CN114965724A - Sulfide element content measuring device - Google Patents
Sulfide element content measuring device Download PDFInfo
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- CN114965724A CN114965724A CN202110218913.0A CN202110218913A CN114965724A CN 114965724 A CN114965724 A CN 114965724A CN 202110218913 A CN202110218913 A CN 202110218913A CN 114965724 A CN114965724 A CN 114965724A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/56—Packing methods or coating methods
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/60—Construction of the column
- G01N30/6052—Construction of the column body
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/201—Injection using a sampling valve multiport valves, i.e. having more than two ports
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/56—Packing methods or coating methods
- G01N2030/562—Packing methods or coating methods packing
Abstract
The invention relates to the field of analytical chemistry, and provides a sulfide element content measuring device, which comprises: a dosing container; the chromatographic column is provided with a chromatographic column inlet and a chromatographic column outlet and is filled with a chromatographic column filler; a carrier gas supply unit; a detector; the multi-way valve is respectively communicated with the first opening, the second opening, the chromatographic column inlet, the chromatographic column outlet, the carrier gas supply part and the detector to form at least two switchable first gas flow paths and second gas flow paths, wherein the first gas flow paths are formed by sequentially communicating the carrier gas supply part, the quantitative container, the chromatographic column inlet, the chromatographic column outlet and the detector; the second gas flow path is formed by communicating a carrier gas supply part, a chromatographic column outlet, a chromatographic column inlet and a detector in sequence. By means of forward separation and back flushing of the chromatographic column, the sulfide element content measuring device provided by the invention can rapidly, accurately and stably measure the sulfide element content.
Description
Technical Field
The invention relates to the field of analytical chemistry, in particular to a sulfide element content measuring device.
Background
How to accurately measure the content of a specific element in a mixture gas is an important problem facing the chemical industry at present. For example, natural gas is a cleaner energy source than crude oil, but sulfur impurities contained in natural gas corrode pipelines in the process of conveying natural gas and affect the service life of a catalyst used when natural gas is used as a raw material to produce other compounds, so how to accurately measure the content of sulfur in natural gas is an important issue to be solved.
However, methane, which is a main component of natural gas, can be an interference gas for sulfur content measurement, and especially can cause quenching effect on a Flame Photometric Detector (FPD) which is generally used for measurement. Specifically, if the combustion gas introduced into the FPD contains both methane and a sulfide component, the peak intensity of the sulfide component is greatly reduced or even becomes negative, which may ultimately seriously affect the accuracy of the elemental sulfur content measurement.
One prior art device for measuring the content of elemental sulfur in natural gas is to measure the sulfide content of natural gas, such as hydrogen sulfide (H) 2 S), carbonyl sulfide (COS), methyl mercaptan, etc. are separated from methane by chromatographic column, and the sulfur content of each sulfide is added to obtain the total sulfur content. The main problem with this measurement method is that the time required to separate the individual sulphide components is long, typically requiring more than 30 minutes, which will seriously affect the efficiency of the measurement.
Another prior art device uses a specific type of detector, such as a Sulfur Chemiluminescence Detector (SCD) that does not create methane quenching problems. However, SCDs require frequent maintenance due to stability problems and are difficult to popularize and use on a large scale.
Therefore, how to provide a sulfide element content measuring device capable of rapidly, accurately and stably measuring the sulfide element content is a technical problem to be solved in the field.
Disclosure of Invention
In order to quickly, accurately and stably measure the content of the sulfide element, the invention provides a sulfide element content measuring device which can solve the problems in the prior art.
The sulfide element content measuring device provided by the invention is used for measuring the content of an element to be measured in sample gas, and comprises:
a quantitative container having a first opening and a second opening and collecting a sample gas;
the chromatographic column comprises a chromatographic column inlet and a chromatographic column outlet, wherein a chromatographic column filler is filled in the chromatographic column, the chromatographic column filler can separate a first gas to be detected and an interference gas contained in a sample gas, and the flow rate of a second gas to be detected contained in the sample gas in the chromatographic column filler is lower than that of the first gas to be detected and the interference gas;
a carrier gas supply unit;
a detector;
a multi-way valve which is respectively communicated with the first opening, the second opening, the quantitative container, the chromatographic column inlet, the chromatographic column outlet, the carrier gas supply part and the detector, and forms a first gas flow path and a second gas flow path which can be switched, wherein,
the first gas flow path is formed by communicating a carrier gas supply part, a quantitative container, a chromatographic column inlet, a chromatographic column outlet and a detector in sequence;
the second gas flow path is formed by communicating a carrier gas supply part, a chromatographic column outlet, a chromatographic column inlet and a detector in sequence.
