CN102628846B - Gas chromatography detection system and method for analyzing trace impurities in ultrahigh pure gas - Google Patents
Gas chromatography detection system and method for analyzing trace impurities in ultrahigh pure gas Download PDFInfo
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Abstract
The invention relates to detection equipment and technology for a gas chromatography instrument, in particular to a gas chromatography detection system and method for analyzing trace impurities in ultrahigh pure gas. A first molecular sieve chromatographic column (51) is arranged between a switching valve VI (1) and a switching valve VII (2); a second molecular sieve chromatographic column (52) is arranged between a switching valve VII (2) and a switching valve VIV (4); and a second column separator (62) is arranged between the switching valve VIII (3) and switching valve VIV (4). A secondary sampling way is adopted for sample gas, and a main component is pre-cut during primary sample feeding of a ten-way switching valve VI (1) and subjected to back flushing during secondary sample feeding of the ten-way switching valve VI (1); and the main component is separated and switched, and enters a helium ion detector (8) for analyzing. The gas chromatography detecting system is controlled through each valve, the sequence of actions is executed by using an event draw-up program, the entire analyzing process is controlled automatically, actions are rapid, consistent and reliable, and the data repeatability and accuracy of the system are ensured through a stable flow gas channel and accurate valve switching.
Description
Technical field
The present invention relates to a kind of gas chromatograph checkout equipment and detection technique, relate in particular to gas-chromatography detection system and the method for Analysis of Micro-amount Impurities In Liquid in ultra-pure gas.
Background technology
At present, the domestic gas chromatograph for Analysis of Gases of High Purity, generally all uses and adopts traditional TCD and FID or Zirconia detector; Their detecting device is technology tradition or backwardness mostly, and very strong to impurity analysis selectivity in gas, a kind of gas is often wanted many stratographic analyses, and the flow process abbreviated analysis component of analyzing repeatedly, system is less demanding to gas circuit, makes the large reduction of detection sensitivity of system; Gas chromatographic analysis, in multi-dimensional chromatograph isolation technics scheme, often requires nearly 5-6 to prop up chromatographic resolution pillar; And gas circuit between multi-dimensional chromatograph pillar connects special transfer valve again and realizes; Particularly be applied in gas separation chromatograph the requirement that the design of many gas circuits independence temperature control post case has solved different column temperatures.
Along with the fast development of China's industrial economy, gas has the title of " blood " in commercial production, supply and demand two is prosperous, the production of high-purity gas and ultra-pure gas makes in recent years new gas industry national standard with supply, after particularly 2006,2008,2009 etc., promulgate in the standard of carrying out, as high (superelevation) pure hydrogen, height (superelevation) purity nitrogen, high-purity (superelevation) argon, high-purity (superelevation) helium, high-purity (superelevation) oxygen; Industrial gasses and the used in electronic industry gas such as liquid nitrogen, liquid argon, liquid oxygen, in standard because having stipulated use ng/g(ppb) level highly sensitive PDHID helium ionization detector (being called for short PDD herein), this especially guarantees in gas that to whole chromatographic analysis system trace or vestige component enter PDHID detector response effectively, is that current pendulum is researched and developed a new problem in face of Analysis of Gases of High Purity chromatogram at home; Company designs a set of suitable for China for this reason, user accepts, analyzes required ultra-pure gas chromatographic analysis flow process that is exclusively used in, and improves the gas-chromatography detection method of Analysis of Micro-amount Impurities In Liquid in ultra-pure gas.
