WO2022242669A1 - 一种天然气中含硫化合物含量的火焰光度在线检测的方法及系统 - Google Patents

一种天然气中含硫化合物含量的火焰光度在线检测的方法及系统 Download PDF

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WO2022242669A1
WO2022242669A1 PCT/CN2022/093508 CN2022093508W WO2022242669A1 WO 2022242669 A1 WO2022242669 A1 WO 2022242669A1 CN 2022093508 W CN2022093508 W CN 2022093508W WO 2022242669 A1 WO2022242669 A1 WO 2022242669A1
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sulfur
valve port
column
port
natural gas
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PCT/CN2022/093508
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English (en)
French (fr)
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沈琳
王晓琴
周理
李晓红
黄灵
陈正华
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中国石油天然气股份有限公司
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Priority to JP2023571872A priority Critical patent/JP2024519902A/ja
Priority to GB2319090.3A priority patent/GB2622511A/en
Priority to US18/561,850 priority patent/US20240241091A1/en
Priority to DE112022002640.5T priority patent/DE112022002640T5/de
Publication of WO2022242669A1 publication Critical patent/WO2022242669A1/zh

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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
    • 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
    • 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
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/22—Devices for withdrawing samples in the gaseous state
    • 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
    • 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
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/22—Fuels; Explosives
    • G01N33/225—Gaseous fuels, e.g. natural gas
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/22—Devices for withdrawing samples in the gaseous state
    • G01N2001/2285—Details of probe structures
    • 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
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/025—Gas chromatography
    • 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
    • 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
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8804—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 automated systems
    • 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
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
    • G01N2030/8854—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds involving hydrocarbons
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0047—Organic compounds

Definitions

  • the invention belongs to the technical field of natural gas detection, and in particular relates to a flame photometric online detection method and system for the content of sulfur-containing compounds in natural gas.
  • the total sulfur content of the purified gas in each purification plant ranges from 10mg/m 3 to 100mg/m 3 , and most of the H 2 S content is less than 6mg/m 3 .
  • the key to reducing the sulfur content is to reduce carbon dioxide, sulfur and content of mercaptans etc. Therefore, new requirements are put forward for the natural gas purification process, and at the same time, it must be accompanied by fast and accurate measurement methods.
  • the object of the present invention is to provide a flame photometric online detection system for the content of sulfur compounds in natural gas.
  • the system can quickly and effectively realize the on-line analysis and test of the content of at least 6 kinds of sulfur compounds in natural gas.
  • the present invention provides a flame photometric online detection system for the content of sulfur-containing compounds in natural gas, wherein the system includes:
  • the sampling device is used to obtain the natural gas to be analyzed in the natural gas pipeline online;
  • the flame photometric detector is used to burn each component delivered into the flame photometric detector, detect the light transmittance and convert it into an electrical signal to detect the content of sulfur compounds in the natural gas to be analyzed;
  • the chromatographic column system is provided with a carrier gas input pipeline and a chromatographic column is provided in the chromatographic column system, and the chromatographic column includes a boiling point column and a sulfur column (for example, consists of a boiling point column and a sulfur column);
  • the output port of the sampling device communicates with the input port of the decompression system through the first delivery pipeline, and the output port of the decompression system communicates with the input port of the boiling point column through a controllable on-off connection pipeline,
  • the input port of the boiling point column and the input port of the sulfur column are respectively communicated with the carrier gas input pipeline through a controllable connection pipeline, and the output port of the boiling point column is connected with the input port of the sulfur column through a controllable connection pipeline.
  • the on-off connection pipeline is connected, and the sulfur column output port is connected to the boiling point column input port through a controllable on-off connection pipeline, and the boiling point column output port and the sulfur column output port are respectively connected to the flame photometer
  • the input port of the detector is connected through a connection pipeline that can be controlled to be on or off.
  • the flame photometric online detection system for the content of sulfur-containing compounds in natural gas provided by the present invention is well suited for on-line analysis of the content of sulfur-containing compounds in natural gas pipelines, and can realize the content testing of at least six kinds of sulfur-containing compounds.
