction of the clock port 1C, port 2C, port 3C ..., it is logical
Mouth 6C.
According to the present invention, port 6C, port 1C, the second color of the second end of the second pre-separation column and the second six-way valve
One end connection of column is composed, the other end of the second chromatographic column is connected by port 2C, port 3C and the TCD detector of the second six-way valve
It connects.
Under this state, the carrier gas from third carrier gas inlet is used to purge the CH in the second pre-separation column4、H2、O2、N2、
CO、CO2, and by CH therein4、H2、O2、N2, CO be sent into the second chromatographic column in, due to H2It is not stopped in the second chromatographic column,
It directly can be detected to obtain by TCD detector.
According to the present invention, port 6C, the port 5C and second of the second end of the second pre-separation column and the second six-way valve
One end of empty chromatographic column connects, and the other end of the second empty chromatographic column is detected by port 4C, the port 3C and TCD of the second six-way valve
Device connection.
Carrier gas from third carrier gas inlet is used to purge the CH in the second pre-separation column4、H2、O2、N2、CO、CO2, and will
CH therein4、H2、O2、N2, CO be sent into the second chromatographic column, and by CO2It stays in the second pre-separation column, adjusts the second six-way valve
Port position under this state, by CO2It is sent into the second empty chromatographic column, then is detected to obtain by TCD detector.Work as CO2Completely
After appearance, the port position of the second six-way valve is adjusted again, will be left in the CH in the second chromatographic column using carrier gas4、O2、N2, CO blows
It sweeps into TCD detector, is then detected.
The present invention also provides a kind of qualitative and quantitative analysis analysis method of gas component, the method is based on above-mentioned
Device is tested and analyzed, described method includes following steps:
1) the port state of the first six-way valve and ten-way valve is adjusted, so that the first six-way valve and ten-way valve series connection, gas to be measured
Body enters from the first gas import to be measured, is entered in the first quantitative loop and the second quantitative loop by the first six-way valve and ten-way valve, complete
At the loading process of under test gas；
2) the port state of the first six-way valve is adjusted, so that will be in the first quantitative loop from the carrier gas that the first carrier gas inlet enters
Under test gas bring into the first chromatographic column and separated, after separation through constituent part in fid detector detection under test gas and
Content；
3) the port state of ten-way valve and the second six-way valve is adjusted, so that the carrier gas entered from the second carrier gas inlet is by second
Under test gas in quantitative loop brings the first pre-separation column into, carries out pre-separation in the second pre-separation column, and by from third carrier gas
The carrier gas that import enters brings the constituent part in the second pre-separation column in the second six-way valve into be separated, through TCD after separation
Detector detects constituent part and content under test gas.
According to the present invention, contain C in the under test gas1-C4Hydrocarbons, H2、O2、N2、CO、CO2, oxygenatedchemicals steam
The gas detections such as vapour.The oxygenatedchemicals for example can be methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, the tert-butyl alcohol, formaldehyde,
Acetaldehyde, propionic aldehyde, butyraldehyde, acetone, butanone, propylene oxide, ethylene oxide, formic acid, acetic acid, propionic acid, butyric acid, tert-butyl hydroperoxide
Hydrogen, di-tert-butyl peroxide (DTBP), iso-butyl formate (TBF), iso-butyl formate (IBF) etc..
Preferably, according to the property of above-mentioned each component, wherein CH4、H2、O2、N2、CO、CO2TCD detector quilt can be passed through
It detects, C1-C4Hydrocarbons and oxygenatedchemicals can be detected by fid detector.
According to the present invention, step 1) specifically:
The port state of the first six-way valve and ten-way valve is adjusted, so that the first six-way valve and ten-way valve series connection, by gas to be measured
Body is sent into the first gas import to be measured, and it is quantitative into first that under test gas passes sequentially through the port 6A of the first six-way valve, port 1A
Ring is loaded, passed sequentially through after the completion of loading the port 4A of the first six-way valve, the port 5A of the first six-way valve, ten-way valve it is logical
Mouthful 10B, ten-way valve port 1B enter the second quantitative loop and be loaded, extra under test gas passes through ten-way valve after the completion of loading
Port 8B, port 9B from gas to be measured export be discharged, that is, realize the loading process under test gas in quantitative loop.
According to the present invention, step 2) specifically:
The port state of the first six-way valve is adjusted, so that it is logical to pass sequentially through the one or six from the carrier gas that the first carrier gas inlet enters
Port 2A, the port 1A of valve enter in the first quantitative loop, the under test gas in the first quantitative loop are taken away, and pass sequentially through first
Port 4A, the port 3A of six-way valve, which inject in the first chromatographic column, to be separated, through in fid detector detection under test gas after separation
C1-C4Hydrocarbons and oxygenatedchemicals and content.
According to the present invention, step 3) further includes following steps:
3 ') the port state of ten-way valve is adjusted, so that will be in the first pre-separation column from the carrier gas that the second carrier gas inlet enters
Remaining constituent part is brought into the first empty chromatographic column, and emptying processing is carried out.
According to the present invention, step 3) specifically:
The port state of ten-way valve and the second six-way valve 3-1) is adjusted, so that successively leading to from the carrier gas that the second carrier gas port enters
Port 7B, the port 8B for crossing ten-way valve bring the under test gas in the second quantitative loop in the first pre-separation column into be separated, to
It surveys gas and obtains first group of component and second group of component through the first pre-separation post separation, wherein first group of component contains CH4、H2、
O2、N2、CO、CO2At least one of, second group is divided into C1-C4Hydrocarbons and oxygenatedchemicals；
3-2) when first group of group separates the first pre-separation column and fully enter the second pre-separation column, second group of group at this time
Still fractionation adjusts the port state of ten-way valve in the first pre-separation column, so that successively leading to from the carrier gas that the second carrier gas port enters
Port 7B, the port 6B for crossing ten-way valve enter in the first pre-separation column, the second group of component band that will be left in the first pre-separation column
It walks, and passes through the port 2B of ten-way valve, port 3B, the first empty chromatographic column and drain emptying；Meanwhile entering from third carrier gas port
Carrier gas pass sequentially through the first damper tube, the port 4B of ten-way valve, port 5B for first group of component band in the second pre-separation column
Enter in the second six-way valve.
