CN1172187C - Gas chromatographic analysis process of micro and trace CO and CO2 - Google Patents

Gas chromatographic analysis process of micro and trace CO and CO2 Download PDF

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CN1172187C
CN1172187C CNB011158247A CN01115824A CN1172187C CN 1172187 C CN1172187 C CN 1172187C CN B011158247 A CNB011158247 A CN B011158247A CN 01115824 A CN01115824 A CN 01115824A CN 1172187 C CN1172187 C CN 1172187C
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post
way valve
sample
trace
flow process
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CN1384356A (en
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芬 叶
叶芬
许国旺
赵欣捷
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention provides a gas chromatographic analysis process of micro and trace CO and CO2 in low carbon hydrocarbon. The chromatographic analysis process is selected, and therefore, a fixed phase and a column switching program of a chromatographic column are selected. A switching process is simple and clear, and the debugging is convenient. An auxiliary gas path is adopted to provide supporting gas used for reversely blowing, and methane and oxygen are effectively removed. The present invention can be suitable for low carbon hydrocarbon samples with different ingredients. The accurate quantitation of micro and trace CO and CO2 can be ensured. The present invention is suitable for not only industrial flow analysis but also laboratory analysis.

Description

Trace and trace carbon monoxide, carbon dioxide gas chromatographic analysis flow process
Technical field
The invention belongs to a kind of stratographic analysis flow process, relate in particular to trace and trace CO, CO in a kind of lower carbon number hydrocarbons 2Gas chromatographic analysis process.
Background technology
In petrochemical complex and catalytic reaction, carbon monoxide, carbon dioxide (CO, CO in the lower carbon number hydrocarbons 2) analysis often paid close attention to by people, it directly reflects the degree that hydrocarbon is oxidized, no matter in order to improve reaction yield, to calculate selectivity, carries out still that material is permanent to be calculated, all accurate metering CO, CO 2To from a large amount of hydrocarbon, detect CO, the CO of trace 2(＞tens ppm) can adopt gas chromatography multicolumn switched system, gets rid of the interference of hydrocarbon, oxygen, goes up at general thermal conductivity cell detector (TCD) and detects.If will from a large amount of hydrocarbon, detect CO, the CO of trace 2(＜tens ppm-ppb) then needs CO, the CO that will separate 2Be separately converted to methane and water, go up at highly sensitive hydrogen flame detector (FID) and detect.
Trace CO, CO in the industrial detection lower carbon number hydrocarbons 2Ripe flow process is trace amounts of CO, CO in day GC-S161 ethene of island proper Tianjin company, the propylene 2Analytic system based on the gas chromatography GC-14BPF of FID, adopts the dual flow path flow process (see figure 1) of 4 valves, 14 root chromatogram columns, 2 converters and 2 fid detector couplings, debugs very complicated.Not only resistance is difficult to coupling, and does not usually know CO, CO 2At any root pillar, so that be difficult to debugging.
The HP5890II-NICAT system of U.S.'s Agilent (Agilent) company adopts a ten-way valve, two root chromatogram columns, nickel catalysis system and FID to detect CO, the CO of trace 2(Fig. 2).Though this flow process is very simple, do not excise methane and oxygen, when a large amount of methane and oxygen existed, oxygen changed into the methane that the CO in water and the sample changes into and goes out the peak simultaneously, disturb CO quantitatively; And a large amount of methane can be covered the CO that the back goes out the peak in the sample 2, directly influence CO 2Detect.Moreover, the variation of resistance also can influence baseline in the handoff procedure, causes the uncertainty of chromatographic peak area.
Summary of the invention
The purpose of this invention is to provide trace and trace CO, CO in a kind of lower carbon number hydrocarbons 2Gas chromatographic analysis process, switching flow of the present invention is simple and clear, and debugging is convenient, can be applicable to the different lower carbon number hydrocarbons samples of forming respectively, guarantees trace and trace CO, CO 2Accurately quantitatively.
