CN105588897A - Underwater gas chromatography system for realizing in-situ test for H2 and CH4 in seawater and operation method thereof - Google Patents
Underwater gas chromatography system for realizing in-situ test for H2 and CH4 in seawater and operation method thereof Download PDFInfo
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- CN105588897A CN105588897A CN201610095995.3A CN201610095995A CN105588897A CN 105588897 A CN105588897 A CN 105588897A CN 201610095995 A CN201610095995 A CN 201610095995A CN 105588897 A CN105588897 A CN 105588897A
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Abstract
The invention relates to an underwater gas chromatography system for realizing in-situ test for H2 and CH4 in seawater and an operation method thereof. The underwater gas chromatography system comprises a seawater automatic sampling and gas membrane extracting unit, a multi-component gas automatic detecting and self-correcting unit and an exhaust gas recovering unit, wherein the seawater automatic sampling and gas membrane extracting unit is mounted on an instrument cabin end cover; the multi-component gas automatic detecting and self-correcting unit and the exhaust gas recovering unit are packaged in a high-pressure sealing instrument cabin; the seawater automatic sampling and gas membrane extracting unit is used for separating and extracting gas from a seawater sample and the gas is applied to the subsequent assay determination of a gas automatic detection device; the multi-component gas automatic detecting and self-correcting unit is used for quantitatively analyzing and determining the content of the gas in the seawater by using a pulse helium ionization detector; the exhaust gas recovering unit is used for storing the exhaust gas discharged from the system in an exhaust gas bottle, keeping the system pressure within a suitable numerical range and ensuring the normal running of all functional components in the system. According to the invention, the gas chromatographic technique is applied to underwater position and can be used for performing underwater accurate in-situ test on various dissolvable gases in deep sea and truly reflecting the content of the in-situ gases on seabed.
Description
Technical field
The invention belongs to gas chromatographic analysis technique field, be specifically related to one and can realize H in seawater2、CH4Deng gas chromatography system under water and the method for operating thereof of gas in-situ test.
Background technology
Submarine hydrothermal activity can spray a large amount of CH4、H2、CO2Deng gas, the disturbance of gas hydrates is decomposed also can discharge a large amount of CH4Deng hydrocarbon gas, thereby cause these spike gases in seawater to occur that abnormal high-load distributes. By the abnormal distribution characteristics of quick detection and these spike gases of tracking, can be fast and effectively scientific basis of the Resource Supplies such as searching and rational evaluation submarine hydrothermal solution sulfide and gas hydrates. Meanwhile, CH in ocean4、H2And CO2Deng gas or biological important energy source, the variation characteristics such as its content are effective tracers that recourse marine physics, chemistry and bioprocess change, and are the important information carriers of the circulation of research marine biogeochemistry and global climate Environment Change process.
From the method for testing of current deep-sea gas, the methods of analyzing again after shipborne system sampling that adopt more, the device that can carry out at present gas in-situ investigation under deep-sea high-pressure environment is little, comparatively ripe is some sensor technologies, surveys and not yet realize at present underwater in-situ as the important means-gas chromatographic technique of gas test.
Gas chromatographic technique is applied to seabed by the present invention, uses the gas component in membrane separation technique separation and Extraction seawater, adopts highly sensitive PDHID detector, realizes H in seawater2、CH4Deng the in situ detection of dissolved gas.
Summary of the invention
The object of the present invention is to provide a kind of in-situ test system and method for operating thereof of dissolved gas under water, gas chromatographic technique is applied under water, use the gas component in membrane separation technique separation and Extraction seawater, employing PDHID detector under water original position accurately detects H in seawater2、CH4Deng the content of gas. Test macro uses extraneous Power supply, can with the ROV of underwater remote-control robot or manned underwater vehicle HOV supporting operation, also can dock with submarine observation network as required, realize long-term in-situ observation.