According to the present invention, step 3) further includes following steps:
The port state for 3-3) adjusting the second six-way valve, so that H2Port 6C, the port 1C of the second six-way valve are entered through,
Again through the second chromatographic column, then detected by TCD by port 2C, the port 3C of the second six-way valve；At this point, CH4、O2、N2, CO into
Enter the port 6C by the second six-way valve, port 1C, into the second chromatographic column, CO2Still in the second pre-separation column；
The port state for 3-4) adjusting the second six-way valve, so that CO2Enter through port 6C, the port of the second six-way valve
5C is detected into the second empty chromatographic column, then by port 2C, the port 3C of the second six-way valve by TCD；
The port state for 3-5) adjusting the second six-way valve, so that CH4、O2、N2, CO enter through the port of the second six-way valve
6C, port 1C are detected into the second chromatographic column, then by port 2C, the port 3C of the second six-way valve by TCD.
According to the present invention, first chromatographic column, the second chromatographic column and third chromatographic column, which are that this field is conventional, to use
Contain C in realization1-C4Hydrocarbons, H2、O2、N2、CO、CO2, oxygenatedchemicals steam gas detection chromatographic column.
Illustratively, first chromatographic column removes CH for separating4、H2、O2、N2、CO、CO2C in addition2-C4Hydrocarbon
At least one of matter, oxygenatedchemicals；Select the chromatographic column known in the art that can separate said components, such as institute
The model for stating the first chromatographic column can be 1701 chromatographic columns, 0.25mm*0.25 μm of * 30m of specification.
Illustratively, second chromatographic column is for separating CH4、H2、O2、N2, CO and CO2At least one of；Select this
The chromatographic column of said components can be separated known to field, such as second column model can be MS-13X chromatography
Column, specification 80/100mesh, 3.2mm*2.1mm*3.0m.
According to the present invention, the first pre-separation column and the second pre-separation column are that conventional can be used to implement in this field contains
There is C1-C4Hydrocarbons, H2、O2、N2、CO、CO2, oxygenatedchemicals steam gas detection pre-separation chromatographic column.
Illustratively, the first pre-separation column and the second pre-separation column are used for pre-separation CH4、H2、O2、N2, CO and CO2In extremely
Few one kind；Select the chromatographic column known in the art that can separate said components, such as the first pre-separation column and
Two pre-separation column type numbers are PN column, specification 80/100mesh3.2mm*2.1mm*1.0m.
According to the present invention, first damping column, the first empty chromatographic column and the second empty chromatographic column are void column pipe.
According to the present invention, the analysis and detection device can be chromatograph.
According to the present invention, the chromatographic post case: 35~70 DEG C of initial temperature, for example, 60 DEG C holding 5min, with 2-
20 DEG C/min, for example, 10 DEG C/min rises to 100~180 DEG C, for example, 130 DEG C, keeps 5min.
According to the present invention, the temperature of the first under test gas import is 80~200 DEG C, for example, 150 DEG C.
According to the present invention, split ratio: 5:1~150:1, for example, 10:1.
According to the present invention, the detection temperature of the fid detector is 150-250 DEG C, for example, 200 DEG C.
According to the present invention, the detection temperature of the TCD detector: 170 DEG C；Electric current: 60mA；Polarity: "-".
According to the present invention, the carrier gas of first carrier gas inlet injection is nitrogen, flow velocity 1-5mL/min, for example,
2.0mL/min；The carrier gas of the second carrier gas inlet injection is argon gas, flow velocity 10-40mL/min, for example, 25.0mL/
min；The carrier gas of the third carrier gas inlet injection is argon gas, flow velocity 1-5mL/min, for example, 3.0mL/min.
Beneficial effects of the present invention:
The present invention provides the qualitative and quantitative analysis analytical equipments and method of a kind of gas component.The detection and analysis dress
It sets and the quantitative of gas component, qualitative detection may be implemented with method, in addition, the detection and analysis device and method are suitable for simultaneously
Contain C1-C4Hydrocarbons, H2、O2、N2、CO、CO2, the gas detections such as oxygenatedchemicals steam.The oxygenatedchemicals for example may be used
Be methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, the tert-butyl alcohol, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, acetone, butanone, propylene oxide,
Ethylene oxide, formic acid, acetic acid, propionic acid, butyric acid, tert-butyl hydroperoxide, di-tert-butyl peroxide (DTBP), iso-butyl formate
(TBF), iso-butyl formate (IBF) etc..The method is opened by different time sections different using system gas chromatography
Valve, it is different according to retention time difference and the polarity of pillar into different chromatographic columns, to realize qualitative and quantitative analysis.
It is described test and analyze device and method prepared especially suitable for oxidation of isobutane the gas component in the reaction of the tert-butyl alcohol it is qualitative,
Quantitative detecting analysis；And the qualitative and quantitative analysis of the gas component suitable for the reaction that propylene oxidation prepares propylene oxide
Analysis and isobutene prepare the qualitative and quantitative analysis analysis of the gas component in the reaction of the methyl tert-butyl alcohol.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that device is tested and analyzed described in a preferred embodiment of the invention.
Fig. 2 is the fid detector chromatogram of under test gas shown in the embodiment of the present invention 3.
Fig. 3 is the TCD detector chromatogram of under test gas shown in the embodiment of the present invention 3.
Specific embodiment
Further detailed description is done to method of the invention below in conjunction with specific embodiment.It should be appreciated that following
Embodiment is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.All bases
In the range of the technology that above content of the present invention is realized is encompassed by the present invention is directed to protect.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
In the description of the present invention, it should be noted that term " first ", " second ", " third " etc. are only used for description mesh
, and do not indicate that or imply relative importance.