  • the flame photometric online detection system for the above-mentioned content of sulfur-containing compounds in natural gas provided by the present invention has the following beneficial effects:
  • the natural gas in the natural gas pipeline can be obtained in real time through the set sampling device, and transported to the decompression system, the pressure of the natural gas is reduced through the decompression system, thereby adjusting the flow rate of the natural gas, so that the natural gas enters the chromatographic column system
  • the flow rate is moderate, and the carrier gas is used to drive it to be separated in the chromatographic column.
  • the sulfur-containing compounds in natural gas can be separated better through the set sulfur column and boiling point column, and then the flame photometric detector is used to burn each component. , detect the light transmittance, and convert it into an electrical signal, so that the content of sulfur compounds in natural gas can be easily detected;
  • the separation of at least 6 different sulfur-containing compounds in natural gas can be realized more quickly and accurately, thereby improving the efficiency and accuracy of detection of sulfur-containing compounds in natural gas
  • the chromatographic separation characteristics based on different components in natural gas can be realized, so that some components in natural gas can be separated using a primary boiling point column and a primary sulfur column in turn , some components are separated by using two boiling point columns and one sulfur column, specifically using boiling point column, sulfur column and boiling point column in sequence, and some components are separated only by one boiling point column;
  • the detection cost of the enterprise can be reduced through this system, so that the enterprise can independently detect the sulfur compounds in the natural gas, and the detection is very convenient and efficient.
  • the sampling device includes a mounting base and a sampling probe, the sampling probe is fixedly connected to the mounting base, and the sampling probe is connected to the
  • the above-mentioned first delivery pipeline is connected; the sampling device can be fixed on the natural gas pipeline by installing the mounting base on the natural gas pipeline, so that the online acquisition of natural gas in the natural gas pipeline can be realized through the sampling probe placed in the natural gas pipeline.
  • the sampling probe is provided with a self-heating pressure reducer. This optimal technical scheme is more helpful for sampling the weather gas in the natural gas pipeline, and the sampling effect is good.
  • the first delivery pipeline is provided with a first valve, and the first delivery pipeline is opened or closed by the first valve.
  • a filter is provided in the first delivery pipeline.
  • the decompression system includes a primary decompression component and a secondary decompression component connected in sequence, and the input of the secondary decompression component
  • the port communicates with the output port of the primary decompression component through the second delivery pipeline;
  • the input port of the primary decompression component serves as the input port of the decompression system and the output port of the sampling device through the first A delivery pipeline communicates;
  • the output port of the secondary decompression component is used as the output port of the decompression system to communicate with the input port of the boiling point column through a controllable on-off connection pipeline;
  • the above preferred technical solution by setting the first-level decompression component and the second-level decompression component to decompress the natural gas to be analyzed, can be better suitable for online analysis of sulfur compounds in natural gas in natural gas pipelines, and realize the analysis of sulfur compounds obtained from natural gas pipelines. Precise control of natural gas pressure reduction, better adjustment of natural gas flow rate;
  • the primary decompression components include a primary decompression tank, a first heating membrane pressure reducer, a second heating membrane pressure reducer, a first pressure gauge and a second pressure gauge, the first The heating membrane pressure reducer, the second heating membrane pressure reducer, the first pressure gauge and the second pressure gauge are all arranged in the first-stage pressure reducing box; the first heating membrane pressure reducer A first communication pipe is provided between the pressure reducer and the second heating film pressure reducer, one end of the first communication pipe communicates with the output port of the first heating film pressure reducer, and the other end communicates with the output port of the first heating film pressure reducer.