Lower carbon number hydrocarbons of the present invention is that carbon number is 1-4, a small amount of methane is meant＜20%, and a large amount of and high concentration methane is meant＞20%, a spot of oxygen is meant than CO content in the sample and hangs down an order of magnitude, high concentration oxygen be meant with sample in CO content with the order of magnitude or be higher than the content of CO, trace amounts of CO, CO 2Be meant 0.01-1%, trace CO, CO 2Be meant＜0.01%.
For achieving the above object, the present invention adopts following technical scheme:
(principle is seen Fig. 3 by selecting stratographic analysis flow process, the stationary phase of selecting chromatographic column and post changeover program, wherein the effect of thermal conductivity detector (TCD) (TCD) is each component flow state of monitoring), the debugging of easy flow process, adopt auxiliary air passage (Aux) to provide carrier gas to carry out blowback, excise methane and oxygen effectively.
The concrete technical scheme that the lower carbon number hydrocarbons sample that difference is formed adopts is:
1) do not contain in the lower carbon number hydrocarbons or when containing a small amount of methane and oxygen, adopt two post flow process (see figure 4)s, the stream of this flow process has two posts, a ten-way valve, first post (post 1 #) can adopt 1-4m, the HayeSep Q of internal diameter φ 2-3mm or class as the porous polymer bead filler, as PorapakQ, Chromosorb 102 etc.; Second post (post 2 #) can adopt 1-5m, the HayeSep Q of internal diameter φ 2-3mm or class as the porous polymer bead filler, as Porapak Q, Chromosorb102 etc.; This flow process gas circuit is when blowback, and separating column 2 in the flow process #Carrier gas provide by auxiliary air passage (Aux) 1 because auxiliary air passage (Aux) 1 pressure adjusts to and post 2 in advance #The intake pressure balance is not so blowback causes post 2 #Pressure surge so not only can not influence post 2 #Separation, and reduce blowback coupled columns 2 #Impact, can prolong post 2 #Life-span.Its analysis process is: when valve is in when just blowing, sample is blown into post 1 from sample hose #After the outflow, valve changes blowback over to, and heavy constituent are from post 1 #Oppositely blow out system, CO, CH 4, CO 2Through post 2 #After the separation, be detected at detecting device.
When 2) containing a large amount of methane in the lower carbon number hydrocarbons, at separating column 2 #Middle methane can be covered the CO of back 2, at this moment therefore a large amount of methane excisions must be adopted three post flow process (see figure 7)s, that is, and the second post (post 2 in the two post flow processs #) be exported between the hydrocarbon converter series connection one the 3rd post (post 3 #).The stream of this flow process has three posts, a ten-way valve and a six-way valve, post 1 # Post 1 with two post flow processs #, post 2 #With post 3 # Post 2 with two post flow processs #This flow process center pillar 1 #Blowback CO 2After heavy constituent, post 2 #Heartcut CH 4, post 3 #Further separation of C O, CH 4, CO 2Its analysis process is: when valve is in when just blowing, sample is blown into post 1 from sample hose #, as CO, CH 4, CO 2From post 1 #After the outflow, valve changes blowback over to, and heavy constituent are from post 1 #Oppositely blow out system, CO, CH 4, CO 2Through post 2 #After the separation, by valve 2 with most of CH 4In cut emptying, do not cut clean CH 4With CO, CO 2Through post 3 #Further separating the back is detected at detecting device.
When 3) containing high concentration methane and oxygen in the lower carbon number hydrocarbons, a large amount of methane is at separating column 3 #In can cover the CO of back 2, a large amount of oxygen go out the peak simultaneously with CO, and the water that oxygen changes into can disturb the detection of CO, so adopts five post flow processs (seeing Figure 11), that is, and with the use of connecting with the sample inlet of two post flow processs of the sample export of three post flow processs.This flow process is made up of two streams: stream 1 Analysis for CO 2, three posts are arranged, a ten-way valve, a six-way valve.Post 1 #Blowback CO 2After heavy constituent, post 2 #With CO 2The light constituent fore blow emptying of front, post 3 #Further with residual CH 4And CO 2Separately; Its analysis process is: by ten-way valve post 1 #Blowback CO 2After heavy constituent, by six-way valve post 2 #With CO 2The light constituent fore blow emptying of front, post 3 #Further with residual CH 4And CO 2Separately.