The one that the present invention proposes can realize H in seawater2、CH4Deng the gas chromatography system under water of gas in-situ test, comprise that seawater auto injection and gas film extraction unit, multicomponent gas detect and self-correcting unit and waste heat recovery unit automatically, wherein: multicomponent gas automatically detects and self-correcting unit, waste heat recovery unit are all packaged in high pressure sealing instrument room, and seawater auto injection and gas film extraction unit are installed on instrument room end cap;
Seawater auto injection and gas film extraction unit by water inflow filter 1, film sampling device, water pump 3, go out water filter 4 and form, in film sampling device, be provided with seawater sample storehouse 2 and gas storehouse 6, between seawater sample storehouse 2 and gas storehouse 6, pellicle 5 is set, the film that described pellicle 5 is permeable watertight, by withstand voltage encapsulation, can be automatically by the gas separation and Extraction in seawater sample storehouse 2 in gas storehouse 6; Water inflow filter 1 connects seawater sample storehouse 2 by pipeline, and seawater sample storehouse 2 is connected water filter 4 by pipeline with water pump 3;
Multicomponent gas automatically detects and self-correcting unit comprises sample introduction module, chromatographic column and post case 24a, pulse helium ionized detector 24b, pressure-reducing valve 15, gas bottle 16, gas purifier 17 and carrier gas bottle 18, wherein: sample introduction module by the first magnetic valve 7, anti-drip valve 8, water leakage detection sensor 9, syringe pump 19, two six lead to film valves 10, quantitatively encircle 12 and multithread road selective membrane valve 13 form; Gas storehouse 6 is connected water leakage detection sensor 9 by pipeline with anti-drip valve 8, water leakage detection sensor 9 connects 3 mouthfuls of two six logical film valves 10 by pipeline, 2 mouthfuls of two six logical film valves 10 connect the C mouth of multithread road selective membrane valve 13 by pipeline, 1 mouthful of two six logical film valves 10 connects chromatographic column and post case 24a by pipeline, 4 mouthfuls of two six logical film valves 10 connect gas purifier 17 by pipeline, and gas purifier 17 is connected carrier gas bottle 18 with valve by pipeline; Two six logical film valves 10 are connected gas bottle 16 by the second magnetic valve 11, pressure-reducing valve 15 successively with pipeline; 4 mouthfuls of multithread road selective membrane valve 13 are connected gas bottle 16 with pipeline with pressure-reducing valve 15 by pipeline; 2 mouthfuls of multithread road selective membrane valve 13 connect syringe pump 19 by pipeline; 3 mouthfuls of multithread road selective membrane valve 13 connect gas purifier 17 by pipeline; the P mouth of multithread road selective membrane valve 13 connects two six logical film valves 10 by pipeline, quantitatively encircles 12 and is positioned on two six logical film valves 10; Pulse helium ionized detector 24b connects the 4th magnetic valve 14b;
Waste heat recovery unit is made up of waste gas pump 20a, pressure sensor 20b, the first two two-port valve 21a, the second two two-port valve 21b, check valve 22 and waste gas bottles 23, pressure sensor 20b connects waste gas pump 20a, the gas outlet of waste gas pump 20a is divided into two-way, the pipeline of leading up to connects the first two two-port valve 21a, the pipeline of separately leading up to connects the second two two-port valve 21b, and the second two two-port valve 21b are connected waste gas bottle 23 by check valve 22 with pipeline.
The first magnetic valve 7, anti-drip valve 8, water leakage detection sensor 9, two six logical film valves 10, the second magnetic valve 11, quantitatively encircle 12, multithread road selective membrane valve 13, the 3rd magnetic valve, the 4th magnetic valve, pressure-reducing valve 15, gas bottle 16, gas purifier 17, carrier gas bottle 18, syringe pump 19, waste gas pump 20a, pressure sensor 20b, the first two two-port valve 21a, the second two two-port valve 21b, check valve 22, waste gas bottle 23,24a is that chromatographic column is connected respectively central control unit 25 with post case 24a, pulse helium ionized detector 24b.
In the present invention, carrier gas is high-purity helium, from carrier gas bottle 18 gas coming through gas purifiers 17, obtains high-purity helium of 99.9999%; Gas bottle spirit is high-purity helium, and certain density H is provided2、CH4Deng standard mixture.
In the present invention, for preventing that the gas in environment from polluting film valve, two six logical film valves 10 and multithread road selective membrane valve 13 are band from the film valve that purges function, high-purity helium that sweep gas is 99.9999%, and driving gas is the calibrating gas in gas bottle.
In the present invention, leak once water leakage detection sensor 9 detects, stop valve 8, at once in off-state, prevents that seawater is leaked into instrument room; In wakeup process, system detects hypertonia, and waste gas pump 20a works immediately, and waste gas is retracted in waste gas bottle 23.