Embodiment 1
The present embodiment provides a kind of qualitative and quantitative analysis analytical equipment of gas component, described device includes first to be measured
Gas import, gas to be measured outlet, the first carrier gas inlet, the second carrier gas inlet, third carrier gas inlet, the first quantitative loop, second quantify
Ring, the first six-way valve, the second six-way valve, ten-way valve, fid detector, TCD detector, the first damper tube, the second empty chromatographic column,
Pipeline between first pre-separation column, the second pre-separation column, the first chromatographic column, the second chromatographic column and connecting components；
The first gas import to be measured is connect by the first six-way valve with the first end of the first quantitative loop, the first quantitative loop
Second end is connect by the first six-way valve and ten-way valve with the first end of the second quantitative loop, and the second end of the second quantitative loop passes through ten
Port valve and gas to be measured outlet connect；
First carrier gas inlet is connect by the first six-way valve with the first end of the first quantitative loop, and the of the first quantitative loop
Two one end are connect by the first six-way valve with the first end of the first chromatographic column, and the second end and FID of first chromatographic column detect
Device connection；
Second carrier gas inlet is connect by ten-way valve with the second end of the second quantitative loop, the first end of the second quantitative loop
It is connect by ten-way valve with the first end of the first pre-separation column, the second end of the first pre-separation column passes through ten-way valve and second
The connection of pre-separation column first end；
The third carrier gas inlet is connect by the first damper tube with ten-way valve, the ten-way valve and the second pre-separation column
First end connection；
The second end of second pre-separation column is connect by the second six-way valve with the second chromatographic column or the second empty chromatographic column, described
Second chromatographic column or the second empty chromatographic column are connect by the second six-way valve with TCD detector.
In a preferred embodiment of the invention, described device further includes the first empty chromatographic column and drain, and described the
Two carrier gas inlets are connect by ten-way valve with the second end of the first pre-separation column, and the first end of the first pre-separation column passes through ten
Port valve is connect with the first end of the first empty chromatographic column, and the second end of the described first empty chromatographic column is connect with drain.
In a preferred embodiment of the invention, first chromatographic column is for separating C1-C4Hydrocarbons and containing oxidation
Close at least one of object；The first pre-separation column, the second pre-separation column and the second chromatographic column are for separating CH4、H2、O2、
N2, CO and CO2At least one of.
In a preferred embodiment of the invention, the first gas import to be measured by the port 6A of the first six-way valve,
Port 1A is connect with the first end of the first quantitative loop, the second end of the first quantitative loop pass sequentially through the first six-way valve port 4A,
The port 10B connection of port 5A and ten-way valve, the port 10B of ten-way valve pass through the port 1B of ten-way valve and the second quantitative loop the
One end connection, the second end of the second quantitative loop passes sequentially through the port 8B of ten-way valve, port 9B and gas to be measured outlet connects.This shape
Under state, the loading process of gas to be measured may be implemented using the first quantitative loop and the second quantitative loop.It specifically can be with the as shown in figure 1 the 1st
Valve connection relationship representated by solid line in port valve and ten-way valve.
In a preferred embodiment of the invention, first carrier gas inlet passes sequentially through the port of the first six-way valve
2A, port 1A are connect with the first end of the first quantitative loop, and the second end of the first quantitative loop passes sequentially through the port of the first six-way valve
4A, port 3A are connect with the first end of the first chromatographic column, and the second end of first chromatographic column is connect with fid detector.This shape
Under state, the carrier gas that first carrier gas inlet is passed through for example can be nitrogen, be used to purge the gas to be measured in the first quantitative loop
Body, and carry it into and carry out separation detection in the first chromatographic column.
In a preferred embodiment of the invention, second carrier gas inlet passes through port 7B, the port 8B of ten-way valve
It is connect with the second end of the second quantitative loop, the first end of the second quantitative loop is pre- by port 1B, the port 2B and first of ten-way valve
The first end of splitter connects, and the second end of the first pre-separation column passes sequentially through the port 6B of ten-way valve, port 5B and the
The first end of two pre-separation columns connects, and the second end of the second pre-separation column is connect with the second six-way valve.Under this state, described second
The carrier gas that carrier gas inlet is passed through for example can be nitrogen, be used to purge the under test gas in the second quantitative loop, and carry it into
Pre-separation is carried out in first pre-separation column and the second pre-separation column, i.e. realization CH4、H2、O2、N2、CO、CO2、C1-C4Hydrocarbons
With the separation of oxygenatedchemicals, specifically can be C2-C4Hydrocarbons and oxygenatedchemicals stay in the first pre-separation column, will
CH4、H2、O2、N2、CO、CO2It is sent into the second pre-separation column and is separated again.
In a preferred embodiment of the invention, second carrier gas inlet passes through port 7B, the port 6B of ten-way valve
It is connect with the second end of the first pre-separation column, the first end of the first pre-separation column passes through port 2B, the port 3B of ten-way valve
It is connect with one end of the first empty chromatographic column, the other end of the described first empty chromatographic column is connect with drain.Under this state, described
The carrier gas that two carrier gas inlets are passed through for example can be nitrogen, be used to purge remaining C in the first pre-separation column1-C4Hydrocarbons
And oxygenatedchemicals.
In a preferred embodiment of the invention, the third carrier gas inlet passes through the logical of the first damper tube and ten-way valve
Mouth 4B, port 5B are connect with the first end of the second pre-separation column, and the second end of the second pre-separation column is connect with the second six-way valve.This
Under state, the carrier gas that the third carrier gas inlet is passed through for example can be nitrogen, be used to purge in the second pre-separation column
CH4、H2、O2、N2、CO、CO2, and be sent in the second chromatographic column and then detected to obtain by TCD detector.
In a preferred embodiment of the invention, described device further includes automatic flow controller, the automatic flow
Controller is connect with the first carrier gas inlet, for controlling the carrier gas flux for passing through the first carrier gas inlet.
In a preferred embodiment of the invention, described device further includes automatic pressure controller, the automatic pressure
Controller is connect with the second carrier gas inlet and third carrier gas inlet, passes through the second carrier gas inlet and third carrier gas inlet for controlling
Carrier gas flux.The quantity of the automatic pressure controller is, for example, two, respectively with the second carrier gas inlet and third carrier gas into
Mouth connection, each carrier gas flux for controlling corresponding carrier gas inlet.