  • the input port of the second heating membrane pressure reducer is communicated;
  • the first pressure gauge is installed on the first communication pipe and communicated with the first communication pipe;
  • the other end of the first delivery pipeline Penetrate into the primary decompression tank and communicate with the input port of the first heating film pressure reducer;
  • one end of the second delivery pipeline penetrates into the primary decompression tank and communicate with the input port of the first heating film pressure reducer;
  • the output port of the second heating membrane pressure reducer is connected, and the second pressure gauge is installed on the second delivery pipeline and communicated with the second delivery pipeline;
  • the primary decompression component It further includes a first-level insulation layer, and the first-level insulation layer is laid on the inner wall of the first-level decompression box;
  • the above preferred technical solution by setting the first heating membrane pressure reducer and the second heating membrane pressure reducer, forms a dual function, which makes the depressurization effect remarkable and efficient, and is more conducive to online analysis of sulfur in natural gas in natural gas pipelines Depressurization of natural gas during compounding process;
  • the secondary decompression components include a secondary decompression tank, a knob-type pressure reducer, a second communication pipe and a third pressure gauge, and the knob-type decompression device, the second communication pipe and the The third pressure gauges are all arranged in the secondary decompression tank; one end of the second conveying pipeline penetrates into the secondary decompression tank and communicates with the input port of the knob-type decompressor.
  • the secondary decompression component further includes a secondary thermal insulation layer, and the secondary thermal insulation layer is laid on the On the inner wall of the secondary decompression tank;
  • the preferred technical solution above is to reduce the pressure for the second time through the knob-type pressure reducer, so that the pressure of the natural gas to be analyzed is further reduced, which is more conducive to the flow rate of the natural gas during the online analysis of sulfur compounds in the natural gas pipeline. control.
  • the system for on-line detection of flame photometry of the content of sulfur-containing compounds in natural gas further includes a circulating heat tracing pipe, and the decompression system is further provided with a heat tracing Assemblies, the circulating heat tracing pipe communicates with the heat tracing component of the decompression system to heat the natural gas to be analyzed in the decompression system; Condensation occurs when natural gas is depressurized in the process of sulfur compounds;
  • a primary heating pipe and a primary exhaust pipe are provided between the circulating heat tracing pipe and the primary decompression component, one end of the primary heating pipe communicates with the circulating heat tracing pipe, and the other end communicates with the circulating heat tracing pipe.
  • One end of the first-stage decompression part is connected, one end of the first-stage discharge pipe is connected with the other end of the first-stage decompression part, and the other end of the first-stage discharge pipe is connected with the circulation heating pipe.
  • a secondary heating pipe and a secondary discharge pipe are arranged between the circulating heat tracing pipe and the secondary decompression component, one end of the secondary heating pipe communicates with the circulating heat tracing pipe, and the other end communicates with the secondary decompression One end of the component is communicated, one end of the secondary exhaust pipe is communicated with the other end of the secondary decompression component, and the other end of the secondary exhaust pipe is communicated with the circulating heating pipe;
  • one end of the primary heating pipe is in communication with the circulating heat tracing pipe, and the other end of the primary heating pipe is respectively connected to the inlet of the heating part of the first heating film pressure reducer and to the second heating film pressure reducer.
  • the inlet of the heating part of the device is connected to heat the first heating film pressure reducer and the second heating film pressure reducer, so as to prevent the condensation of the natural gas to be analyzed during the decompression process;
  • one end of the first-stage discharge pipe is connected with the circulation The heating pipe is connected, and the other end of the first-stage discharge pipe is respectively connected with the outlet of the heating part of the first heating film pressure reducer and the outlet of the heating part of the second heating film pressure reducer;
  • one end of the secondary heating pipe communicates with the circulating heat tracing pipe, and the other end of the secondary heating pipe communicates with the inlet of the heating portion of the knob-type pressure reducer, thereby heating the knob-type pressure reducer, thereby To prevent condensation during the decompression process of the natural gas to be analyzed; one end of the secondary discharge pipe is connected with the circulating heating pipe, and the other end of the secondary discharge pipe is connected with the outlet of the heating part of the knob-type pressure reducer.
  • a quantitative tube is provided in the chromatographic column system, and the quantitative tube is used to temporarily store the natural gas to be analyzed entering the chromatographic column system, so as to realize the Quantification of analyte natural gas for the separation of sulfur compounds using a chromatographic column system.