The method of operating of the gas chromatography system under water that the present invention proposes system after power supply energising, when system is during in holding state, 5A molecular sieve column 24a flow is 50ml/min, 30 DEG C/min is warming up to 180 DEG C, keeps 2 hours, is down to 60 DEG C, remains unchanged. PDHID24b is warmed up to rapidly 150 DEG C, remains unchanged. Specific works flow process comprises: 1. wake up, 2. clean, 3. marked gas or extract film divided gas flow, 4. test, 5. self-correcting, 6. standby;
1. wake up: waken system, pressure sensor 20b detects environmental pressure, when higher than 1.2bar, waste gas pump 20a starts work, the first two two-port valve 21a open, and to release the pressure, waste gas pump 20a are started the impact of moment, subsequently, close the first two two-port valve 21a, open the second two two-port valve 21b, waste gas is discharged by the second two two-port valve 21b and check valve 22, enters in waste gas bottle 23, until cabin body internal pressure comes back to 1bar, waste gas pump 20a quits work;
After system environments pressure detecting is normal, the 3rd magnetic valve 14a and the 4th magnetic valve 14b open, helium in carrier gas bottle 18 becomes high-purity helium of 99.9999% after gas purifier 17 purifies, high-purity helium is divided into two-way: the magnetic valve 14a of leading up to purges two six logical film valves 10 and multithread road selective membrane valve 13, another road enters chromatographic column 24a and PDHID detector 24b by 4 mouthfuls and 1 mouthful of two six logical film valves 10 successively successively as carrier gas, and is discharged in the body of cabin by the 4th magnetic valve 14b; Calibrating gas in gas bottle 16 is divided into two kinds: a road directly passes into 4 mouthfuls of multithread road selective membrane valve 13, and another road is as driving the moving multithread of gas drive road selective membrane valve 13 to work;
2. clean: system stream is cleaned. The first magnetic valve 7 is opened, multithread road selective membrane valve 13 switches makes its C mouth be communicated with 3 mouthfuls, 3 mouthfuls by multithread road selective membrane valve 13 and C mouth, two six logical film valves 10 2 mouthfuls successively of carrier gas, quantitatively encircle 12,3 mouthfuls, gas storehouse 6 of two six logical film valves 10, be discharged in the body of cabin finally by the first magnetic valve 7, realize the cleaning in quantitative ring 12 and gas storehouse 6;
3. marked gas or extraction film divided gas flow: after system stream has cleaned, can enter as required marked gas flow process or extract film divided gas flow flow process;
If enter marked gas flow process, multithread road selective membrane valve 13 switches makes C mouth be communicated with 4 mouthfuls, calibrating gas through gas bottle 16 out after, enter successively 4 mouthfuls of multithread road selective membrane valve 13 and C mouth, two six 102 mouthfuls, logical film valves, quantitatively encircle 12, two six 103 mouthfuls, logical film valves, gas storehouses 6, be discharged in the body of cabin by magnetic valve 7, make quantitatively in ring, to be full of calibrating gas. Then shut electromagnetic valve 7, system is carried out following testing process, and carrier gas enters PDHID24b with the calibrating gas in quantitative ring 12 and detects after chromatographic column 24a separates, and determines certain density H2、CH4Deng appearance time, peak height and the peak area of gas with various component, for detecting, the gasometry to be measured in later stage provides foundation.
If enter film separation and Extraction gas flow process, magnetic valve 7 cuts out, and the water pump 3 in seawater auto injection and gas film extraction unit is worked, and seawater is drawn into seawater sample storehouse 2 from water inflow filter 1, then discharges from going out water filter 4. Draw water and finish and after balance waits for a period of time, the gas in 2 water bodys of seawater sample storehouse can see through the gas storehouse 6 that semipermeable membrane enters opposite side and store. Subsequently, multithread road selective membrane valve 13 switches C mouth and communicates with 2 mouthfuls, syringe pump 19 extracts gas in gas storehouse, gas from gas storehouse 6 successively through 3 mouthfuls of two six logical film valves 10, quantitatively encircle 12,2 mouthfuls of two six logical film valves 10, the C mouth of multithread road selective membrane valve 13 and 2 mouthfuls enter syringe pump 19, make quantitatively in ring 12, to be full of the gas extracting from seawater.
4. test: after above-mentioned flow process finishes, system switches to sample introduction test mode. Open magnetic valve 11, make the calibrating gas in gas bottle 16 be driven two six logical film valves 10 to work, two six logical film valves 10 switch at once 4 mouthfuls and 1 mouthful and communicate with quantitative ring 12, C mouth and any a bite of multithread road selective membrane valve 13 are obstructed, carrier gas flow through successively 4 mouthfuls of two six logical film valves 10, quantitatively encircle 12,1 mouthfuls, bring into and after chromatographic column 24a separates, enter pulse helium ionized detector PDHID24b and detect analysis being stored in gas in quantitative ring 12, and testing result is shown in to display screen.