Since the first gas flow path is formed by communicating the carrier gas supply portion, the quantitative container, the column inlet, the column outlet and the detector in this order, the carrier gas blown out from the carrier gas supply portion can be blown into the column in the forward direction with the sample gas in the quantitative container. Because the retention capacity of the chromatographic column filler on the second gas to be detected is stronger than that of the first gas to be detected and the interference gas, the first gas to be detected and the interference gas blow out of the chromatographic column from the outlet of the chromatographic column before the second gas to be detected, and are carried into the detector by the carrier gas for analysis. Because the chromatographic column filler can separate the first gas to be detected and the interference gas contained in the sample gas, and the time periods of the first gas to be detected and the interference gas entering the detector are different, the interference gas does not interfere with the peak intensity of the first gas to be detected (for example, methane does not quench the peak intensity of hydrogen sulfide), and the accuracy of measurement can be guaranteed.
Since the second gas flow path is formed by communicating the carrier gas supply section, the column outlet, the column inlet, and the detector in this order, when the second gas flow path is switched to conduction, the carrier gas blown out by the carrier gas supply section can blow out the second gas to be measured remaining in the column in the reverse direction. With the arrangement, the second gas to be measured (for example, a high-boiling-point component with strong holding capacity in the chromatographic column) can be blown out to the detector in a reverse direction for detection without waiting for the second gas to be measured to run out of the whole chromatographic column, so that the measurement efficiency is improved.
In addition, the sulfide element content measuring device provided by the invention can reduce or even avoid the negative influence of interference gas, so that the types of usable detectors are expanded. Even if a detector such as an FPD which is excellent in stability but is susceptible to quenching is used, the measurement result can be obtained accurately.
In conclusion, the sulfide element content measuring device provided by the invention can rapidly, accurately and stably measure the sulfide element content.
In a preferred embodiment of the present invention, the apparatus further comprises a control device that controls the multi-way valve to switch from the first gas flow path to the second gas flow path when the first gas flow path is on, the first measurement gas and the interference gas flow from the chromatography column into the detector, and the second measurement gas is retained in the chromatography column.
In the sulfide element content measuring device provided by the invention, if the flow path is switched too early, the first gas to be measured and the interference gas cannot be completely separated or are partially left in the chromatographic column, so that the measuring result has deviation; if the flow path is switched too late, the time required for measurement increases. According to the preferred technical scheme, the control device for automatically switching the flow path is arranged, so that the switching time of the flow path can be accurately controlled according to the signal response of the detector, and the problem that the switching time of the flow path is difficult to accurately grasp is effectively solved.
In a preferred technical scheme of the invention, the multi-way valve is provided with at least 10 ports including a first port to a tenth port according to the sequence of adjacent end-to-end connection, and when the first gas flow path is communicated, the first port and the second port, the third port and the fourth port, the fifth port and the sixth port, the seventh port and the eighth port, and the ninth port and the tenth port are respectively communicated; when the second gas flow path is on, the first port and the tenth port, the second port and the third port, the fourth port and the fifth port, the sixth port and the seventh port, and the eighth port and the ninth port communicate with each other, respectively.
The multi-way valve with the structure of at least 10 ports is adjacent to each other in an end-to-end sequence, can reliably realize the flow path connection and switching functions of the first gas flow path and the second gas flow path, comprises a collecting and blowing flow path for sample gas in a quantitative container, a flow path for carrying the sample gas to pass through a chromatographic column in a forward direction, a flow path for back-blowing the chromatographic column to enter a detector and the like, and can ensure that the whole structure of the flow path with the functions is not excessively complicated.