  • a ten-way valve is provided in the chromatographic column system, and the communication relationship between the components in the chromatographic column is controlled by the ten-way valve. broken;
  • the ten-way valve is clockwise provided with a first valve port, a second valve port, a third valve port, a fourth valve port, a fifth valve port, a sixth valve port, a seventh valve port and an eighth valve port , the ninth valve port and the tenth valve port;
  • the ten-way valve is an adjustable valve, through the gear position control of the ten-way valve, it can realize the connection between the first valve port and the second valve port in one gear position, and the connection between the third valve port and the The four valve ports are connected, the fifth valve port is connected with the sixth valve port, the seventh valve port is connected with the eighth valve port, the ninth valve port is connected with the tenth valve port, and the tenth valve port of the other gear position is connected with the first valve port.
  • valve port is connected, the second valve port is connected with the third valve port, the fourth valve port is connected with the fifth valve port, the sixth valve port is connected with the seventh valve port, the eighth valve port is connected with the ninth valve port; ten-way valve One of the tenth valve port and the ninth valve port is connected with the output port of the decompression system through the third delivery pipeline.
  • the natural gas to be analyzed enters through the tenth or ninth valve port of the ten-way valve, and the tenth valve port of the ten-way valve is connected to the The other of the ninth valve port is used to discharge excess gas; there is a quantitative pipe between the first valve port of the ten-way valve and the eighth valve port of the ten-way valve for temporarily storing the natural gas to be analyzed to realize the quantification of the natural gas to be analyzed.
  • the first valve port of the one-way valve is connected with the eighth valve port of the ten-way valve through the quantitative tube;
  • the carrier gas input pipeline is connected with the second valve port of the ten-way valve;
  • the fourth valve port of the ten-way valve communicates with the seventh valve port of the ten-way valve through the boiling point column;
  • the sulfur column is arranged between the third valve port of the ten-way valve and the sixth valve port of the ten-way valve, so that The third valve port of the ten-way valve communicates with the sixth valve port of the ten-way valve through the sulfur column;
  • the fifth valve port of the ten-way valve communicates with the flame photometric detector;
  • the ten-way valve is clockwise provided with a first valve port, a second valve port, a third valve port, a fourth valve port, a fifth valve port, a sixth valve port, a seventh valve port, a Eight valve ports, ninth valve port and tenth valve port;
  • the ten-way valve is an adjustable valve, through the gear position control of the ten-way valve, the first valve port in one of the gear positions can be connected to the second valve port, and the third valve port can be connected to the second valve port.
  • the port is connected with the fourth valve port, the fifth valve port is connected with the sixth valve port, the seventh valve port is connected with the eighth valve port, the ninth valve port is connected with the tenth valve port, and the tenth valve port of the other gear position It communicates with the first valve port, the second valve port communicates with the third valve port, the fourth valve port communicates with the fifth valve port, the sixth valve port communicates with the seventh valve port, and the eighth valve port communicates with the ninth valve port;
  • the output port of the decompression system is connected with the tenth valve port of the ten-way valve through the third delivery pipeline, and the natural gas to be analyzed enters through the tenth valve port of the ten-way valve; the ninth valve port of the ten-way valve is used to discharge excess gas;
  • a quantitative pipe is provided between the first valve port of the ten-way valve and the eighth valve port of the ten-way valve to temporarily store the natural gas to be analyzed to realize the quantification of the natural gas to be analyzed.
  • the first valve port of the ten-way valve passes through the quantitative pipe and the eighth The valve port is connected; the carrier gas input pipeline is connected with the second valve port of the ten-way valve; the boiling point column is set between the fourth valve port of the ten-way valve and the seventh valve port of the ten-way valve, so that the fourth valve port of the ten-way valve passes The boiling point column communicates with the seventh valve port of the ten-way valve; the sulfur column is set between the third valve port of the ten-way valve and the sixth valve port of the ten-way valve, so that the third valve port of the ten-way valve passes through the sulfur column and the first valve port of the ten-way valve.