In a preferred embodiment of the invention, the second end of the second pre-separation column and the port of the second six-way valve
One end connection of 6C, port 1C, the second chromatographic column, the other end of the second chromatographic column pass through port 2C, the port of the second six-way valve
3C is connect with TCD detector.Under this state, the carrier gas from third carrier gas inlet is used to purge the CH in the second pre-separation column4、
H2、O2、N2、CO、CO2, and by CH therein4、H2、O2、N2, CO be sent into the second chromatographic column in, due to H2Do not have in the second chromatographic column
There is stop, directly can be detected to obtain by TCD detector.
In a preferred embodiment of the invention, the second end of the second pre-separation column and the port of the second six-way valve
6C, port 5C connects with one end of the second empty chromatographic column, the other end of the second empty chromatographic column pass through the port 4C of the second six-way valve,
Port 3C is connect with TCD detector.Carrier gas from third carrier gas inlet is used to purge the CH in the second pre-separation column4、H2、O2、
N2、CO、CO2, and by CH therein4、H2、O2、N2, CO be sent into the second chromatographic column, and by CO2It stays in the second pre-separation column,
The port position of the second six-way valve is adjusted under this state, by CO2It is sent into the second empty chromatographic column, is then examined by TCD detector
It measures.Work as CO2After complete appearance, the port position of the second six-way valve is adjusted again, will be left in the second chromatographic column using carrier gas
In CH4、O2、N2, CO purging enter TCD detector, be then detected.
Embodiment 2
The present embodiment provides a kind of qualitative and quantitative analysis analysis method of gas component, the method is based on above-mentioned reality
The analytical equipment of example is applied, described method includes following steps:
1) the port state of the first six-way valve and ten-way valve is adjusted, so that the first six-way valve and ten-way valve series connection, it will be to be measured
Gas is sent into the first gas import to be measured, and it is fixed into first that under test gas passes sequentially through the port 6A of the first six-way valve, port 1A
Amount ring is loaded, and the port 4A of the first six-way valve, the port 5A of the first six-way valve, ten-way valve are passed sequentially through after the completion of loading
Port 10B, ten-way valve port 1B enter the second quantitative loop and be loaded, extra under test gas is logical by ten after the completion of loading
Port 8B, the port 9B of valve are exported from gas to be measured and are discharged, that is, realize the loading process under test gas in quantitative loop.
2) the port state of the first six-way valve is adjusted, so that passing sequentially through the one or six from the carrier gas that the first carrier gas inlet enters
Port 2A, the port 1A of port valve enter in the first quantitative loop, and the under test gas in the first quantitative loop is taken away, and pass sequentially through the
Port 4A, the port 3A of one six-way valve, which inject in the first chromatographic column, to be separated, and detects under test gas through fid detector after separation
Middle C1-C4Hydrocarbons and oxygenatedchemicals and content.
The port state of ten-way valve and the second six-way valve 3-1) is adjusted, so that successively leading to from the carrier gas that the second carrier gas port enters
Port 7B, the port 8B for crossing ten-way valve bring the under test gas in the second quantitative loop in the first pre-separation column into be separated, to
It surveys gas and obtains first group of component and second group of component through the first pre-separation post separation, wherein first group of component contains CH4、H2、
O2、N2、CO、CO2At least one of, second group is divided into C1-C4Hydrocarbons and oxygenatedchemicals；
3-2) when first group of group separates the first pre-separation column and fully enter the second pre-separation column, second group of group at this time
Still fractionation adjusts the port state of ten-way valve in the first pre-separation column, so that successively leading to from the carrier gas that the second carrier gas port enters
Port 7B, the port 6B for crossing ten-way valve enter in the first pre-separation column, the second group of component band that will be left in the first pre-separation column
It walks, and passes through the port 2B of ten-way valve, port 3B, the first empty chromatographic column and drain emptying；Meanwhile entering from third carrier gas port
Carrier gas pass sequentially through the first damper tube, the port 4B of ten-way valve, port 5B for first group of component band in the second pre-separation column
Enter in the second six-way valve.
The port state for 3-3) adjusting the second six-way valve, so that H2Port 6C, the port 1C of the second six-way valve are entered through,
Again through the second chromatographic column, then detected by TCD by port 2C, the port 3C of the second six-way valve；At this point, CH4、O2、N2, CO into
Enter the port 6C by the second six-way valve, port 1C, into the second chromatographic column, CO2Still in the second pre-separation column；
The port state for 3-4) adjusting the second six-way valve, so that CO2Enter through port 6C, the port of the second six-way valve
5C is detected into the second empty chromatographic column, then by port 2C, the port 3C of the second six-way valve by TCD；
The port state for 3-5) adjusting the second six-way valve, so that CH4、O2、N2, CO enter through the port of the second six-way valve
6C, port 1C are detected into the second chromatographic column, then by port 2C, the port 3C of the second six-way valve by TCD.
Embodiment 3
The present embodiment provides a kind of qualitative and quantitative analysis analytical equipment of gas component, described device includes first to be measured
Gas import, gas to be measured outlet, drain, the first carrier gas inlet, the second carrier gas inlet, third carrier gas inlet, the first quantitative loop,
Two quantitative loops, the first six-way valve, the second six-way valve, ten-way valve, fid detector, TCD detector, the first damper tube, the first empty color
It is each to compose column, the second empty chromatographic column, the first pre-separation column, the second pre-separation column, the first chromatographic column, the second chromatographic column and connection
Pipeline between component；
First six-way valve remember in the direction of the clock including port 1A, port 2A, port 3A ..., port 6A, it is described
Ten-way valve remember in the direction of the clock including port 1B, port 2B, port 3B ..., port 10B；Second six-way valve is by suitable
Clockwise be denoted as port 1C, port 2C, port 3C ..., port 6C；
The first gas import to be measured pass sequentially through the first six-way valve port 6A, port 1A and the first quantitative loop first
The port 10B of end connection, port 4A, port 5A and ten-way valve that the second end of the first quantitative loop passes sequentially through the first six-way valve connects
It connecing, the port 10B of ten-way valve is connect by the port 1B of ten-way valve with the first end of the second quantitative loop, and the second of the second quantitative loop
End passes sequentially through port 8B, the port 9B of ten-way valve and gas to be measured outlet connects.