In a preferred technical scheme of the invention, a first opening and a second opening of the quantitative container are respectively communicated with a first port and an eighth port of the multi-way valve; the element content measuring device also comprises a sample gas inlet and a sample gas outlet, wherein the sample gas inlet is communicated with the tenth port of the multi-way valve, and the sample gas outlet is communicated with the ninth port of the multi-way valve.
When the second gas flow path is communicated, the tenth port is communicated with the first port, the eighth port is communicated with the ninth port, the sample gas sequentially flows through the tenth port, the first port, the quantitative container, the eighth port and the ninth port and finally flows out from the sample gas outlet, and sampling operation can be performed, so that the quantitative container collects the sample gas with determined volume; when the first gas flow path is conducted, the ninth port is communicated with the tenth port, and the sample gas flows in from the tenth port and then directly flows out from the ninth port without sampling. By switching the multi-way valve, the sampling operation can be intermittently performed, the long-term contact between the internal elements of the equipment and the sample gas is avoided, and the service life of the equipment is prolonged.
In a preferred embodiment of the present invention, the carrier gas supply portion is communicated with a seventh port of the multi-way valve; the chromatographic column inlet of the chromatographic column is communicated with the second port of the multi-way valve; a chromatographic column outlet of the chromatographic column is communicated with a sixth port of the multi-way valve; the detector is communicated with a third port of the multi-way valve through a first pipeline; the detector is also in communication with a fifth port of the multi-way valve via a second conduit.
In a preferred embodiment of the present invention, the carrier gas supply unit is further communicated with the fourth port via a third line.
In the process of switching from the conduction of the first gas flow path to the conduction of the second gas flow path, part of gas containing the element to be measured may remain in the second pipeline, because the carrier gas supply part is communicated with the fourth port, the fourth port is communicated with the fifth port, the fifth port is communicated with the detector, and the carrier gas can continuously blow out the gas remained in the second pipeline when the first gas flow path is conducted through the flow path, so that the problem of inaccurate measurement caused by too long gas flow path of the second pipeline and more residues is avoided. Similarly, in the process of switching from the conduction of the second gas flow path to the conduction of the first gas flow path, the residue in the first pipeline can be blown out, and the measurement accuracy is improved.
In a preferred embodiment of the present invention, the device for measuring elemental sulfide content further includes a pressure balancing device disposed in a flow path through which the sample gas inlet communicates with the tenth port of the multi-way valve.
By adding a pressure balance device in the flow path where the sample gas inlet communicates with the tenth port, the quantitative performance of the quantitative container can be improved, and the consistency of the molar quantity of the sample gas in each measurement can be improved.
In a preferred technical scheme of the invention, the filler of the chromatographic column is divinylbenzene-ethylene glycol dimethacrylate polymer (or similar filler), and the length of the chromatographic column is less than 1.2 meters. The divinyl benzene-ethylene glycol dimethacrylate polymer or similar filler is used as the filler of the chromatographic column, the length of the chromatographic column can be shortened to be within 1.2 m, so that the passing time of the first gas to be detected and the interfering gas is greatly shortened, the time required by measurement is effectively shortened, and the detection efficiency is improved. In addition, the volume of the device can be effectively reduced, which is beneficial to the miniaturization of equipment.
In the preferred technical scheme of the invention, the first gas to be detected is hydrogen sulfide gas, the second gas to be detected is sulfide gas with a boiling point higher than that of the hydrogen sulfide gas, the interference gas is methane gas, the sample gas is natural gas, and the detector is a flame photometric detector. The sulfide element content measuring device provided by the better technical scheme can effectively improve the measuring efficiency and accuracy of the flame photometric detector during the total sulfur analysis of natural gas, and reduce the influence of methane on the quenching effect of the flame photometric detector on the total sulfur analysis.
Drawings
Fig. 1 is a schematic structural view of a sulfide element content measuring apparatus according to an embodiment of the present invention.
Fig. 2 is a schematic view of a flow path structure of the sulfide element content measuring apparatus according to the embodiment of the present invention in a standby state.