Summary of the invention
The present invention is directed to gas chromatograph detector technologies tradition common in prior art or fall behind, and very strong to impurity analysis selectivity in gas, a kind of gas is often wanted many stratographic analyses, and the flow process abbreviated analysis component of analyzing repeatedly, system is less demanding to gas circuit, makes the shortcoming such as the large reduction of detection sensitivity of system provide a kind of and completes by sub-sampling switching gas circuit the ultra high purity gas analysis chromatography processes flow process that in ultra-pure gas, all impurity compositions are analyzed.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals:
The gas-chromatography detection system of Analysis of Micro-amount Impurities In Liquid in ultra-pure gas, comprise carry 1, carry 2, carry 3, carry 4 gas circuits, transfer valve V I and transfer valve V II, transfer valve V III and transfer valve V IV, be provided with the first molecular sieve chromatography post between transfer valve V I and transfer valve V II; Between transfer valve V II and transfer valve V IV, be provided with the second molecular sieve chromatography post; Between transfer valve V I and transfer valve V III, be provided with needle-valve, between transfer valve V III and transfer valve V IV, be provided with the second pillar separation vessel; Carry that 1 gas circuit is connected with the 4. number interface of transfer valve V I, year 2 gas circuits are connected with the 7. number interface of transfer valve V I; Sample inlet is connected with the 1. number interface of transfer valve V I, and sample export is connected with the 2. number interface of transfer valve V I, and the 10. number interface of transfer valve V I is connected by pipeline with 3. number interface, is also provided with quantity tube on this pipeline; Carry 1 gas circuit and be connected with the 4. number interface of transfer valve V I, the 5. number interface of transfer valve V I is provided with the first pillar separation vessel with the pipeline that 9. number interface is connected; The upper end of needle-valve is connected with the 8. number interface of transfer valve V I, and lower end is connected with the 1. number interface of transfer valve V III; Carrying 2 gas circuits is connected with the 7. number interface of transfer valve V I; One end of the first molecular sieve chromatography post is connected with the 6. number interface of transfer valve V I, and the other end is connected with the 1. number interface of transfer valve V II; Carrying 3 gas circuits is connected with the 3. number interface of transfer valve V II; One end of the second molecular sieve chromatography post is connected with the 2. number interface of transfer valve V II, and the other end is connected with the 3. number interface of transfer valve V IV; 4. number interface of transfer valve V II is connected by pipeline with 5. number interface, and the 6. number interface of transfer valve V II is connected with variable valve A; Carrying 4 gas circuits is connected with the 3. number interface of transfer valve V III; 4. number interface of transfer valve V III is connected by pipeline with 5. number interface, and the 6. number interface of transfer valve V III is connected with variable valve B; One end of the second pillar separation vessel is connected with the 2. number interface of transfer valve V III, and the other end is connected with the 1. number interface of transfer valve V IV.
As preferably, the 2. number interface of transfer valve V IV is connected with helium ion detector, and the 4. number interface of transfer valve V IV is connected by pipeline with 5. number interface, and the 6. number interface of transfer valve V IV is connected with variable valve C.
As preferably, transfer valve V I is ten logically to purge pneumatic transfer valve, and transfer valve V II, V III, V IV are six logically to purge pneumatic transfer valve, carries 1, carries 2, carries 3, carries in 4 gas circuits and be respectively equipped with damper tube.Adopt Valco band to purge pneumatic transfer valve; Guarantee the counter-infiltration of air in gas circuit handoff procedure; Adopt Valco six direction changeover valves, four-way valve, makes the gas circuit stroke in valve body the shortest relatively; Adopting 316LValco1/16 " 0.13mm makes damping pipeline, the good and stability of flow of impermeability; The 5A chromatogram pillar that the research and development of employing company are produced, technological innovation and product quality not only ensure but also reliable; Adopt two heartcut systems, object emptying main component, guarantees that baseline is steady as much as possible; Adopt ten-way valve just blowing mode, feature is that the gas circuit flow of native system changes little after valve body switches; Adopt stainless steel metering pin valve, not only can control emptying flow but also can suppress the reverse osmosis of air; Adopt outside detached column case, make different chromatogram pillars there is independent temperature controlling function.
The gas-chromatography detection method of Analysis of Micro-amount Impurities In Liquid in ultra-pure gas, comprises the gas-chromatography detection system of Analysis of Micro-amount Impurities In Liquid in above-mentioned ultra-pure gas, adopts the sample introduction of sample gas secondary, and main component is opened H in the ten direction changeover valve V I pre-cuttings of sample introduction for the first time
2, O
2, Ar, N
2, CH
4, the component of CO and the CO of sample introduction blowback for the second time
2, C
2+, H
2o component; After separating again, switch and enter the analysis of helium ion detector, concrete steps are as follows:
A, transfer valve V I adopt forward sample introduction to change gas circuit with the mode of blowback and flow to and link pipeline, utilize the first pillar separation vessel to carrying component in 1 gas circuit main body gas separately and after transfer valve: gas circuit changes stream goes other component blowbacks to separate to the first molecular sieve chromatography post, by carrying 2 gas circuit reverse blows, go out remaining gas ingredients and flow into the second pillar separation vessel;
B, transfer valve V II are made the first heartcut to main component, the most main peak of emptying, and successively impurity component is put into the second molecular sieve chromatography post go separate; And control well and repeatedly switching time of valve impurity component is dropped on baseline and goes out peak, to improve its detection sensitivity;
C, transfer valve V III be as the second cutting center, is also mainly that component that blowback is come carries out secondary and excises all the other main peaks, and the component that emptying is not wanted, as trace water or sulfide, mainly by CO
2or C
2+ on the second pillar separation vessel, separated;
D, transfer valve V IV are switched to the second molecular sieve chromatography post and impurity component separation on the second pillar separation vessel respectively and in helium ion detector, go to respond out peak.