Such connection type forms route 1, and the dress of gas to be measured may be implemented using the first quantitative loop and the second quantitative loop
Load process, gas to be measured are entered in described device by the first gas import to be measured, pass sequentially through port 6A, the port of the first six-way valve
1A, the first quantitative loop, the port 4A of the first six-way valve, port 5A, the port 10B of ten-way valve, port 1B, the second quantitative loop, ten
Port 8B, the port 9B of port valve are exported from gas to be measured and are discharged, and the first quantitative loop and the second quantitative loop may be implemented in this process
Under test gas is loaded in the first quantitative loop and the second quantitative loop by loading condition.
Loading, which completes, to be started to detect the gas to be measured in quantitative loop immediately, at this point, adjusting the logical of the first six-way valve
Mouth state to first carrier gas inlet passes sequentially through the port 2A of the first six-way valve, the first end of port 1A and the first quantitative loop
Connection, the second end of the first quantitative loop pass sequentially through the first end of the port 4A of the first six-way valve, port 3A and the first chromatographic column
Connection, the second end of first chromatographic column are connect with fid detector.
Such connection type forms route 2, and nitrogen (carrier gas) enters in described device from the first carrier gas inlet, successively leads to
Port 2A, port 1A, the first quantitative loop, the port 4A of the first six-way valve, the port 3A, the first chromatographic column of the first six-way valve are crossed,
It is brought into the first chromatographic column by the way that under test gas therein will be temporarily stored in after the first quantitative loop and is separated, the first chromatographic column is available
The component that can be detected by fid detector in separation table 2；
The port state for adjusting ten-way valve passes through port 7B, the port 8B and second of ten-way valve to second carrier gas inlet
The second end of quantitative loop connects, and the first end of the second quantitative loop passes through port 1B, the port 2B and the first pre-separation column of ten-way valve
First end connection, the second end of the first pre-separation column pass sequentially through the port 6B of ten-way valve, port 5B and second in advance divide
First end connection from column, the second end of the second pre-separation column are connect with the second six-way valve；Such connection type forms route
3, nitrogen (carrier gas) enters in described device from the second carrier gas inlet, passes sequentially through the port 7B of ten-way valve, port 8B, second fixed
Measure ring, the port 1B of ten-way valve, port 2B, the first pre-separation column, the port 6B of ten-way valve, port 5B, the second pre-separation column, the
Two six-way valves；The carrier gas being passed through from the second carrier gas inlet is used to purge under test gas in the second quantitative loop, and carries it into the
Pre-separation is carried out in one pre-separation column and the second pre-separation column, i.e. realization CH4、H2、O2、N2、CO、CO2、C1-C4Hydrocarbons and
The separation of oxygenatedchemicals, specifically by C2-C4Hydrocarbons and oxygenatedchemicals stay in the first pre-separation column, by CH4、H2、
O2、N2、CO、CO2It is sent into the second pre-separation column and is separated again.
The port state for adjusting ten-way valve passes through port 7B, the port 6B and first of ten-way valve to second carrier gas inlet
The second end of pre-separation column connects, and the first end of the first pre-separation column passes through port 2B, the port 3B and first of ten-way valve
One end of empty chromatographic column connects, and the other end of the described first empty chromatographic column is connect with drain.Such connection type forms line
Road 4, the carrier gas that second carrier gas inlet is passed through is for purging remaining C in the first pre-separation column1-C4Hydrocarbons and oxygen-containing
Compound.
Adjust the port state of ten-way valve to the third carrier gas inlet by the port 4B of the first damper tube and ten-way valve,
Port 5B is connect with the first end of the second pre-separation column, and the second end of the second pre-separation column is connect with the second six-way valve.It is such
Connection type forms route 5, and the carrier gas that the third carrier gas inlet is passed through is used to purge the CH in the second pre-separation column4、H2、O2、
N2、CO、CO2, and be sent in the second chromatographic column and then detected to obtain by TCD detector.
The port state of the second six-way valve is adjusted to the second end of the second pre-separation column and the port of the second six-way valve
One end connection of 6C, port 1C, the second chromatographic column, the other end of the second chromatographic column pass through port 2C, the port of the second six-way valve
3C is connect with TCD detector.Such connection type forms route 6, and the carrier gas from third carrier gas inlet is for purging second
CH in pre-separation column4、H2、O2、N2、CO、CO2, and by CH therein4、H2、O2、N2, CO be sent into the second chromatographic column in, due to H2
It is not stopped in the second chromatographic column, directly can be detected to obtain by TCD detector.
The port state of the second six-way valve is adjusted to the second end of the second pre-separation column and the port of the second six-way valve
6C, port 5C connects with one end of the second empty chromatographic column, the other end of the second empty chromatographic column pass through the port 4C of the second six-way valve,
Port 3C is connect with TCD detector.Such connection type forms route 7, and the carrier gas from third carrier gas inlet is for purging
CH in second pre-separation column4、H2、O2、N2、CO、CO2, and by CH therein4、H2、O2、N2, CO be sent into the second chromatographic column in, and
By CO2It stays in the second pre-separation column, adjusts the port position of the second six-way valve under this state, by CO2It is sent into the second empty chromatography
In column, then detected to obtain by TCD detector.Work as CO2After complete appearance, the port position of the second six-way valve is adjusted again, benefit
It will be left in the CH in the second chromatographic column with carrier gas4、O2、N2, CO purging enter TCD detector, be then detected.
Embodiment 4
Under test gas is pressed into the described two quantitative loops of embodiment 2 by under test gas import, using the detection of embodiment 3
Method completes the detection under test gas, and the parameter of the gas chromatograph is as follows:
First chromatographic column: capillary column (1701)；Second chromatographic column: molecular sieve column (MS-13X)；First pre-separation column: it fills out
Fill column (P-N)；Second preseparation chromatography column: packed column (P-N)；First damper tube is empty chromatographic column；
Post case: 60 DEG C of holding 5min of initial temperature rise to 130 DEG C with 10 DEG C/min, keep 5min.