Fig. 3 is a schematic view of a flow path structure when a sampling step is performed by the elemental sulfide content measuring apparatus according to the embodiment of the present invention.
Fig. 4 is a schematic view of a flow path structure when a chromatographic separation step is performed by the elemental sulfide content measuring apparatus according to the embodiment of the present invention.
Fig. 5 is an analysis result of natural gas in the embodiment of the present invention.
Fig. 6 is a schematic view of a flow path structure when the sulfide element content measuring apparatus provided in the embodiment of the present invention performs a back-flushing step.
Reference numerals
1 first port
2 second port
3 third port
4 fourth port
5 fifth port
6 sixth port
7 seventh port
8 eighth port
9 ninth port
10 tenth port
11 quantitative container
110 first opening
111 second opening
12 chromatographic column
Inlet of 120 chromatographic column
121 chromatography column outlet
13 carrier gas supply part
14 detector
15 pressure balancing device
16 sample gas inlet
17 sample gas outlet
18 first pipeline
19 second pipeline
20 third pipeline
21 six-way valve
22 ten-way valve
23 first gas flow path
24 second gas flow path
25 first gas to be measured
26 second gas to be measured
27 interfering gas
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present embodiment provides a sulfide element content measuring device for measuring the total content of sulfur elements in natural gas, which uses an FPD as a detector 14, and natural gas as a sample gas contains at least low-boiling sulfide gas such as hydrogen sulfide gas, main component methane gas, and high-boiling sulfide gas such as carbonyl sulfide and methyl mercaptan. Among them, the low boiling point sulfide gas hydrogen sulfide is the first gas to be detected 25 in the present embodiment; the methane gas, which causes a quenching effect on the detection of the sulfur element of the FPD, is the interfering gas 27 in the present embodiment; the high-boiling sulfide gas is the second gas to be measured 26 in the present embodiment; the carrier gas is an inert gas such as nitrogen or helium.
Fig. 1 is a schematic structural diagram of a sulfide element content measuring apparatus according to an embodiment of the present invention. In the present embodiment, the multi-way valve is a ten-way valve 22 having 10 ports including a first port 1 to a tenth port 10 in the order of being adjacent to each other end to end.
The ten-way valve 22 can be switched between two different communication states to form two switchable gas flow paths, i.e., a first gas flow path 23 and a second gas flow path 24, respectively. When the first gas flow path 23 is conducted, the first port 1 and the second port 2, the third port 3 and the fourth port 4, the fifth port 5 and the sixth port 6, the seventh port 7 and the eighth port 8, and the ninth port 9 and the tenth port 10 are communicated with each other, and the ten-way valve 22 is in a first communication state; when the second gas flow path 24 is communicated, the first port 1 and the tenth port 10, the second port 2 and the third port 3, the fourth port 4 and the fifth port 5, the sixth port 6 and the seventh port 7, and the eighth port 8 and the ninth port 9 are communicated with each other, and the ten-way valve 22 is in the second communication state.
Referring to fig. 1, a dosing container 11, for example a dosing ring, has a first opening 110 and a second opening 111 communicating with the first port 1 and the eighth port 8, respectively, of the multi-way valve; the sulfide element content measuring device further comprises a sample gas inlet 16 and a sample gas outlet 17, wherein the sample gas inlet 16 is communicated with the tenth port 10 of the multi-way valve through a pressure balancing device 15, and the sample gas outlet 17 is communicated with the ninth port 9 of the multi-way valve; the column inlet 120 of the chromatography column 12 communicates with the second port 2 of the multi-way valve; the column outlet 121 of the chromatography column 12 communicates with the sixth port 6 of the multi-way valve; the detector 14 communicates with the third port 3 of the multi-way valve via a first conduit 18; the detector 14 also communicates with the fifth port 5 of the multi-way valve via a second line 19; the carrier gas supply portion 13 communicates with the seventh port 7 of the multi-way valve and also communicates with the fourth port 4 of the multi-way valve via a third line 20.
Fig. 2 is a schematic view of a flow path structure of the sulfide element content measuring apparatus according to the present embodiment in a standby state. Referring to fig. 2, in the standby state, the carrier gas supply section 13 is closed, the ten-way valve 22 is switched to the first communication state, and the sample gas flows in from the sample gas inlet 16, passes through the tenth port 10 and the ninth port 9, and then flows out from the sample gas outlet 17.