  • the six valve ports are connected; the fifth valve port of the ten-way valve is connected with the flame photometric detector;
  • the ten-way valve is clockwise provided with a first valve port, a second valve port, a third valve port, a fourth valve port, a fifth valve port, a sixth valve port, a seventh valve port, a Eight valve ports, ninth valve port and tenth valve port;
  • the ten-way valve is an adjustable valve, through the gear position control of the ten-way valve, the first valve port in one of the gear positions can be connected to the second valve port, and the third valve port can be connected to the second valve port.
  • the port is connected with the fourth valve port, the fifth valve port is connected with the sixth valve port, the seventh valve port is connected with the eighth valve port, the ninth valve port is connected with the tenth valve port, and the tenth valve port of the other gear position It communicates with the first valve port, the second valve port communicates with the third valve port, the fourth valve port communicates with the fifth valve port, the sixth valve port communicates with the seventh valve port, and the eighth valve port communicates with the ninth valve port;
  • the output port of the decompression system is connected with the ninth valve port of the ten-way valve through the third delivery pipeline, and the natural gas to be analyzed enters through the ninth valve port of the ten-way valve; the tenth valve port of the ten-way valve is used to discharge excess gas;
  • a quantitative pipe is provided between the first valve port of the ten-way valve and the eighth valve port of the ten-way valve to temporarily store the natural gas to be analyzed to realize the quantification of the natural gas to be analyzed.
  • the first valve port of the ten-way valve passes through the quantitative pipe and the eighth The valve port is connected; the carrier gas input pipeline is connected with the second valve port of the ten-way valve; the boiling point column is set between the fourth valve port of the ten-way valve and the seventh valve port of the ten-way valve, so that the fourth valve port of the ten-way valve passes The boiling point column communicates with the seventh valve port of the ten-way valve; the sulfur column is set between the third valve port of the ten-way valve and the sixth valve port of the ten-way valve, so that the third valve port of the ten-way valve passes through the sulfur column and the first valve port of the ten-way valve.
  • the six valve ports are connected; the fifth valve port of the ten-way valve is connected with the flame photometric detector.
  • the boiling point column is a squalane chromatographic column. More preferably, the length of the boiling point column is not less than 0.8m, more preferably 0.6m. This preferred technical scheme is beneficial to the separation of sulfur compounds in natural gas.
  • the sulfur column is an oxydipropionitrile chromatographic column. More preferably, the length of the sulfur column is not less than 1.7m. This preferred technical scheme is beneficial to the separation of sulfur compounds in natural gas.
  • the system of flame photometric online detection of sulfur-containing compound content in natural gas further includes a display, and the display is fixedly connected to the flame photometric detector Above, the display is electrically connected to the flame photometric detector, and the display displays the detection results of the flame photometric detector.
  • the system for online flame photometric detection of sulfur-containing compound content in natural gas further includes an alarm linkage device and a combustible gas detection alarm device, and the alarm linkage
  • the device and the combustible gas detection and alarm device are electrically connected to the flame photometric detector, and the combustible gas detection and alarm device is used to detect whether there is a combustible gas leakage near the flame photometric detector, thereby avoiding potential safety hazards
  • the alarm linkage device is a control When the combustible gas detection and alarm device detects a combustible gas leakage, it will close the first delivery pipeline in time so that the gas to be detected stops being transported for detection, avoiding further safety accidents;
  • the beneficial effect of adopting the above further solution is: avoiding the leakage of combustible gas and avoiding safety accidents.
  • the system of flame photometric online detection of sulfur-containing compound content in natural gas further includes a standard gas substance storage bottle, and the standard gas substance storage bottle is connected with A standard gas substance delivery pipe is provided between the chromatographic column systems, one end of the standard gas substance delivery pipe communicates with the input port of the chromatographic column system, and the other end communicates with the output port of the standard gas substance storage bottle,
  • the standard gas substance delivery pipe is provided with a second valve, and the standard gas substance delivery pipe is opened or closed by the second valve;
  • This optimal technical solution is convenient to use standard gas substances for calibration in each batch or every day, so as to further improve the detection accuracy of sulfur compounds in the natural gas to be analyzed.