Stream 2 Analysis for CO have two posts, a ten-way valve, the 4th post (post 4 #) heavy constituent of blowback CO back, the 5th post (post 5 #) further separate O 2And CO, just can get rid of O by above two streams 2And CH 4Interference.Its analysis process is: by ten-way valve post 4 #The heavy constituent of blowback CO back, post 5 #Further separate O 2And CO.
Wherein, post 1 #, 2 #, 3 #All with three post flow processs, analytical column 4 #Can adopt 1-3m, the TXD-01 of internal diameter φ 2-3mm or class as the carbonaceous molecular sieve filler, as CARBOSIEVE etc., analytical column 5 #Can adopt 1-5m, the TXD-01 of internal diameter φ 2-3mm or class as the carbonaceous molecular sieve filler, as CARBOSIEVE etc.
Description of drawings
For detail knowledge content of the present invention, below with the drawings and Examples explanation.
Fig. 1, Fig. 2 are the process flow diagram of known technology,
Fig. 3 is a principle of the invention synoptic diagram,
Fig. 4 is the present invention's two post process flow diagrams,
Fig. 5 is two post flow process center pillars 1 #+ TCD+ post 2 #Chromatogram,
Fig. 6 is two post flow process center pillars 1 #Blowback+post 2 #Final chromatogram,
Fig. 7 is the present invention's three post process flow diagrams,
Fig. 8 is three post flow process center pillars 1 #+ TCD+ post 2 #+ post 3 #Chromatogram,
Fig. 9 is three post flow process center pillars 1 #Blowback+post 2 #+ TCD+ post 3 #Chromatogram,
Figure 10 is three post flow process center pillars 1 #Blowback+post 2 #In cut+post 3 #+ TCD chromatogram,
Figure 11 is the present invention's five post process flow diagrams,
Figure 12 is five post flow process streams, 1 center pillars 1 #+ TCD+ post 2 #+ post 3 #Chromatogram,
Figure 13 is five post flow process streams, 1 center pillars 1 #Blowback+post 2 #+ TCD+ post 3 #Chromatogram,
Figure 14 is five post flow process streams, 1 center pillars 1 #Blowback+post 2 #Fore blow+post 3 #+ TCD chromatogram,
Figure 15 is five post flow process streams, 2 center pillars 4 #+ TCD+ post 5 #Chromatogram
Figure 16 is five post flow process streams, 2 center pillars 4 #Blowback+post 5 #+ TCD chromatogram,
Figure 17 is the stack chromatogram of five post flow process streams 1 and stream 2.
Embodiment
1: two post flow process of embodiment, this stream is applicable to O 2, CH 4The situation that content is lower.
Analytical column: 1 #3m *φ 2mm HayeSep Q 80/100
2 #3m *φ2mm?HayeSep?Q?80/100
Chromatographic condition: T Post=60 ℃, carrier gas: H 230mL/min, 130-200 blowback second, sample: coal gas; Sample introduction 50 μ l, P=0.22Mpa.Analysis of spectra is seen Fig. 5 and Fig. 6.
The process of analytic sample is as follows: when valve is in when just blowing, sample is blown into post 1 from sample hose #After the outflow, valve changes blowback over to, and heavy constituent are from post 1 #Oppositely blow out system.CO, CH 4, CO 2Through post 2 #After the separation, be detected at detecting device.O as can be seen from this two width of cloth spectrogram 2Go out the peak simultaneously with CO, have only O 2Compare with CO, just can ignore O when its content has the difference of the order of magnitude 2Influence, otherwise must adopt other flow process.
Consider post 1 #All blowback emptying of heavy constituent, the blowback time should adopt 140 seconds, and be 320 seconds analysis time, 500 seconds each times spent in cycle.CO, CO 2Appearance time was respectively 1.303 minutes and 3.113 minutes.