Fig. 3 is a schematic view of a flow path structure when the sulfide element content measuring apparatus according to the present embodiment performs a sampling step.
Referring to fig. 3, in performing the sampling step, the ten-way valve 22 is switched to the second communication state. The sample gas flows in from the sample gas inlet 16, passes through the pressure equalizer 15, the tenth port 10, the first port 1, the first opening 110 of the quantitative container 11, the second opening 111 of the quantitative container 11, the eighth port 8, and the ninth port 9 in this order, and finally flows out from the sample gas outlet 17.
After the sample gas is introduced for a predetermined time, it is estimated that the gas in the quantitative container 11 has been completely replaced with the sample gas, and a certain volume of the sample gas corresponding to the volume of the quantitative container 11 is stored therein. Since the pressure balance device 15 is additionally provided in the flow path where the sample gas inlet 16 communicates with the tenth port 10, the quantitative performance of the quantitative container 11 can be further improved in the case where both the volume and the pressure are determinable, to ensure the consistency of the molar amount of the sample gas at each measurement.
Referring to fig. 2 and 3, by switching the ten-way valve 22 between the first communication state and the second communication state, the sampling operation can be performed intermittently, the long-term contact between the internal components of the apparatus and the sample gas is avoided, and the service life of the apparatus is prolonged.
Fig. 4 is a schematic view of the flow path structure when the apparatus for measuring the elemental sulfide content according to the present embodiment performs a chromatographic separation step.
Referring to fig. 4, in the chromatographic separation step, the carrier gas supply section 13 is turned on, the ten-way valve 22 is switched to the first communication state, and the ten-way valve switched to the first communication state can conduct the first gas flow path 23.
When the first gas flow path 23 is turned on, the carrier gas supply unit 13 communicates with the seventh port 7 of the multi-way valve, the seventh port 7 communicates with the eighth port 8, the eighth port 8 communicates with the second opening 111 of the quantitative container 11, the first opening 110 of the quantitative container 11 communicates with the first port 1, the first port 1 communicates with the second port 2, the second port 2 communicates with the column inlet 120, the column outlet 121 communicates with the sixth port 6, the sixth port 6 communicates with the fifth port 5, and the fifth port 5 communicates with the detector 14 via the second conduit 19, so that the carrier gas can carry the sample gas in the forward direction into the column 12, and the first gas to be measured 25 and the interfering gas 27 separated from the column 12 are introduced into the detector 14 for measurement. Because the first gas to be measured 25 and the interfering gas 27 are separated and then introduced into the detector 14 at intervals, interference on the measurement result caused when the interfering gas 27 and the first gas to be measured 25 are simultaneously introduced into the detector 14 can be avoided, so that the content of the sulfur element contributed by the first gas to be measured can be separately measured.
Specifically, fig. 5 shows the results of the analysis of the natural gas in the present embodiment, and the abscissa of fig. 5 represents time and the ordinate represents the normalized intensity value. Referring to fig. 5, in the chromatographic separation step, the methane and the hydrogen sulfide gas are respectively introduced into the detector 14 to generate peaks in different time periods, the quenching peak of the methane and the position of the generated peak of the hydrogen sulfide are separated from each other, and the influence of the quenching peak is shielded only in the processes of calculating and leveling the baseline, so that a more accurate measurement result can be obtained.
Although methane appears to peak before hydrogen sulfide in this embodiment, hydrogen sulfide may appear to peak before methane in other embodiments of the present invention, as long as the peak locations of the two are clearly separated from each other and the influence of the quenching peak can be shielded. The above should not be excluded from the scope of the present invention without departing from the gist of the present invention.
Fig. 6 is a schematic view of a flow path structure when the apparatus for measuring a content of a sulfide element performs a blowback step according to the embodiment.
Referring to fig. 6, when the back flushing step is performed, the ten-way valve 22 is switched to the second communication state, and the ten-way valve switched to the second communication state can conduct the second gas flow path 24.