  • the invention provides a method for flame photometric online detection of the content of sulfur-containing compounds in natural gas, wherein the method comprises:
  • step S2 The decompressed natural gas obtained in step S2 is transported to the chromatographic column system, and the decompressed natural gas is separated by the boiling point column and the sulfur column in turn under the drive of the carrier gas, and the separated components are transported to the flame photometric detector for flame photometric detection Instrument combustion detection, to obtain detection spectrum;
  • step S4 until after the carbonyl sulfide (being carbon oxysulfide) component in the natural gas leaves the sulfur column, the carrier gas is transferred to the input port of the sulfur column, the output port of the sulfur column is connected with the input port of the boiling point column, and the output port of the boiling point column It is connected with the input port of the flame photometric detector.
  • the carrier gas the remaining components continue to be separated by the chromatographic column system, and the components separated by the output port of the boiling point column are sent to the flame photometric detector for combustion detection by the flame photometric detector. , to obtain the detection map;
  • the flame photometric online detection method for the content of sulfur-containing compounds in natural gas can carry out online detection of sulfur-containing compounds in natural gas.
  • the detection operation is simple, and the content of sulfur-containing compounds in natural gas can be obtained only by simple calculation, so that enterprises can It can be operated by itself without sending it to the implementation room for inspection, which reduces the production cost of the enterprise, and at the same time speeds up the detection efficiency of sulfur compounds in natural gas and improves the detection accuracy of sulfur compounds in natural gas.
  • step S3 the decompressed natural gas driven by the carrier gas is separated using a boiling point column and a sulfur column in sequence, hydrogen sulfide, carbonyl sulfide, Methyl mercaptan and ethyl mercaptan are sequentially discharged from the boiling point column (wherein the time difference between the hydrogen sulfide and carbonyl sulfide components is almost extremely small) and enter the sulfur column for separation to further increase the separation time difference between the components, hydrogen sulfide, carbonyl sulfide After being discharged from the sulfur column in turn, it enters the flame photometric detector and is burned and detected by the flame photometric detector.
  • step S4 until the carbonyl sulfide component in the natural gas leaves the sulfur column (at this time, the ethyl sulfide component is about to exit the boiling point column), the carrier gas is transferred to the input port of the sulfur column, and the sulfur column output port is connected to the boiling point column input port.
  • the port is connected, the output port of the boiling point column is connected with the input port of the flame photometric detector, and the remaining components continue to be separated by the chromatographic column system under the drive of the carrier gas.
  • the components are sequentially discharged from the boiling point column and enter the flame photometric detector to be burned and detected by the flame photometric detector.
  • the pressure of the decompressed natural gas obtained in step S2 is 0.18-0.25 MPa (for example, 0.2 MPa).
  • the obtained natural gas transported in the natural gas pipeline is transported to the primary decompression component through the first transmission pipeline, and the pressure of the natural gas is reduced to 1.8-2.5 MPa (such as 2MPa), and then transported to the secondary decompression part through the second delivery pipeline, and the pressure of the natural gas is reduced to 0.18-0.25MPa (for example, 0.2MPa) through the secondary decompression part to obtain decompressed natural gas.
  • the working temperature of the sulfur column is 55-65° C. (eg, 62° C.).
  • the working temperature of the boiling point column is 65-75°C (for example, 70°C).
  • nitrogen is used as the carrier gas.
  • the flow rate of the carrier gas is 22ml/min.
  • the separated components are transported to the flame photometric detector, and the combustion detection of the flame photometric detector is realized in the following manner:
  • the separated components are transported to the flame photometric detector, filled with hydrogen gas with a pressure of 0.24MPa and a flow rate of 40ml/min and air with a pressure of 0.24MPa and a flow rate of 80ml/min, and burn at 150°C using a flame photometric detector detection.