As preferably, the detection of trace impurity in nitrogen, sample introduction for the first time, comprises the steps:
A, switch V I ten-way valve and carry High Purity Nitrogen sample gas in 1 gas circuit series connection quantity tube and enter into the first pillar separation vessel and cut in advance pillar pre-separation and go out H
2, O
2/ Ar, containing N
2main body peak, CH
4, CO being put in the first molecular sieve chromatography post goes;
B, V I switching gas circuit then, carry 1 gas circuit and oppositely enter into the first pillar separation vessel and blow out remaining nitrogen and the CO comprising
2/ C
2+ remaining component; At this moment carry the H that 2 gas circuits enter into the first molecular sieve chromatography post and go first separating off nitrogen
2, O
2/ Ar, puts in the second molecular sieve chromatography post (52) and goes to continue to separate, and waits N
2in the time of just will going out the first molecular sieve chromatography post, switch V II valve emptying N
2peak, waits and is diffused in N
2in CH
4while going out the first molecular sieve chromatography post, switch V II valve, put into CH
4enter in the second molecular sieve chromatography post and go to separate;
C, similarly continue the remaining N of transfer valve emptying
2, wait and be diffused in N
2in CO switch V II valve will go out the first molecular sieve chromatography post time, put into CO and enter the second molecular sieve chromatography post and go to separate;
D, emptying N each time
2under time, adjusting to well can be by analyzed N
2in CH
4, CO is diluted to and on baseline, goes out peak by carrying helium in 3;
E, the isolated H of the second molecular sieve chromatography post pillar
2, O
2/ Ar, CH
4, CO component switched and enters in helium ion detector and respond by V IV valve; In this process the first pillar separation vessel blow out remaining nitrogen and comprise in CO
2/ C
2+ remaining component all by V II valve switch emptying fall.
As preferably, the detection of trace impurity in nitrogen, sample introduction switches ten direction changeover valve V I again by external event clock control for the second time, carries High Purity Nitrogen sample gas in 1 gas circuit series connection quantity tube and enters into the first pillar separation vessel and cut in advance pillar pre-separation and go out H
2, O
2/ Ar, containing N
2main body peak, CH
4, CO being put in the one the first molecular sieve chromatography column molecular sieve chromatographic columns goes, and by transfer valve V II, switch whole emptying and fall; Then control transfer valve V I switching gas circuit, year 1 gas circuit oppositely enters into the first pillar separation vessel and blows out remaining nitrogen and the CO comprising
2/ C
2+ remaining component; By the emptying of transfer valve V III, blow out remaining nitrogen, wait CO
2while isolating the first pillar separation vessel (61), switching transfer valve V III (3) puts in the second pillar separation vessel pillar and removes separation of C O
2or C
2+ component, at this moment transfer valve V IV performs in advance and switches CO
2or C
2+ enter in helium ion detector and respond.
As preferably, in the gas circuit after sub-sampling blowback, needle-valve can be used to regulate and carries 1 with to carry 2 flow velocity balances consistent in transfer valve V I valve, and it is laggard identical to flow in helium ion detector that transfer valve V IV is switched, and its base flow changes not quite.
The present invention is switched by just blowing with blowback of ten direction changeover valves and six direction changeover valves, the switching action of heartcut is all completed by system countercharge chromatographic work station, the corresponding external event of each valve is controlled, the order of its action is also by the event execution that programs, holistic approach automatic process control system like this, action is fast consistent reliable, the Data duplication of system and accuracy by stable flow gas circuit and accurately valve switch to guarantee.
Accompanying drawing explanation
Fig. 1 is gas-chromatography detection system of the present invention and method flow schematic diagram.
Fig. 2 is ten-way valve sampling and blowback CO
2, C
2+, H
2o waits until the first pillar separation vessel schematic diagram.
Fig. 3 is ten-way valve sample introduction and cuts in advance H
2, N
2, CH
4to the first molecular sieve chromatography post schematic diagram.
Fig. 4 is that transfer valve V II first is cut center emptying the first molecular sieve chromatography post main peak and the detected peak of purging enters into the second molecular sieve chromatography post schematic diagram.