5. self-correcting: system also has self-correcting function, can enter self-correcting flow process automatically according to setting in advance after the sample of the complete some of every detection. This flow process occur in stream clean finish after, by calibrating gas test compare realize self-correcting, concrete steps are consistent with marked gas flow process.
6. standby: after testing process finishes, the second magnetic valve 11, the 3rd magnetic valve 14a and the 4th magnetic valve 14b disconnect, two six logical film valves 10 switch to 3 mouthfuls and 2 mouthfuls and communicate with quantitative ring 12, open the first magnetic valve 7, and syringe pump 19 resets. Finally, close the first magnetic valve 7, system enters holding state, waits for next circulation.
Beneficial effect of the present invention is gas chromatographic technique to be applied under water, can carry out in situ detection accurately to the multiple dissolved gas in deep-sea under water. Detectability using 3 times of signal to noise ratios as system, the detection of methane is limited to 2.27nmol/L, and the detection of hydrogen is limited to 0.17nmol/L.
Brief description of the drawings
Fig. 1 is system principle schematic diagram of the present invention.
Fig. 2 is fundamental diagram and the gas flow circuit diagram of two six logical film valves and multithread road selective membrane valve in the present invention.
Fig. 3 is PDHID chromatogram in embodiment.
Number in the figure: 1 is water inflow filter, 2 is seawater sample storehouse, 3 is water pump, 4 for going out water filter, 5 is pellicle, 6 is gas storehouse, 7 is the first magnetic valve, 8 is anti-drip valve, 9 is water leakage detection sensor, 10 is two six logical film valves, 11 is the second magnetic valve, 12 is quantitatively to encircle, 13 is multithread road selective membrane valve, 14a and 14b are respectively the 3rd, the 4th magnetic valve, 15 is pressure-reducing valve, 16 is gas bottle, 17 is gas purifier, 18 is carrier gas bottle, 19 is syringe pump, 20a is waste gas pump, 20b is pressure sensor, 21a and 21b are respectively first, the second two two-port valves, 22 is check valve, 23 is waste gas bottle, 24a is chromatographic column and post case (5A molecular sieve column), 24b is pulse helium ionized detector (PDHID), 25 is central control unit.
Detailed description of the invention
Further illustrate by reference to the accompanying drawings the present invention below by embodiment.
Embodiment 1:
As shown in Figure 1, gas chromatography system is made up of 3 major parts under water, and seawater auto injection and gas film extraction unit, multicomponent gas automatically detect and self-correcting unit, waste heat recovery unit. Wherein the automatic detection of multicomponent gas and self-correcting unit, waste heat recovery unit are all packaged in high pressure sealing instrument room, and seawater auto injection and gas film extraction unit are installed on instrument room end cap.
Seawater auto injection and gas film extraction unit by water inflow filter 1, film sampling device, water pump 3, go out water filter 4 and form, wherein film sampling device comprises seawater sample storehouse 2, pellicle 5, gas storehouse 6.
Be packaged in that multicomponent gas in high pressure sealing instrument room detects automatically and self-correcting unit comprises the parts such as sample introduction module, chromatographic column and post case 5A molecular sieve column 24a, pulse helium ionized detector 24b, the second magnetic valve 11, the 3rd magnetic valve 14a, the 4th magnetic valve 14b, pressure-reducing valve 15, gas bottle 16, gas purifier 17, carrier gas bottle 18, wherein sample introduction module by the first magnetic valve 7, anti-drip valve 8, water leakage detection sensor 9, syringe pump 19, band purge two six lead to film valves 10, quantitatively encircle 12 and multithread road selective membrane valve 13 form.
Waste heat recovery unit is made up of waste gas pump 20a, pressure sensor 20b, the first two two-port valve 21a and the second two two-port valve 21b, check valve 22, waste gas bottles 23.
The first magnetic valve 7, anti-drip valve 8, water leakage detection sensor 9, two six logical film valves 10, the second magnetic valve 11, quantitatively encircle 12, multithread road selective membrane valve 13, the 3rd magnetic valve, the 4th magnetic valve, pressure-reducing valve 15, gas bottle 16, gas purifier 17, carrier gas bottle 18, syringe pump 19, waste gas pump 20a, pressure sensor 20b, the first two two-port valve 21a, the second two two-port valve 21b, check valve 22, waste gas bottle 23,24a is that chromatographic column is connected respectively central control unit 25 with post case 24a, pulse helium ionized detector 24b.