2: three post flow processs of embodiment, this stream is applicable to CH 4The situation that content is high.
Analytical column: 1 #2m *φ 2mm HayeSep Q 80/100
2 #3m *φ2mm?Porapak?Q?80/100
3 #3m *φ2mm?HayeSep?Q?80/100
Chromatographic condition: T Post=50 ℃, carrier gas: H 220mL/min (H2), P=0.16Mpa, valve 13.2-4 divide blowback, and valve 2 2.6-4.8 cut in dividing.Sample: coal gas, sample introduction 50 μ l.Analysis of spectra is seen Fig. 8 to Figure 10.
The process of analytic sample is as follows: when valve is in when just blowing, sample is blown into post 1 from sample hose #, as CO, CH 4, CO 2From post 1 #After the outflow, valve changes blowback over to, and heavy constituent are from post 1 #Oppositely blow out system.CO, CH 4, CO 2Through post 2 #After the separation, by valve 2 with most of CH 4In cut emptying, do not cut clean CH 4With CO, CO 2Through post 3 #Further separating the back is detected at detecting device.CO, CO 2Appearance time was respectively 2.533 minutes and 6.913 minutes, and be 8 minutes whole analysis time, and one-period is 12 minutes.
3: five post flow processs of embodiment, this stream is applicable to O 2, CH 4The content condition with higher, chromatographic condition: T Post=50 ℃, carrier gas: H 220mL/min, sample: coal gas, sample introduction 50 μ l.
This flow process is made up of two streams:
Stream 1 Analysis for CO 2, three posts are arranged, a ten-way valve, six-way valve.By ten-way valve post 1 #130-200 blowback second CO 2After heavy constituent, by six-way valve post 2 #4.8 divide with CO 2The light constituent fore blow emptying of front, post 3 #Further with residual CH 4And CO 2Separately.
Stream 2 Analysis for CO have two posts, a ten-way valve.By ten-way valve post 4 #2.5 divide blowback CO the heavy constituent of back, post 5 #Further separate O 2And CO.
Stream 1:CO 2Analyze
Analytical column: 1 #2m *φ 2mm HayeSep Q 80/100
2 #3m *φ2mm?HayeSep?Q?80/100
3 #3m *φ2mm?HayeSep?Q?80/100
Chromatogram is seen Figure 12 to Figure 14.
Stream 2:CO analyzes
Chromatographic column: 4 #TDX-01 1m *φ 2mm 60/80
5 #TDX-01?2m *φ2mm?60/80
Chromatogram is seen Figure 15 to Figure 16.
With CO and CO 2The spectrogram stack of cutting latter two stream shows CO and CO as Figure 17 2Separate fully, and can get rid of the interference of methane and oxygen.
CO, CO 2Appearance time was respectively 5.492 minutes and 6.913 minutes.Be 10 minutes whole analysis time, and one-period is 12 minutes.
From the separating property of flow process as can be seen: this flow process can detect CO, the CO the air (comprising oxygen) equally 2And CO, CO in the coal gas (comprising methane gas, rock gas) 2
CO, CO in sample 2When content is higher (more than tens ppm), can adopt the TCD detecting device directly to detect.CO, CO 2Content must be installed hydrocarbon converter (methanator or Raney nickel system), with CO, CO between chromatographic column outlet and detecting device when the ppm-ppb level 2Change into CH 4, detect by highly sensitive detecting device FID (hydrogen flame detector) then.
With general CO, CO 2What industrial chromatograph was different is: switching flow of the present invention is simple and clear, and debugging is convenient, not only is suitable for the industrial flow analysis, also is suitable for lab analysis; With present commercial CO, CO 2What special-purpose chromatograph was different is: each component concentrations can change in a big way in the sample, O wherein 2And CH 4Can not disturb CO, CO 2Detection.