Fig. 5 is that transfer valve V II the first cutting center will be detected peak and put in the second molecular sieve chromatography post and remove to separate schematic diagram.
Fig. 6 is that transfer valve V III second is cut remaining main peak and H in center emptying the first pillar separation vessel
2o, C
2+ etc.
Fig. 7 is transfer valve V III the second cutting center incision CO
2or C
2+ in the second pillar separation vessel, separate.
Fig. 8 is H in transfer valve V IV
2, O
2, N
2, CH
4, CO switches and enters into helium ion detector.
Fig. 9 is CO in transfer valve V IV
2or C
2+ switching enters into helium ion detector.
Wherein 1-transfer valve V I, 2-transfer valve V II, 3-transfer valve V III, 4-transfer valve V IV, 8-helium ion detector, 9-needle-valve, 11-damper tube, 21-damper tube, 31-damper tube, 41-damper tube, the 51-the first molecular sieve chromatography post, the 52-the second molecular sieve chromatography post, the 61-the first pillar separation vessel, the 62-the second pillar separation vessel, 71-variable valve A, 72-variable valve B, 73-variable valve C.
Embodiment
Below in conjunction with accompanying drawing 1 to accompanying drawing 9 and embodiment, the present invention is described in further detail:
The gas-chromatography detection system of Analysis of Micro-amount Impurities In Liquid in ultra-pure gas, comprise carry 1, carry 2, carry 3, carry 4 gas circuits, the logical purging between pneumatic transfer valve V I 1 and the pneumatic transfer valve V II 2 of six logical purgings of transfer valve V I 1 and transfer valve V II 2, transfer valve V III 3 and transfer valve V IV 4, ten is provided with the first molecular sieve chromatography post 51; Between transfer valve V II 2 and transfer valve V IV 4, be provided with the second molecular sieve chromatography post 52; Between transfer valve V I 1 and transfer valve V III 3, be provided with needle-valve 9, between transfer valve V III 3 and transfer valve V IV 4, be provided with the second pillar separation vessel 62.After carrier gas 1, carrier gas 2, carrier gas 3, carrier gas 4 are all done damping by microporous pipe, computer tube line length is carried out constant flow practical management, and this mode gas circuit stability of flow is accurate; Can measure by the adjustment of every 5-10cm length the subtle change of 2-3ml/min flow.Refer to accompanying drawing 1.
Carry that 1 gas circuit is connected with the 4. number interface of transfer valve V I 1, year 2 gas circuits are connected with the 7. number interface of transfer valve V I 1; Sample inlet is connected with the 1. number interface of transfer valve V I 1, and sample export is connected with the 2. number interface of transfer valve V I 1, and the 10. number interface of transfer valve V I 1 is connected by pipeline with 3. number interface, is also provided with quantity tube 12 on this pipeline; Carry 1 gas circuit and be connected with the 4. number interface of transfer valve V I 1, the 5. number interface of transfer valve V I 1 is provided with the first pillar separation vessel 61 with the pipeline that 9. number interface is connected; The upper end of needle-valve 9 is connected with the 8. number interface of transfer valve V I 1, and lower end is connected with the 1. number interface of transfer valve V III 4; Carrying 2 gas circuits is connected with the 7. number interface of transfer valve V I 1; One end of the first molecular sieve chromatography post 51 is connected with the 6. number interface of transfer valve V I 1, and the other end is connected with the 1. number interface of transfer valve V II 2.
Carrying 3 gas circuits is connected with the 3. number interface of transfer valve V II 2; One end of the second molecular sieve chromatography post 52 is connected with the 2. number interface of transfer valve V II 2, and the other end is connected with the 3. number interface of transfer valve V IV 4; 4. number interface of transfer valve V II 2 is connected by pipeline with 5. number interface, and the 6. number interface of transfer valve V II 2 is connected with variable valve A71.
Carrying 4 gas circuits is connected with the 3. number interface of transfer valve V III 3; 4. number interface of transfer valve V III 3 is connected by pipeline with 5. number interface, and the 6. number interface of transfer valve V III 3 is connected with variable valve B72; One end of the second pillar separation vessel 62 is connected with the 2. number interface of transfer valve V III 3, and the other end is connected with the 1. number interface of transfer valve V IV 4.
2. number interface of transfer valve V IV 4 is connected with helium ion detector 8, and the 4. number interface of transfer valve V IV 4 is connected by pipeline with 5. number interface, and the 6. number interface of transfer valve V IV 4 is connected with variable valve C73.