  • the sulfur-containing compound standard gas substance is taken, and the sulfur-containing compound content in the sulfur-containing compound standard gas substance is detected to obtain the sulfur-containing compound content standard curve, including the following steps:
  • Step S11 taking hydrogen sulfide, carbonyl sulfide, methyl mercaptan, ethanethiol, ethyl sulfide, n-butanethiol and methane to configure standard gas substances together, and taking at least 4 groups of standard gas substances with different concentrations of sulfur-containing compounds;
  • Step S12 For the detection of each standard gas substance obtained in step S11, obtain the corresponding response peak area value data, take the concentration of each sulfur-containing compound as the ordinate, and take the corresponding response peak area value of each sulfur-containing compound as the abscissa, draw each Sulfur-containing compound content standard curve;
  • the sulfur-containing compound selected in the standard gas substance can be determined based on the type of the sulfur-containing compound in the natural gas to be detected;
  • Standard gas substances generally have a large number of components as the base gas.
  • the standard gas substances of sulfur compounds in natural gas are configured with reference to the actual components in natural gas; a large number of components in natural gas are methane, so when configuring sulfur compound standards For gaseous substances, use methane as base gas or make-up gas to obtain standard gaseous substances with specific content of sulfur compounds;
  • Adopting this preferred technical solution is more conducive to calculating the content of sulfur-containing compounds in natural gas.
  • Fig. 1 is a schematic structural diagram of a flame photometric online detection system for the content of sulfur compounds in natural gas provided by an embodiment of the present invention.
  • Fig. 2 is a schematic structural diagram of a primary decompression component in an embodiment of the present invention.
  • Fig. 3 is a schematic structural diagram of a secondary decompression component in an embodiment of the present invention.
  • Fig. 4A is a schematic diagram of the connection structure of the ten-way valve in an embodiment of the present invention.
  • Fig. 4B is a schematic diagram of the connection structure of the ten-way valve in an embodiment of the present invention.
  • Fig. 4C is a schematic diagram of the connection structure of the ten-way valve in an embodiment of the present invention.
  • Fig. 4D is a schematic diagram of the connection structure of the ten-way valve in an embodiment of the present invention.
  • Fig. 5A-Fig. 5J are schematic workflow diagrams of the flame photometric online detection system for the content of sulfur-containing compounds in natural gas in an embodiment of the present invention.
  • Fig. 6A is a standard curve diagram of hydrogen sulfide in an embodiment of the present invention.
  • Fig. 6B is a standard curve diagram of carbon oxysulfide in an embodiment of the present invention.
  • Fig. 6C is a standard curve diagram of methyl mercaptan in an embodiment of the present invention.
  • Fig. 6D is a standard curve diagram of ethanethiol in an embodiment of the present invention.
  • Fig. 6E is a standard curve diagram of diethyl sulfide in an embodiment of the present invention.
  • Fig. 6F is a standard curve diagram of n-butanethiol in an embodiment of the present invention.
  • the present embodiment provides the system of flame photometric on-line detection of sulfur-containing compound content in natural gas, and this system comprises: Sampling device, decompression system, chromatographic column system 38 and flame photometric detector (FPD) 14; mid-term chromatographic column system 38 is provided with carrier gas input pipeline and is provided with chromatographic column in chromatographic column system 38, and chromatographic column comprises boiling point column 40 and sulfur column 41 (for example, chromatographic column is made up of boiling point column 40 and sulfur column 41) .
  • FPD flame photometric detector
  • the sampling end of the sampling device is placed in the natural gas pipeline 1, and the natural gas transported in the natural gas pipeline 1 is obtained online, and the natural gas in the natural gas pipeline 1 enters the sampling device along with the natural gas transmission power part.
  • a first delivery pipeline 5 is provided between the sampling device and the decompression system.
  • One end of the first delivery pipeline 5 is fixedly connected and communicated with the output port of the sampling device, and the other end is fixedly connected and communicated with the input port of the decompression system, thereby sampling
  • the natural gas obtained by the device enters the decompression system through the first delivery pipeline 5 for decompression treatment.