Claims (2)

1, a kind of trace and trace carbon monoxide, carbon dioxide gas chromatographic analysis flow process, stationary phase and the post changeover program of it is characterized in that selecting the stratographic analysis flow process, selecting chromatographic column, adopt auxiliary air passage to provide carrier gas to carry out blowback, the flow process of the lower carbon number hydrocarbons sample that difference is formed is:
1) do not contain in the lower carbon number hydrocarbons or contain＜20% methane and adopt two post flow processs during than the oxygen of the low order of magnitude of CO content in the sample;
The stream of described flow process has two analytical columns, a ten-way valve, and its analysis process is: when valve is in when just blowing, after sample was blown into first post and flows out from sample hose, valve changed blowback over to, and heavy constituent oppositely blow out system from first post, CO, CH 4, CO 2After the separation of second post, be detected at detecting device;
2) contain in the lower carbon number hydrocarbons＞adopt three post flow processs during 20% methane, that is, second column outlet in the two post flow processs is to series connection one the 3rd post between the hydrocarbon converter;
The stream of described flow process has three analytical columns, a ten-way valve and a six-way valve, and its analysis process is: when ten-way valve is in when just blowing, sample is blown into first post from sample hose, as CO, CH 4, CO 2After the outflow of first post, ten-way valve changes blowback over to, and heavy constituent oppositely blow out system from first post, CO, CH 4, CO 2After separating through second post, by six-way valve with most of CH 4In cut emptying, do not cut clean CH 4With CO, CO 2After further separating, the 3rd post is detected at detecting device;
3) contain in the lower carbon number hydrocarbons＞20% methane and with sample in CO content adopt five post flow processs with the order of magnitude or when being higher than the oxygen of content of CO, that is, and with the use of connecting with the sample inlet of two post flow processs of the sample export of three post flow processs;
Described flow process is made up of two streams, wherein:
Stream 1 has three analytical columns, a ten-way valve and a six-way valve, and its analysis process is: by the ten-way valve first post blowback CO 2After heavy constituent, by six-way valve second post with CO 2The light constituent fore blow emptying of front, the 3rd post is further with residual CH 4And CO 2Separately;
Stream 2 has two analytical columns, a ten-way valve, and its analysis process is: by the heavy constituent of ten-way valve the 4th post blowback CO back, the 5th post further separates O 2And CO;
Described trace amounts of CO, CO 2Be meant 0.01-1%;
Described trace CO, CO 2Be meant＜0.01%;
Described lower carbon number hydrocarbons is that carbon number is 1-4.
2, trace according to claim 1 and trace carbon monoxide, carbon dioxide gas chromatographic analysis flow process is characterized in that described analytical column is:
First post adopts 1-4m, the HayeSep Q of internal diameter φ 2-3mm, Porapak Q or Chromosorb 102;
Second post and the 3rd post adopt 1-5m, the HayeSep Q of internal diameter φ 2-3mm, Porapak Q or Chromosorb 102;
The 4th post adopts 1-3m, TXD-01 or the CARBOSIEVE of internal diameter φ 2-3mm;
The 5th post adopts 1-5m, TXD-01 or the CARBOSIEVE of internal diameter φ 2-3mm.
CNB011158247A 2001-05-08 2001-05-08 Gas chromatographic analysis process of micro and trace CO and CO2 Expired - Fee Related CN1172187C (en)

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Publication number Priority date Publication date Assignee Title
CN100478686C (en) * 2004-08-13 2009-04-15 中国科学院沈阳应用生态研究所 Method of deter mining N2O concentration of gas gample using back flush in double sample injection mouthes
CN101923098B (en) * 2010-08-20 2012-12-26 南京特种气体厂有限公司 Continuous on-line analysis device of benzene, total hydrocarbons, methane and CO in carbon dioxide
CN102621251A (en) * 2011-01-31 2012-08-01 中国石油化工股份有限公司 Trace helium, neon and hydrogen gas analysis method and device
CN103604897B (en) * 2013-10-31 2014-12-03 陕西延长石油(集团)有限责任公司研究院 On-line multidimensional gas chromatographic analysis device universal for low carbon catalytic conversion reaction

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