The gas-chromatography detection system of Analysis of Micro-amount Impurities In Liquid and method in ultra-pure gas, the sample introduction of employing sample gas secondary, main component is opened H in the ten direction changeover valve V I 1 pre-cuttings of sample introduction for the first time
2, O
2, Ar, N
2, CH
4, the component of CO and the CO of sample introduction blowback for the second time
2, C
2+, H
2o component; After separating again, switch and enter helium ion detector 8 and analyze, concrete steps are as follows:
A, transfer valve V I 1 adopt forward sample introduction and the mode of blowback to change gas circuit and flow to and link pipeline, utilize the first pillar separation vessel 61 to carrying component in 1 gas circuit main body gas separately and after transfer valve: gas circuit changes stream goes other component blowbacks to separate to the first molecular sieve chromatography post 51, by carrying 2 gas circuit reverse blows, go out remaining gas ingredients and flow into the second pillar separation vessel 62;
B, transfer valve V II 2 are made the first heartcut to main component, the most main peak of emptying, and successively impurity component is put into the second molecular sieve chromatography post 52 go separate; And control well and repeatedly switching time of valve impurity component is dropped on baseline and goes out peak, to improve its detection sensitivity;
Transfer valve V II 2 is as the first cutting center, i.e. the first molecular sieve chromatography post 51 and the second molecular sieve chromatography post 52 of 5A molecular sieve chromatography pillar of each series connection before and after valve, the first molecular sieve chromatography post 51 is used for the most of main body of pre-separation and emptying peak, remaining a small amount of main body peak the impurity peaks comprising by relatively emptying several times with put into the second molecular sieve chromatography post 52 and come removing impurities peak, the impurity peaks of analyzing is got back on horizontal base line, improved the detection sensitivity of impurity peaks.As shown in accompanying drawing 4,5.
C, transfer valve V III 3, as the second cutting center, are also mainly that the component that blowback is come carries out remaining its main peak of secondary excision, and the component that emptying is not wanted, as trace water or sulfide, mainly by CO
2or C
2+ on the second pillar separation vessel 62, separated;
Adopted V III six-way valve as the second cutting center, feature is an accurate stainless steel metering pin valve that damping is used of series connection before valve, is equal to the resistance of chromatographic column, and a special separation of C O of coming of the second pillar separation vessel 62 connects after V III valve
2, also can be used to separation of C
2+; The valve action of V III be emptying do not want be spread in the first pillar separation vessel 61 and remaining main body that blowback goes out and component thereof as trace water or sulfide etc.Refer to accompanying drawing 6,7 valves and switch schematic diagram.
D, transfer valve V IV 4 are switched to the second molecular sieve chromatography post 52 and impurity component separation on the second pillar separation vessel 62 respectively and in helium ion detector, go to respond out peak.
Adopted V IV six-way valve to switch the isolated H of the first molecular sieve chromatography post 51 pillar
2, O
2/ Ar, N
2, CH
4, CO component and the isolated CO of the second pillar separation vessel 62 pillar
2or C
2+ component enters helium ion detector 8 and responds, thereby measures the signal value of each impurity composition.Refer to accompanying drawing 8,9 valves and switch schematic diagram.Described ten logically all adopt the modular, pneumatically powered valve of the blowing and sweeping type Valco of VICI company with six direction changeover valves, its principal character is in cavity, to design the sweep gas protection gas circuit of positive-pressure type, guarantee that the air that the valve body rotor gap that mechanical seal causes when switching gas circuit has cannot diffuse into by reverse osmosis, the malleation of protection gas is cut completely from carrier gas and the possible contact of air; Guarantee that the switching in valve body hole and hole just carries out between carrier gas.
Sample introduction for the first time, comprises the steps:
A, switch V I ten-way valve and carry High Purity Nitrogen sample gas in 1 gas circuit series connection quantity tube 12 and enter into the first pillar separation vessel 61 and cut in advance pillar pre-separation and go out H
2, O
2/ Ar, containing N
2main body peak, CH
4, CO being put in the first molecular sieve chromatography post 51 goes; As shown in Figure 3.