Carrier gas: the carrier gas of the first carrier gas inlet injection is nitrogen, flow velocity 1.0mL/min；The injection of second carrier gas inlet
Carrier gas is argon gas, flow velocity 25.0mL/min；The carrier gas of third carrier gas inlet injection is argon gas, flow velocity 3.0mL/min.Gasification
The temperature of room is 150 DEG C.Split ratio: 10:1.The detection temperature of fid detector is 200 DEG C.The detection temperature of TCD detector:
170℃；Electric current: 60mA；Polarity: "-".
Time-program(me):
1 time-program(me) of table
| Time | Equipment | Event | Setting value |
| 0.01 | Relay | Relay 2 (0:Off/1:On) | 1 |
| 0.01 | Relay | Relay 1 (0:Off/1:On) | 1 |
| 1.00 | Relay | Relay 1 (0:Off/1:On) | 0 |
| 2.35 | Relay | Relay 2 (0:Off/1:On) | 0 |
| 3.00 | Relay | Relay 3 (0:Off/1:On) | 1 |
| 4.80 | Relay | Relay 3 (0:Off/1:On) | 0 |
The included component of under test gas material is as shown in table 2 below:
2 the included component of under test gas material of table
Constituent part shown in above-mentioned table 2 can be detected to obtain by fid detector, and constituent part can be detected by TCD
Device detects to obtain.Wherein, the concentration of each component detected by fid detector is obtained by area normalization method,
The concentration of each component detected by TCD detector is obtained by Standard Gases external standard method.
Using the method for the device and embodiment 3 of embodiment 2, the component that two detectors detect such as table 3 and table 4,
And shown in Fig. 2 and Fig. 3.
The component that 3 fid detector of table detects
| Peak number | Chemical combination name | Retention time | Area | Area % | Separating degree (USP) |
| 1 | Methane | 2.372 | 209484 | 0.765 | -- |
| 2 | Iso-butane | 2.459 | 25951231 | 94.714 | 2.22 |
| 3 | Normal butane | 2.775 | 10565 | 0.039 | 7.597 |
| 4 | Acetone | 3.370 | 38899 | 0.142 | 13.62 |
| 5 | Isopropanol | 3.518 | 13193 | 0.048 | 3.1 |
| 6 | TBA | 3.782 | 1094960 | 3.996 | 4.533 |
| 7 | DTBP/IBF | 6.064 | 2048 | 0.007 | 38.642 |
| 8 | Acetic acid | 6.383 | 10228 | 0.037 | 6.033 |
| 9 | TBHP | 8.069 | 69058 | 0.252 | 34.091 |
The component that 4 TCD detector of table detects
| Peak number | Chemical combination name | Retention time | Area | Concentration | Area % | Separating degree (USP) |
| 1 | Hydrogen | 2.402 | 14116 | 0.140 | 15.172 | -- |
| 2 | Vavle switching peak 1 | 2.614 | 1066 | - | 1.146 | 2.686 |
| 3 | Carbon dioxide | 4.32 | 5669 | 0.871 | 6.093 | 11.417 |
| 4 | Vavle switching peak 2 | 4.819 | 13104 | - | 14.085 | 3.161 |
| 5 | Oxygen | 5.704 | 10580 | 0.444 | 11.372 | 9.296 |
| 6 | Nitrogen | 6.964 | 28621 | 0.862 | 30.763 | 7.44 |
| 7 | Methane | 9.052 | 16705 | 0.606 | 17.955 | 9.667 |
| 8 | Carbon monoxide | 10.142 | 3176 | 0.390 | 3.414 | 4.4 |
From table 3 and table 4 and Fig. 2 and Fig. 3 can be seen that using the gaseous component of the application detection and analysis device and
The qualitative and quantitative detection of gaseous component may be implemented in method, and detection process is controllable, can be realized pair using a chromatograph
The detection of the component of multiple and different properties.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of qualitative and quantitative analysis analytical equipment of gas component, wherein described device include the first gas import to be measured, to
Survey gas outlet, the first carrier gas inlet, the second carrier gas inlet, third carrier gas inlet, the first quantitative loop, the second quantitative loop, the one or six
Port valve, the second six-way valve, ten-way valve, fid detector, TCD detector, the first damper tube, the second empty chromatographic column, the first pre-separation
Pipeline between column, the second pre-separation column, the first chromatographic column, the second chromatographic column and connecting components；
The first gas import to be measured is connect by the first six-way valve with the first end of the first quantitative loop, and the second of the first quantitative loop
End is connect by the first six-way valve and ten-way valve with the first end of the second quantitative loop, and the second end of the second quantitative loop passes through ten-way valve
It exports and connects with gas to be measured；
First carrier gas inlet is connect by the first six-way valve with the first end of the first quantitative loop, and the 2nd 1 of the first quantitative loop the
End is connect by the first six-way valve with the first end of the first chromatographic column, and the second end and fid detector of first chromatographic column connect
It connects；
Second carrier gas inlet is connect by ten-way valve with the second end of the second quantitative loop, and the first end of the second quantitative loop passes through
Ten-way valve is connect with the first end of the first pre-separation column, and the second end of the first pre-separation column passes through pre- point of ten-way valve and second
It is connected from column first end；
The third carrier gas inlet is connect by the first damper tube with ten-way valve, and the first of the ten-way valve and the second pre-separation column
End connection；
The second end of second pre-separation column is connect by the second six-way valve with the second chromatographic column or the second empty chromatographic column, and described second
Chromatographic column or the second empty chromatographic column are connect by the second six-way valve with TCD detector.
2. the apparatus according to claim 1, wherein described device further includes the first empty chromatographic column and drain, and described the
Two carrier gas inlets are connect by ten-way valve with the second end of the first pre-separation column, and the first end of the first pre-separation column passes through ten
Port valve is connect with the first end of the first empty chromatographic column, and the second end of the described first empty chromatographic column is connect with drain.