1. gas is prepared
Preparation H2、O2、N2、CH4The mixture of four kinds of gases, four kinds of gas concentrations are followed successively by: 10ppm, 250ppm, 500ppm, 10ppm, taking high-purity He as background, pack in the gas bottle of 1L.
2. dissolved gas in-situ test under water
Whole system is dropped in pond, make it in floodage. After power supply energising, system is in holding state, and 5A molecular sieve column 24a flow is 50ml/min, and 30 DEG C/min is warming up to 180 DEG C, keeps 2 hours, is down to 60 DEG C, remains unchanged. PDHID24b is warmed up to rapidly 150 DEG C, remains unchanged. In system work process, leakage sensor 9 can detect the situation of leaking, and detects and leaks, and stop valve 8 is at once in off-state, system alarm;
I. system calibrating:
1. wake up: waken system. Pressure sensor 20b detects environmental pressure, higher than 1.2bar, waste gas pump 20a starts work, the first two two-port valve 21a open, and to release the pressure, waste gas pump 20a are started the impact of moment, subsequently, close two two-port valve 21a, open the second two two-port valve 21b, waste gas is discharged by the second two two-port valve 21b and check valve 22, enters in waste gas bottle 23. Until cabin body internal pressure comes back to 1bar, waste gas pump 20a quits work.
After ambient parameter detects normally, the 3rd magnetic valve 14a and the 4th magnetic valve 14b open, helium atmosphere in carrier gas bottle 18 becomes high-purity helium of 99.9999% after gas purifier 17 purifies, high-purity helium is leaded up to magnetic valve 14a two six logical film valves 10 and multithread road selective membrane valve 13 is purged, one tunnel enters chromatographic column 24a and PDHID detector 24b by 4 mouthfuls and 1 mouthful of two six logical film valves 10 successively as carrier gas, and be discharged in the body of cabin by magnetic valve 14b, the baseline stability of PDHID is in 2000 left and right. Certain density H in gas bottle 162、O2、N2、CH4Calibrating gas one tunnel directly passes into 4 mouthfuls of multithread road selective membrane valve 13, and a road is as driving the moving multithread of gas drive road selective membrane valve 13 to work.
2. clean: after system wake-up 2min, system stream is cleaned. Magnetic valve 7 is opened, multithread road selective membrane valve 13 switches makes C mouth be communicated with 3 mouthfuls, 3 mouthfuls by multithread road selective membrane valve 13 and C mouth, two six logical film valves 10 2 mouthfuls and quantitatively encircle 12 and 3 mouthfuls, gas storehouse 6 of two six logical film valves 10 successively of carrier gas, be drained into cabin body finally by magnetic valve 7, realized the cleaning in quantitative ring 12 and gas storehouse 6. The cleaning duration is 7min.
3. enter gas: multithread road selective membrane valve 13 switches makes C mouth be communicated with 4 mouthfuls, calibrating gas through gas bottle 16 out after, enter successively 4 mouthfuls of multithread road selective membrane valve 13 and C mouth, two six logical film valves 10 2 mouthfuls, quantitatively encircle 12 and 3 mouthfuls of two six logical film valves 10, gas storehouse 6 is discharged in the body of cabin by the first magnetic valve 7, makes quantitatively in ring, to be full of calibrating gas. Then shut electromagnetic valve 7.
4. Demarcate Gas: after above-mentioned flow process finishes, system switches to sample introduction test mode. Open the second magnetic valve 11, make the gas in gas bottle 16 be driven two six logical film valves 10, two six logical film valves 10 switch to 4 mouthfuls at once, quantitatively encircle 12,1 mouthfuls communicates, multithread road selective membrane valve 13C mouth and any a bite are obstructed, carrier gas flow through successively 4 mouthfuls of two six logical film valves 10, quantitatively encircle 12 and 1 mouthfuls, bring into and after chromatographic column 24a separates, enter pulse helium ionized detector PDHID24b and start to detect and analyze being stored in calibrating gas in quantitative ring 12, demarcate the parameter such as appearance time, peak area, peak height of each component gas.