B, V I switching gas circuit then, carry 1 gas circuit and oppositely enter into the first pillar separation vessel 61 and blow out remaining nitrogen and the CO comprising
2/ C
2+ remaining component; At this moment carry the H that 2 gas circuits enter into the first molecular sieve chromatography post 51 and go first separating off nitrogen
2, O
2/ Ar, puts in the second molecular sieve chromatography post 52 and goes to continue to separate, and waits N
2in the time of just will going out the first molecular sieve chromatography post 51, switch V II valve emptying N
2peak, waits and is diffused in N
2in CH
4while going out the first molecular sieve chromatography post 51, switch V II valve, put into CH
4enter in the second molecular sieve chromatography post 52 and go to separate;
C, similarly continue the remaining N of transfer valve emptying
2, wait and be diffused in N
2in CO switch V II valve will go out the first molecular sieve chromatography post 51 time, put into CO and enter the second molecular sieve chromatography post 52 and go to separate;
D, emptying N each time
2under time, adjusting to well can be by analyzed N
2in CH
4, CO is diluted to and on baseline, goes out peak by carrying helium in 3;
E, the isolated H of the second molecular sieve chromatography post 52 pillar
2, O
2/ Ar, CH
4, CO component switched and enters in helium ion detector 8 response by V IV valve; In this process the first pillar separation vessel 61 blow out remaining nitrogen and comprise in CO
2/ C
2+ remaining component all by V II valve switch emptying fall.
Sample introduction switches ten direction changeover valve V I 1 again by external event clock control for the second time, carries High Purity Nitrogen sample gas in 1 gas circuit series connection quantity tube 12 and enters into the first pillar separation vessel 61 and cut in advance pillar pre-separation and go out H
2, O
2/ Ar, containing N
2main body peak, CH
4, CO being put in the one the first molecular sieve chromatography post 51 molecular sieve chromatography posts 51 goes, and by transfer valve V II 2, switch whole emptying and fall; Then control transfer valve V I 1 switching gas circuit, year 1 gas circuit oppositely enters into the first pillar separation vessel 61 and blows out remaining nitrogen and the CO comprising
2/ C
2+ remaining component; By 3 emptying of transfer valve V III, blow out remaining nitrogen, wait CO
2while isolating the first pillar separation vessel 61, switching transfer valve V III 3 puts in the second pillar separation vessel 62 pillars and removes separation of C O
2or C
2+ component, at this moment transfer valve V IV 4 performs in advance and switches CO
2or C
2+ enter in helium ion detector 8 response.
In gas circuit after sub-sampling blowback, needle-valve 9 can be used to regulate and carries 1 with to carry 2 flow velocity balances consistent in transfer valve V I 1 valve, and it is laggard identical to flow in helium ion detector that transfer valve V IV 4 is switched, and its base flow changes not quite.
We,, by the impurity proximate analysis of ultra-pure nitrogen (99.9999%) is implemented to this method, reach the object that ultra-pure nitrogen is detected below; Its implementation process is as follows: instrument for the first time automatically sampling switch V I ten-way valve and carry High Purity Nitrogen sample gas in 1 gas circuit series connection 1ml quantity tube and enter into the first pillar separation vessel 61 and cut in advance pillar pre-separation and go out H
2, O
2/ Ar, containing N
2main body peak, CH
4, CO being put in first the first molecular sieve chromatography post 51 goes; Then V I switching gas circuit carries 1 gas circuit and oppositely enters into the first pillar separation vessel 61 and blow out remaining nitrogen and the CO comprising
2/ C
2+ remaining component, C
2+ be mainly alkane and alkene; At this moment carry the H that 2 gas circuits enter into the first molecular sieve chromatography post 51 and go first separating off nitrogen
2, O
2/ Ar, puts in second the second molecular sieve chromatography post 52 and goes to continue to separate, and waits N
2just to go out 51, the first molecular sieve chromatography post and switch V II valve emptying N
2peak, waits and is diffused in N
2in CH
4while going out the first molecular sieve chromatography post 51, switch V II valve, put into CH
4enter in the second molecular sieve chromatography post 52 and go to separate; Similarly continue the remaining N of transfer valve emptying
2, wait and be diffused in N
2in CO switch V II valve will go out the first molecular sieve chromatography post 51 time, put into CO and enter the second molecular sieve chromatography post 52 and go to separate; Emptying N each time
2under time, adjusting to well can be by analyzed N
2in CH
4, CO is diluted to and on baseline, goes out peak by carrying helium in 3; The isolated H of the second molecular sieve chromatography post 52 pillar
2, O
2/ Ar, CH
4, CO component switched and enters in PDHID helium ion detector and respond by V IV valve; In this process the first pillar separation vessel 61 blow out remaining nitrogen and comprise in CO
2/ C
2+ remaining component all by V II valve switch emptying fall.