3. device according to claim 1 or 2, wherein first chromatographic column is for separating C1-C4Hydrocarbons and contain
At least one of oxygen compound；The first pre-separation column, the second pre-separation column and the second chromatographic column are for separating CH4、H2、
O2、N2, CO and CO2At least one of.
4. device according to claim 1-3, wherein first six-way valve remembers to include logical in the direction of the clock
Mouthful 1A, port 2A, port 3A ..., port 6A, the ten-way valve remember in the direction of the clock including port 1B, port 2B, port
3B ..., port 10B；
The first gas import to be measured is connect by port 6A, the port 1A of the first six-way valve with the first end of the first quantitative loop,
The second end of first quantitative loop passes sequentially through the port 10B connection of port 4A, the port 5A and ten-way valve of the first six-way valve, and ten is logical
The port 10B of valve is connect by the port 1B of ten-way valve with the first end of the second quantitative loop, and the second end of the second quantitative loop is successively
It is connected by the port 8B of ten-way valve, port 9B and gas to be measured outlet.
Preferably, first carrier gas inlet pass sequentially through the first six-way valve port 2A, port 1A and the first quantitative loop
One end connection, the second end of the first quantitative loop pass sequentially through the first six-way valve port 4A, port 3A and the first chromatographic column the
One end connection, the second end of first chromatographic column are connect with fid detector.
Preferably, described device further includes automatic flow controller, and the automatic flow controller is connect with the first carrier gas inlet,
For controlling the carrier gas flux for passing through the first carrier gas inlet.
Preferably, second carrier gas inlet is connect by port 7B, the port 8B of ten-way valve with the second end of the second quantitative loop,
The first end of second quantitative loop is connect by port 1B, the port 2B of ten-way valve with the first end of the first pre-separation column, and described the
The second end of one pre-separation column passes sequentially through the port 6B of ten-way valve, port 5B and connect with the first end of the second pre-separation column, the
The second end of two pre-separation columns is connect with the second six-way valve.
Preferably, second carrier gas inlet is connected by port 7B, the port 6B of ten-way valve and the second end of the first pre-separation column
It connecing, the first end of the first pre-separation column is connect by port 2B, the port 3B of ten-way valve with one end of the first empty chromatographic column,
The other end of described first empty chromatographic column is connect with drain.
Preferably, the third carrier gas inlet passes through port 4B, port 5B and the second pre-separation of the first damper tube and ten-way valve
The first end of column connects, and the second end of the second pre-separation column is connect with the second six-way valve.
Preferably, described device further includes automatic pressure controller, the automatic pressure controller and the second carrier gas inlet and
Three carrier gas inlets connection, for controlling the carrier gas flux for passing through the second carrier gas inlet and third carrier gas inlet.
5. device according to claim 1-4, wherein second six-way valve is denoted as port in the direction of the clock
1C, port 2C, port 3C ..., port 6C；It is the port 6C of the second end of the second pre-separation column and the second six-way valve, logical
One end connection of mouthful 1C, the second chromatographic column, the other end of the second chromatographic column by port 2C, the port 3C of the second six-way valve with
The connection of TCD detector.
Preferably, port 6C, the port 5C and the second empty chromatographic column of the second end of the second pre-separation column and the second six-way valve
One end connection, the other end of the second empty chromatographic column connect by port 4C, the port 3C of the second six-way valve with TCD detector.
6. a kind of qualitative and quantitative analysis analysis method of gas component, wherein the method is any based on claim 1-5
Detection and analysis device described in, described method includes following steps:
1) adjust the first six-way valve and ten-way valve port state so that the first six-way valve and ten-way valve series connection, under test gas from
First gas import to be measured enters, and is entered in the first quantitative loop and the second quantitative loop by the first six-way valve and ten-way valve, complete to
Survey the loading process of gas；
2) adjust the port state of the first six-way valve so that the carrier gas entered from the first carrier gas inlet by the first quantitative loop to
Survey gas, which is brought into the first chromatographic column, to be separated, through constituent part and content in fid detector detection under test gas after separation；
3) the port state of ten-way valve and the second six-way valve is adjusted, so that quantifying from the carrier gas that the second carrier gas inlet enters by second
Under test gas in ring brings the first pre-separation column into, carries out pre-separation in the second pre-separation column, and by from third carrier gas inlet
Constituent part in second pre-separation column is brought into the second six-way valve and is separated by the carrier gas of entrance, detects after separation through TCD
Device detects constituent part and content under test gas.
7. according to the method described in claim 6, wherein, containing C in the under test gas1-C4Hydrocarbons, H2、O2、N2、CO、
CO2, the gas detections such as oxygenatedchemicals steam.The oxygenatedchemicals for example can be methanol, ethyl alcohol, propyl alcohol, isopropanol, fourth
Alcohol, the tert-butyl alcohol, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, acetone, butanone, propylene oxide, ethylene oxide, formic acid, acetic acid, propionic acid, fourth
Acid, tert-butyl hydroperoxide, di-tert-butyl peroxide (DTBP), iso-butyl formate (TBF), iso-butyl formate (IBF) etc..
8. method according to claim 6 or 7, wherein step 1) specifically:
The port state of the first six-way valve and ten-way valve is adjusted, so that the first six-way valve and ten-way valve series connection, under test gas is sent
Enter in the first gas import to be measured, under test gas pass sequentially through the port 6A of the first six-way valve, port 1A into the first quantitative loop into
Luggage carries, and the port of the port 4A of the first six-way valve, the port 5A of the first six-way valve, ten-way valve is passed sequentially through after the completion of loading
10B, ten-way valve port 1B enter the second quantitative loop and be loaded, extra under test gas is by ten-way valve after the completion of loading
Port 8B, port 9B are exported from gas to be measured and are discharged, that is, realize the loading process under test gas in quantitative loop.
Preferably, step 2) specifically:
The port state of the first six-way valve is adjusted, so that passing sequentially through the first six-way valve from the carrier gas that the first carrier gas inlet enters
Port 2A, port 1A enter in the first quantitative loop, and the under test gas in the first quantitative loop is taken away, and it is logical to pass sequentially through the one or six
Port 4A, the port 3A of valve, which inject in the first chromatographic column, to be separated, through C in fid detector detection under test gas after separation1-C4
Hydrocarbons and oxygenatedchemicals and content.