5. standby. After demarcation flow process finishes, magnetic valve 1114a14b disconnects, and two six logical film valves 10 switch to quantitative ring 12 and communicate with 3 mouthfuls and 2 mouthfuls, open magnetic valve 7, and syringe pump resets. Finally, shut electromagnetic valve 7, system enters holding state. After 10min, system enters formal water sample testing process.
II. water sample test
1. system is carried out above-mentioned waking up and cleaning process.
2. extract film divided gas flow: magnetic valve 7 cuts out, in seawater auto injection and gas film extraction unit, water pump 3 starts, and seawater is drawn into seawater sample storehouse 2 from water inflow filter 1, then discharges from going out water filter 4. After 2min, water pump 3 quits work, the end of drawing water. Gas in 2 water bodys of seawater sample storehouse can enter through semipermeable membrane the gas warehousing storage of opposite side, waits for 2min, makes the abundant balance of gas of pellicle both sides. Subsequently, multithread road selective membrane valve 13 switches C mouth and communicates with 2 mouthfuls, syringe pump 19 extracts gas in gas storehouse, gas from gas storehouse 6 successively through 3 mouthfuls of two six logical film valves 10, quantitatively encircle 12 and 2 mouthfuls, the C mouth of multithread road selective membrane valve 13 and 2 mouthfuls and enter syringe pump 19, make quantitatively in ring 12, to be full of the gas extracting from seawater.
3. test: after having sampled, system switches to sample introduction test mode. Open the second magnetic valve 11, make the gas in gas bottle 16 be driven two six logical film valves, two six logical film valves 10 switch to 4 mouthfuls at once, quantitatively encircle 12,1 mouthfuls communicates, multithread road selective membrane valve 13C mouth and any a bite are obstructed, carrier gas flow through successively 4 mouthfuls of two six logical film valves 10, quantitatively encircle 12,1 mouthfuls, bring into after chromatographic column 24a separates and enter in pulse helium ionized detector PDHID24b being stored in gas in quantitative ring, start to detect and analyze, and testing result is shown in to display screen. H in the pond water body that Fig. 3 records for PDHID2、O2、N2、CH4The test spectrogram of four kinds of gases.
4. standby: after testing process finishes, the second magnetic valve 11, the 3rd magnetic valve 14a and the 4th magnetic valve 14b disconnect, two six logical film valves switch to quantitative ring and communicate with 3 mouthfuls and 2 mouthfuls, open the first magnetic valve 7, and syringe pump 19 resets. Finally, close the first magnetic valve 7, system enters holding state. After 10min, system enters next water sample test loop.
Claims (5)
1. can realize H in seawater for one kind2、CH4Deng the gas chromatography system under water of gas in-situ test, it is characterized in that comprising that seawater auto injection and gas film extraction unit, multicomponent gas detect and self-correcting unit and waste heat recovery unit automatically, wherein: multicomponent gas automatically detects and self-correcting unit, waste heat recovery unit are all packaged in high pressure sealing instrument room, and seawater auto injection and gas film extraction unit are installed on instrument room end cap;
Seawater auto injection and gas film extraction unit by water inflow filter (1), film sampling device, water pump (3), go out water filter (4) and form, in film sampling device, be provided with seawater sample storehouse (2) and gas storehouse (6), between seawater sample storehouse (2) and gas storehouse (6), pellicle (5) is set, the film that described pellicle (5) is permeable watertight, by withstand voltage encapsulation, can automatically the gas separation and Extraction in seawater sample storehouse (2) be arrived in gas storehouse (6); Water inflow filter (1) connects seawater sample storehouse (2) by pipeline, and seawater sample storehouse (2) are connected water filter (4) by pipeline with water pump (3);