In a word, the foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to the covering scope of patent of the present invention.
Claims (6)
1. the gas-chromatography detection system of Analysis of Micro-amount Impurities In Liquid in ultra-pure gas, comprise carry 1, carry 2, carry 3, carry 4 gas circuits, transfer valve V I (1) and transfer valve V II (2), transfer valve V III (3) and transfer valve V IV (4), is characterized in that: between transfer valve V I (1) and transfer valve V II (2), be provided with the first molecular sieve chromatography post (51); Between transfer valve V II (2) and transfer valve V IV (4), be provided with the second molecular sieve chromatography post (52); Between transfer valve V I (1) and transfer valve V III (3), be provided with needle-valve (9), between transfer valve V III (3) and transfer valve V IV (4), be provided with the second pillar separation vessel (62), carry 3 gas circuits and be connected with the 3. number interface of transfer valve V II (2); One end of the second molecular sieve chromatography post (52) is connected with the 2. number interface of transfer valve V II (2), and the other end is connected with the 3. number interface of transfer valve V IV (4); 4. number interface of transfer valve V II (2) is connected by pipeline with 5. number interface, 6. number interface and the variable valve A(71 of transfer valve V II (2)) be connected; Carry that 1 gas circuit is connected with the 4. number interface of transfer valve V I (1), year 2 gas circuits are connected with the 7. number interface of transfer valve V I (1); Sample inlet is connected with the 1. number interface of transfer valve V I (1), and sample export is connected with the 2. number interface of transfer valve V I (1), and the 10. number interface of transfer valve V I (1) is connected by pipeline with 3. number interface, is also provided with quantity tube (12) on this pipeline; Carry 1 gas circuit and be connected with the 4. number interface of transfer valve V I (1), the 5. number interface of transfer valve V I (1) is provided with the first pillar separation vessel (61) with the pipeline that 9. number interface is connected; The upper end of needle-valve (9) is connected with the 8. number interface of transfer valve V I (1), and lower end is connected with the 1. number interface of transfer valve V III (4); Carrying 2 gas circuits is connected with the 7. number interface of transfer valve V I (1); One end of the first molecular sieve chromatography post (51) is connected with the 6. number interface of transfer valve V I (1), and the other end is connected with the 1. number interface of transfer valve V II (2); Carrying 4 gas circuits is connected with the 3. number interface of transfer valve V III (3); 4. number interface of transfer valve V III (3) is connected by pipeline with 5. number interface, 6. number interface and the variable valve B(72 of transfer valve V III (3)) be connected; One end of the second pillar separation vessel (62) is connected with the 2. number interface of transfer valve V III (3), and the other end is connected with the 1. number interface of transfer valve V IV (4); 2. number interface of transfer valve V IV (4) is connected with helium ion detector (8), and the 4. number interface of transfer valve V IV (4) is connected by pipeline with 5. number interface, 6. number interface and the variable valve C(73 of transfer valve V IV (4)) be connected.
2. the gas-chromatography detection system of Analysis of Micro-amount Impurities In Liquid in ultra-pure gas according to claim 1, it is characterized in that: described transfer valve V I (1) is the pneumatic transfer valve of ten logical purgings, transfer valve V II, V III, V IV (2,3,4) are six logical to purge pneumatic transfer valve, carry 1, carry 2, carry 3, carry in 4 gas circuits and be respectively equipped with damper tube (11,21,31,41).
3. the gas-chromatography detection method of Analysis of Micro-amount Impurities In Liquid in ultra-pure gas, comprise the gas-chromatography detection system of Analysis of Micro-amount Impurities In Liquid in ultra-pure gas claimed in claim 1, it is characterized in that, the sample introduction that adopts sample gas secondary, main component is opened H in ten direction changeover valve V I (1) the pre-cuttings of sample introduction for the first time
2, O
2, Ar, N
2, CH
4, the component of CO and the CO of sample introduction blowback for the second time
2, C
2+, H
2o component; After separating again, switch and enter helium ion detector (8) analysis, concrete steps are as follows:
A, transfer valve V I (1) adopt forward sample introduction to change gas circuit with the mode of blowback and flow to and link pipeline, utilize the first pillar separation vessel (61) to carrying component in 1 gas circuit main body gas separately and after transfer valve: gas circuit changes stream goes other component blowbacks to separate to the first molecular sieve chromatography post (51), by carrying 2 gas circuit reverse blows, go out remaining gas ingredients and flow into the second pillar separation vessel (62);
B, transfer valve V II (2) are made the first heartcut to main component, the most main peak of emptying, and successively impurity component is put into the second molecular sieve chromatography post (52) go separate; And control well and repeatedly switching time of valve impurity component is dropped on baseline and goes out peak, to improve its detection sensitivity;
C, transfer valve V III (3) be as the second cutting center, is also mainly that component that blowback is come carries out secondary and excises all the other main peaks, and the component that emptying is not wanted, as trace water or sulfide, mainly by CO
2or C
2+ on the second pillar separation vessel (62), separated;
D, transfer valve V IV (4) are switched to the second molecular sieve chromatography post (52) and the upper Fen Li impurity component of the second pillar separation vessel (62) respectively and in helium ion detector, go to respond out peak.