When the second gas flow path 24 is turned on, the carrier gas supply unit 13 communicates with the seventh port 7 of the multi-way valve, the seventh port 7 communicates with the sixth port 6, the sixth port 6 communicates with the column outlet 121, the column inlet 120 communicates with the second port 2, the second port 2 communicates with the third port 3, and the third port 3 communicates with the detector 14 via the first pipeline 18, so that the carrier gas can reversely blow out the second gas to be measured 26 retained in the column 12, and the second gas to be measured 26 is introduced into the detector 14 for detection, and the element content contributed by the second gas to be measured 26 is measured. The peak position of the second gas under test 26, i.e., high boiling sulfide, is shown in fig. 5.
Then, by superimposing the element contents of the first gas to be measured 25 and the second gas to be measured 26, the total content of the element to be measured in the sample gas can be calculated, and a reliable and accurate measurement result can be obtained. Moreover, because the mode of reversely blowing the second gas to be detected 26 is adopted in the embodiment, the second gas to be detected 26 does not need to run the whole course of the chromatographic column forward, and the problem that the duration of the sample gas analysis is too long due to too slow passing rate of part of types of second gas to be detected 26, such as high-boiling sulfide, is avoided.
In the present embodiment, the ten-way valve 22 is used as the flow path switching mechanism, so that the flow path connection and switching functions of the first gas flow path 23 and the second gas flow path 24, including the collection and blowing flow path of the sample gas in the quantitative container 11, the flow path for carrying the sample gas in the forward direction through the column 12, the flow path for blowing the column 12 back into the detector 14, and the like, can be realized with high reliability, and the overall structure of the flow path having the above functions can be made not to be excessively complicated.
In addition, in the process of switching from the conduction of the first gas flow path 23 to the conduction of the second gas flow path 24, a part of the gas containing the element to be measured (for example, the first gas to be measured 25 or the second gas to be measured 26) may remain in the second pipeline 19, because the carrier gas supply part 13 is communicated with the fourth port 4, the fourth port 4 is communicated with the fifth port 5, and the fifth port 5 is communicated with the detector 14, the carrier gas can continuously blow out the gas remaining in the second pipeline 19 when the first gas flow path 23 is conducted through the above path, thereby avoiding the problem of inaccurate measurement caused by too long gas flow path and more residues of the second pipeline 19. Similarly, in the process of switching from the conduction of the second gas flow path 24 to the conduction of the first gas flow path 23, the residue in the first pipeline 18 can be blown out, and the measurement accuracy can be improved.
In this embodiment, the packing material of the chromatographic column is divinylbenzene-ethylene glycol dimethacrylate polymer or the like, and the length of the chromatographic column 12 is less than 1.2 m. The divinyl benzene-ethylene glycol dimethacrylate polymer or similar filler is used as the filler of the chromatographic column, the length of the chromatographic column can be shortened to be within 1.2 m, so that the passing time of the first gas to be detected 25 and the interference gas 27 is greatly shortened, the time required by measurement is effectively shortened, and the detection efficiency is improved. In addition, the volume of the device can be effectively reduced, which is beneficial to the miniaturization of equipment.
In the above embodiment of the present invention, the measuring device for measuring the content of elemental sulfide may further include a control device (not shown), and the control device (not shown) is in communication with both the multi-way valve and the detector 14. When the first gas flow path 23 is conducting, the first gas to be measured 25 and the interfering gas 27 are blown from the chromatography column 12 into the detector 14, and the second gas to be measured 26 is retained in the chromatography column 12, the control device (not shown) controls the multi-way valve to switch from the first gas flow path 23 conducting to the second gas flow path 24 conducting.
In the above embodiment, the timing of switching the flow paths needs to be accurately controlled, and if the flow path switching is too early, the first gas to be measured 25 and the interfering gas 27 cannot be completely separated or partially remain in the chromatographic column 12, resulting in deviation of the measurement result; if the flow path is switched too late, the time required for measurement increases. According to the above preferred embodiment, by providing the control device (not shown) for automatically switching the flow path, the timing of switching the flow path can be accurately controlled according to the signal response of the detector 14, thereby effectively solving the problem that the timing of switching the flow path is difficult to accurately grasp.