Multicomponent gas automatically detects and self-correcting unit comprises sample introduction module, chromatographic column and post case (24a), pulse helium ionized detector (24b), pressure-reducing valve (15), gas bottle (16), gas purifier (17) and carrier gas bottle (18), wherein: sample introduction module is made up of the first magnetic valve (7), anti-drip valve (8), water leakage detection sensor (9), syringe pump (19), two six logical film valves (10), quantitatively ring (12) and multithread road selective membrane valves (13), gas storehouse (6) is connected water leakage detection sensor (9) by pipeline with anti-drip valve (8), water leakage detection sensor (9) connects 3 mouthfuls of two six logical film valves (10) by pipeline, 2 mouthfuls of two six logical film valves (10) connect the C mouth of multithread road selective membrane valve (13) by pipeline, 1 mouthful of two six logical film valves (10) connects chromatographic column and post case (24a) by pipeline, 4 mouthfuls of two six logical film valves (10) connect gas purifier (17) by pipeline, gas purifier (17) is connected carrier gas bottle (18) with valve by pipeline, two six logical film valves (10) are connected gas bottle (16) by the second magnetic valve (11), pressure-reducing valve (15) successively with pipeline, 4 mouthfuls of multithread road selective membrane valve (13) are connected gas bottle (16) by pipeline with pressure-reducing valve (15) with pipeline, 2 mouthfuls of multithread road selective membrane valve (13) connect syringe pump (19) by pipeline, 3 mouthfuls of multithread road selective membrane valve (13) connect gas purifier (17) by pipeline, the P mouth of multithread road selective membrane valve (13) connects two six logical film valves (10) by pipeline, and quantitatively ring (12) is positioned on two six logical film valves (10), pulse helium ionized detector (24b) connects the 4th magnetic valve (14b),
Waste heat recovery unit is by waste gas pump (20a), pressure sensor (20b), the first two two-port valves (21a), the second two two-port valves (21b), check valve (22) and waste gas bottle (23) composition, pressure sensor (20b) connects waste gas pump (20) a, the gas outlet of waste gas pump (20) a is divided into two-way, the pipeline of leading up to connects the first two two-port valves (21a), the pipeline of separately leading up to connects the second two two-port valves (21b), the second two two-port valves (21b) are connected waste gas bottle (23) by check valve (22) with pipeline,
The first magnetic valve (7), anti-drip valve (8), water leakage detection sensor (9), two six logical film valves (10), the second magnetic valve (11), quantitatively ring (12), multithread road selective membrane valve (13), the 3rd magnetic valve, the 4th magnetic valve, pressure-reducing valve (15), gas bottle (16), gas purifier (17), carrier gas bottle (18), syringe pump (19), waste gas pump (20a), pressure sensor (20b), the first two two-port valves (21a), the second two two-port valves (21b), check valve (22), waste gas bottle (23), chromatographic column and post case (24a), pulse helium ionized detector (24b) connects respectively central control unit (25).
2. one according to claim 1 can realize H in seawater2、CH4Deng the gas chromatography system under water of gas in-situ test, it is characterized in that carrier gas is high-purity helium, from carrier gas bottle (18) gas coming through gas purifier (17), obtain high-purity helium of 99.9999%; Gas bottle spirit is high-purity helium, and certain density H is provided2、CH4Standard mixture.
3. one according to claim 1 can realize H in seawater2、CH4Deng the gas chromatography system under water of gas in-situ test, it is characterized in that for preventing that the gas in environment from polluting film valve, two six logical film valves (10) and multithread road selective membrane valve (13) are the film valve of band from purging function, sweep gas is high-purity helium of 99.9999%, and driving gas is the calibrating gas in gas bottle.
4. one according to claim 1 can realize H in seawater2、CH4Deng the gas chromatography system under water of gas in-situ test, leak once it is characterized in that water leakage detection sensor (9) detects, stop valve (8), at once in off-state, prevents that seawater is leaked into instrument room; In wakeup process, system detects hypertonia, and waste gas pump (20a) is worked immediately, and waste gas is retracted in waste gas bottle (23).