9. according to the described in any item methods of claim 6-8, wherein step 3) further includes following steps:
3 ') the port state of ten-way valve is adjusted, so that will remain in the first pre-separation column from the carrier gas that the second carrier gas inlet enters
Constituent part bring into the first empty chromatographic column, carry out emptying processing.
Preferably, step 3) specifically:
The port state of ten-way valve and the second six-way valve 3-1) is adjusted, so that passing sequentially through ten from the carrier gas that the second carrier gas port enters
Port 7B, the port 8B of port valve bring the under test gas in the second quantitative loop in the first pre-separation column into be separated, gas to be measured
Body obtains first group of component and second group of component through the first pre-separation post separation, wherein first group of component contains CH4、H2、O2、N2、
CO、CO2At least one of, second group is divided into C1-C4Hydrocarbons and oxygenatedchemicals；
3-2) when first group of group separates the first pre-separation column and fully enter the second pre-separation column, second group of group is still divided at this time
It stays in the first pre-separation column, adjusts the port state of ten-way valve, so that passing sequentially through ten from the carrier gas that the second carrier gas port enters
Port 7B, the port 6B of port valve enter in the first pre-separation column, and the second group of component left in the first pre-separation column is taken away, and
Pass through the port 2B of ten-way valve, port 3B, the first empty chromatographic column and drain emptying；Meanwhile the load entered from third carrier gas port
Gas passes sequentially through the first damper tube, the port 4B of ten-way valve, port 5B and brings first group of component in the second pre-separation column into
In two six-way valves.
Preferably, step 3) further includes following steps:
The port state for 3-3) adjusting the second six-way valve, so that H2Port 6C, the port 1C of the second six-way valve are entered through, then is passed through
Second chromatographic column, then detected by port 2C, the port 3C of the second six-way valve by TCD；At this point, CH4、O2、N2, CO enter it is logical
Port 6C, the port 1C for crossing the second six-way valve, into the second chromatographic column, CO2Still in the second pre-separation column；
The port state for 3-4) adjusting the second six-way valve, so that CO2Port 6C, the port 5C of the second six-way valve are entered through, is entered
Second empty chromatographic column, then detected by port 2C, the port 3C of the second six-way valve by TCD；
The port state for 3-5) adjusting the second six-way valve, so that CH4、O2、N2, CO enter through the port 6C, logical of the second six-way valve
Mouth 1C, is detected into the second chromatographic column, then by port 2C, the port 3C of the second six-way valve by TCD.
10. the method according to claim 6, wherein the model of first chromatographic column can be 1701 colors
Compose column, 0.25mm*0.25 μm of * 30m of specification.
Preferably, second column model can be MS-13X chromatographic column, specification 80/100mesh, 3.2mm*2.1mm*
3.0m。
Preferably, the first pre-separation column and the second pre-separation column type number are PN column, specification 80/100mesh3.2mm*
2.1mm*1.0m。
Preferably, first damping column, the first empty chromatographic column and the second empty chromatographic column are void column pipe.
Preferably, the analysis and detection device can be chromatograph.
Preferably, the chromatographic post case: 35~70 DEG C of initial temperature, for example, 60 DEG C holding 5min, with 2-20 DEG C/min,
For example, 10 DEG C/min rises to 100~180 DEG C, for example, 130 DEG C, keeps 5min.
Preferably, the temperature of the first under test gas import is 80~200 DEG C, for example, 150 DEG C.
Preferably, split ratio: 5:1~150:1, for example, 10:1.
Preferably, the detection temperature of the fid detector is 150-250 DEG C, for example, 200 DEG C.
Preferably, the detection temperature of the TCD detector: 170 DEG C；Electric current: 60mA；Polarity: "-".
Preferably, the carrier gas of the first carrier gas inlet injection is nitrogen, flow velocity 1-5mL/min, for example, 2.0mL/min；
The carrier gas of the second carrier gas inlet injection is argon gas, flow velocity 10-40mL/min, for example, 25.0mL/min；The third
The carrier gas of carrier gas inlet injection is argon gas, flow velocity 1-5mL/min, for example, 3.0mL/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060021940A1 (en) * | 2004-08-02 | 2006-02-02 | Fabrice Bertoncini | Method and device for integrated analysis of a hydrocarbon sample |
| CN202383115U (en) * | 2011-11-01 | 2012-08-15 | 中国石油化工股份有限公司 | Multifunctional gas chromatography detection system for gas analysis |
| CN103123339A (en) * | 2011-11-18 | 2013-05-29 | 上海华谊丙烯酸有限公司 | On-line analysis system and on-line measurement method |
| CN203025161U (en) * | 2013-01-05 | 2013-06-26 | 中国地质科学院矿产资源研究所 | Gas chromatography system for natural gas hydrate |
| CN106248851A (en) * | 2016-08-19 | 2016-12-21 | 中国神华能源股份有限公司 | The gas chromatographic analysis device of MTO reactor product gas and the method for analysis |
-
2019
- 2019-05-06 CN CN201910372997.6A patent/CN110146609A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060021940A1 (en) * | 2004-08-02 | 2006-02-02 | Fabrice Bertoncini | Method and device for integrated analysis of a hydrocarbon sample |
| CN202383115U (en) * | 2011-11-01 | 2012-08-15 | 中国石油化工股份有限公司 | Multifunctional gas chromatography detection system for gas analysis |
| CN103123339A (en) * | 2011-11-18 | 2013-05-29 | 上海华谊丙烯酸有限公司 | On-line analysis system and on-line measurement method |
| CN203025161U (en) * | 2013-01-05 | 2013-06-26 | 中国地质科学院矿产资源研究所 | Gas chromatography system for natural gas hydrate |
| CN106248851A (en) * | 2016-08-19 | 2016-12-21 | 中国神华能源股份有限公司 | The gas chromatographic analysis device of MTO reactor product gas and the method for analysis |
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