So far, the technical scheme of the invention has been described with reference to the attached drawings. However, it will be readily appreciated by those skilled in the art that the scope of the present invention is obviously not limited to the specific embodiments described above. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.
Claims (11)
1. A sulfide element content measuring apparatus for measuring a content of an element to be measured in a sample gas, the sulfide element content measuring apparatus comprising:
a quantitative container having a first opening and a second opening, for collecting a sample gas;
the chromatographic column is provided with a chromatographic column inlet and a chromatographic column outlet, and is filled with a chromatographic column filling material, the chromatographic column filling material can separate a first gas to be detected and an interference gas contained in the sample gas, and the flow rate of a second gas to be detected contained in the sample gas in the chromatographic column filling material is lower than that of the first gas to be detected and the interference gas;
a carrier gas supply unit;
a detector;
a multi-way valve which is communicated with the first opening, the second opening, the quantitative container, the chromatographic column inlet, the chromatographic column outlet, the carrier gas supply unit, and the detector to form a first gas flow path and a second gas flow path which can be switched,
the first gas flow path is formed by communicating the carrier gas supply unit, the quantitative container, the column inlet, the column outlet, and the detector in this order;
the second gas channel is formed by communicating the carrier gas supply unit, the column outlet, the column inlet, and the detector in this order.
2. The elemental sulfide content measuring apparatus according to claim 1, further comprising a control device that controls the multi-way valve to switch from the first gas flow path to the second gas flow path when the first gas flow path is on, the first gas to be measured and the interference gas flow from the chromatography column into the detector, and the second gas to be measured is retained in the chromatography column.
3. The elemental sulfide content measuring apparatus according to claim 1 or 2, wherein the multi-way valve has at least 10 ports including a first port to a tenth port in an order of being adjacent to each other end to end,
when the first gas flow path is conducted, the first port and the second port, the third port and the fourth port, the fifth port and the sixth port, the seventh port and the eighth port, and the ninth port and the tenth port are respectively communicated;
when the second gas flow path is on, the first port and the tenth port, the second port and the third port, the fourth port and the fifth port, the sixth port and the seventh port, and the eighth port and the ninth port communicate with each other, respectively.
4. The elemental sulfide content measuring apparatus according to claim 3,
the first opening and the second opening of the quantitative container are respectively communicated with the first port and the eighth port of the multi-way valve;
the sulfide element content measuring device further comprises a sample gas inlet and a sample gas outlet, the sample gas inlet is communicated with the tenth port of the multi-way valve, and the sample gas outlet is communicated with the ninth port of the multi-way valve.
5. The elemental sulfide content measuring apparatus according to claim 4,
the carrier gas supply part is communicated with a seventh port of the multi-way valve;
the column inlet of the chromatography column is in communication with a second port of the multi-way valve;
the chromatography column outlet of the chromatography column is in communication with a sixth port of the multi-way valve;
the detector is communicated with a third port of the multi-way valve through a first pipeline;
the detector is also in communication with a fifth port of the multi-way valve via a second conduit.
6. The elemental sulfide content measuring apparatus according to claim 5, wherein the carrier gas supply portion further communicates with a fourth port of the multi-way valve via a third line.
7. The elemental sulfide content measuring apparatus according to claim 4, further comprising a pressure equalizing device provided in a flow path in which the sample gas inlet communicates with the tenth port.
8. The elemental sulfide content measuring apparatus according to any one of claims 1 to 7, wherein the column packing is divinylbenzene-ethylene glycol dimethacrylate polymer.
9. The elemental sulfide content measuring apparatus according to claim 8, wherein the length of the chromatographic column is less than 1.2 m.
10. The elemental sulfide content measuring apparatus according to any one of claims 1 to 7, wherein the first gas to be measured is a hydrogen sulfide gas, the second gas to be measured is a sulfide gas having a boiling point higher than that of hydrogen sulfide, and the interfering gas is a methane gas.
11. The elemental sulfide content measuring apparatus according to claim 10, wherein the sample gas is natural gas and the detector is a flame photometric detector.
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