5. the method for operating of a gas chromatography system under water as claimed in claim 1 system after power supply energising, it is characterized in that when system is during in holding state, 5A molecular sieve column (24a) flow is 50ml/min, 30 DEG C/min is warming up to 180 DEG C, keep 2 hours, be down to 60 DEG C, remain unchanged, PDHID (24b) is warmed up to rapidly 150 DEG C, remains unchanged; Specific works flow process comprises: 1. wake up, 2. clean, 3. marked gas or extract film divided gas flow, 4. test, 5. self-correcting, 6. standby;
1. wake up: waken system, pressure sensor (20b) detects environmental pressure, when higher than 1.2bar, waste gas pump (20a) startup work, the first two two-port valves (21a) are opened, to release the pressure, waste gas pump (20a) is started the impact of moment, subsequently, close the first two two-port valves (21a), open the second two two-port valves (21b), waste gas is by the second two two-port valves (21b) and check valve (22) discharge, enter in waste gas bottle (23), until cabin body internal pressure comes back to 1bar, waste gas pump (20a) quits work,
After system environments pressure detecting is normal, the 3rd magnetic valve (14a) and the 4th magnetic valve (14b) are opened, helium in carrier gas bottle (18) becomes high-purity helium of 99.9999% after gas purifier (17) purifies, high-purity helium is divided into two-way: the magnetic valve (14a) of leading up to purges two six logical film valves (10) and multithread road selective membrane valve (13), another road enters chromatographic column (24a) and PDHID detector (24b) by 4 mouthfuls and 1 mouthful of two six logical film valves (10) successively successively as carrier gas, and be discharged in the body of cabin by the 4th magnetic valve (14b), calibrating gas in gas bottle (16) is divided into two kinds: a road directly passes into 4 mouthfuls of multithread road selective membrane valve (13), and another road is as driving moving multithread road selective membrane valve (13) work of gas drive,
2. clean: system stream is cleaned, the first magnetic valve (7) is opened, multithread road selective membrane valve (13) switches makes its C mouth be communicated with 3 mouthfuls, 3 mouthfuls by multithread road selective membrane valve (13) and C mouth, two six logical film valves (10) 2 mouthfuls successively of carrier gas, quantitatively ring (12), two six logical film valves (10) 3 mouthfuls, gas storehouse (6), be discharged in the body of cabin finally by the first magnetic valve (7), realize the quantitatively cleaning of ring (12) and gas storehouse (6);
3. marked gas or extraction film divided gas flow: after system stream has cleaned, can enter as required marked gas flow process or extract film divided gas flow flow process;
If enter marked gas flow process, multithread road selective membrane valve (13) switches makes C mouth be communicated with 4 mouthfuls, calibrating gas through gas bottle (16) out after, enter successively 4 mouthfuls and C mouth of multithread road selective membrane valve (13), two six lead to 2 mouthfuls of film valves (10), quantitatively ring (12), two six lead to 3 mouthfuls of film valves (10), gas storehouse (6), be discharged in the body of cabin by magnetic valve (7), make quantitatively in ring, to be full of calibrating gas, then shut electromagnetic valve (7), system is carried out following testing process, carrier gas enters PDHID (24b) with the calibrating gas in quantitative ring (12) and detects after chromatographic column (24) a separates, determine H2、CH4Deng appearance time, peak height and the peak area of gas with various component, for detecting, the gasometry to be measured in later stage provides foundation;
If enter film separation and Extraction gas flow process, magnetic valve (7) cuts out, water pump (3) work in seawater auto injection and gas film extraction unit, seawater is drawn into seawater sample storehouse (2) from water inflow filter (1), then discharge from going out water filter (4), after end the balance of drawing water waits for a period of time, the gas in the water body of seawater sample storehouse (2) can enter through semipermeable membrane gas storehouse (6) storage of opposite side; Subsequently, multithread road selective membrane valve (13) switches C mouth and communicates with 2 mouthfuls, syringe pump (19) extracts gas in gas storehouse, gas enters syringe pump (19) through 3 mouthfuls of two six logical film valves (10), quantitatively ring (12), two six logical film valves (10) 2 mouthfuls, the C mouth of multithread road selective membrane valve (13) and 2 mouthfuls successively from gas storehouse (6), makes to be full of the gas extracting in quantitative ring (12) from seawater;
4. test: after above-mentioned flow process finishes, system switches to sample introduction test mode, open magnetic valve (11), make the calibrating gas in gas bottle (16) be driven two six logical film valve (10) work, two six logical film valves (10) switch at once 4 mouthfuls and 1 mouthful and communicate with quantitative ring (12), C mouth and any a bite of multithread road selective membrane valve (13) are obstructed, carrier gas is flowed through successively two six and is led to 4 mouthfuls of film valves (10), quantitatively ring (12), two six lead to 1 mouthful of film valves (10), bring into and after chromatographic column (24a) separates, enter pulse helium ionized detector PDHID (24b) and detect analysis being stored in gas in quantitative ring (12), and testing result is shown in to display screen,
5. self-correcting: system also has self-correcting function, can enter self-correcting flow process automatically according to setting in advance after the sample of the complete some of every detection; This flow process occur in stream clean finish after, by calibrating gas test compare realize self-correcting, concrete steps are consistent with marked gas flow process;
6. standby: after testing process finishes, the second magnetic valve (11), the 3rd magnetic valve (14) a and the 4th magnetic valve (14b) disconnect, two six logical film valves (10) switch to 3 mouthfuls and 2 mouthfuls and communicate with quantitative ring (12), open the first magnetic valve (7), syringe pump (19) resets; Finally, close the first magnetic valve (7), system enters holding state, waits for next circulation.
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