4. the gas-chromatography detection method of Analysis of Micro-amount Impurities In Liquid in ultra-pure gas according to claim 3, is characterized in that, the detection of trace impurity in nitrogen, and sample introduction for the first time, comprises the steps:
A, switch V I ten-way valve and carry High Purity Nitrogen sample gas in 1 gas circuit series connection quantity tube (12) and enter into the first pillar separation vessel (61) and cut in advance pillar pre-separation and go out H
2, O
2/ Ar, containing N
2main body peak, CH
4, CO being put in the first molecular sieve chromatography post (51) goes;
B, V I switching gas circuit then, carry 1 gas circuit and oppositely enter into the first pillar separation vessel (61) and blow out remaining nitrogen and the CO comprising
2/ C
2+ remaining component; At this moment carry the H that 2 gas circuits enter into the first molecular sieve chromatography post (51) and go first separating off nitrogen
2, O
2/ Ar, puts in the second molecular sieve chromatography post (52) and goes to continue to separate, and waits N
2in the time of just will having gone out the first molecular sieve chromatography post (51), switch V II valve emptying N
2peak, waits and is diffused in N
2in CH
4while going out the first molecular sieve chromatography post (51), switch V II valve, put into CH
4enter in the second molecular sieve chromatography post (52) and go to separate;
C, similarly continue the remaining N of transfer valve emptying
2, wait and be diffused in N
2in CO switch V II valve will go out the first molecular sieve chromatography post (51) time, put into CO and enter the second molecular sieve chromatography post (52) and go to separate;
D, emptying N each time
2under time, adjusting to well can be by analyzed N
2in CH
4, CO is diluted to and on baseline, goes out peak by carrying helium in 3;
E, the isolated H of the second molecular sieve chromatography post (52) pillar
2, O
2/ Ar, CH
4, CO component switched and enters response in helium ion detector (8) by V IV valve; In this process the first pillar separation vessel (61) blow out remaining nitrogen and comprise in CO
2/ C
2+ remaining component all by V II valve switch emptying fall.
5. the gas-chromatography detection method of Analysis of Micro-amount Impurities In Liquid in ultra-pure gas according to claim 3, it is characterized in that: the detection of trace impurity in nitrogen, sample introduction switches ten direction changeover valve V I (1) again by external event clock control for the second time, carries High Purity Nitrogen sample gas in 1 gas circuit series connection quantity tube (12) and enters into the first pillar separation vessel (61) and cut in advance pillar pre-separation and go out H
2, O
2/ Ar, containing N
2main body peak, CH
4, CO being put in a 5A1 molecular sieve chromatography post (51) goes, and by transfer valve V II (2), switch whole emptying and fall; Then control transfer valve V I (1) switching gas circuit, year 1 gas circuit oppositely enters into the first pillar separation vessel (61) and blows out remaining nitrogen and the CO comprising
2/ C
2+ remaining component; By transfer valve V III (3) emptying, blow out remaining nitrogen, wait CO
2while isolating the first pillar separation vessel (61), switching transfer valve V III (3) puts in the second pillar separation vessel (62) pillar and removes separation of C O
2or C
2+ component, at this moment transfer valve V IV (4) performs in advance and switches CO
2or C
2+ enter response in helium ion detector (8).
6. the gas-chromatography detection method of Analysis of Micro-amount Impurities In Liquid in ultra-pure gas according to claim 3, it is characterized in that: needle-valve in the gas circuit after sub-sampling blowback (9) can be used to regulate in transfer valve V I (1) valve carry 1 consistent with year 2 flow velocity balances, and it is laggard identical to flow in helium ion detector that transfer valve V IV (4) is switched, its base flow changes little.
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