  • a third delivery pipeline 13 is arranged between the chromatographic column system 38 and the decompression system, and one end of the third delivery pipeline 13 is fixedly connected and communicated with the output port of the decompression system, and the other end is fixedly connected with the input port of the chromatographic column system 38 and Connected, the input port of the chromatographic column system 38 is communicated with the input port of the boiling point column 40 through a controllable on-off connecting pipeline, and the input port of the boiling point column 40 and the input port of the sulfur column 41 are respectively connected with the carrier gas input pipeline through a controllable
  • the on-off connection pipeline is connected, the output port of the boiling point column 40 is connected with the input port of the sulfur column 41 through a controllable on-off connection pipeline, the output port of the sulfur column 41 is connected with the input port of the boiling point column 40 through a controllable on-off connection pipeline Communication, the output port of the boiling point column 40 and the output port of the sulfur column 41 are respectively communicated with the input port of the flame photometric detector 14
  • the flame photometric detector 14 is used to burn each component, detect the light transmittance and convert it into an electrical signal to detect the content of sulfur compounds in the natural gas to be analyzed; Burn detection.
  • Flame photometric detector 14 is known instrument, a kind of high sensitivity, the high selectivity detector that only produces detection signal to organic matter containing sulfur and phosphorus.
  • the principle of sulfur detection in the hydrogen-rich flame, sulfur-containing organic matter emits characteristic blue-violet light after burning, with a wavelength of 350nm-430nm and a maximum intensity of 394nm, which is filtered by a filter and then measured by a photomultiplier tube. The change in the intensity of the sulfur is converted into an electrical signal, and the sulfur content can be detected.
  • the sampling device includes a mounting base 3 and a sampling probe 4, the sampling probe 4 is fixedly connected to the mounting base 3, the sampling probe 4 is provided with a self-heating pressure reducer, the sampling probe 4 is connected to the first
  • the transmission pipeline 5 is connected, and the mounting seat 3 is installed on the natural gas pipeline 1, wherein the natural gas pipeline 1 is provided with a detection port 2, wherein the mounting seat 3 and the detection port 2 are provided with a connecting flange, which can be easily connected through the connecting flange, and the sampling probe 4 is placed in the natural gas pipeline 1, wherein the sampling probe 4 communicates with the first delivery pipeline 5, and the natural gas in the natural gas pipeline 1 enters the sampling probe 4 by itself, and then enters the first delivery pipeline 5.
  • the first delivery pipeline 5 is provided with a first valve 6 and a filter screen; the first valve 6 is installed on the first delivery pipeline 5, and the first delivery pipeline is opened or closed by the first valve 6 5.
  • the first valve 6 is a solenoid valve, which can be controlled by electric signals, so that the operation is more convenient; the filter screen is a 120-160 mesh filter screen, which can filter out particulate impurities contained in natural gas.
  • the decompression system includes a primary decompression component 8 and a secondary decompression component 10; a first delivery pipeline 5 is provided between the primary decompression component 8 and the sampling device, and the first delivery pipeline 5 One end of the sampling device is fixedly connected and communicated with the output port of the sampling device, and the other end is fixedly connected and communicated with the input port of the primary decompression component 8 as the input port of the decompression system, so that the natural gas obtained by the sampling device passes through the first delivery pipeline 5 Enter the primary decompression unit 8 for decompression treatment.
  • a second delivery pipeline 9 is provided between the secondary decompression component 10 and the primary decompression component 8, and one end of the second delivery pipeline 9 is fixedly connected and communicated with the output port of the primary decompression component 8, and the other end is connected with the secondary decompression component 8.
  • the input port of the decompression component 10 is fixedly connected and connected, and the natural gas is decompressed by the primary decompression component 8 and then enters the secondary decompression component 10 for secondary decompression.
  • the primary decompression component 8 includes a primary decompression box 21, a primary thermal insulation layer 22, a first heating film pressure reducer 23, a second heating film pressure reducer Compressor 28, first pressure gauge 26 and second pressure gauge 29, the primary insulation layer 22 is paved on the inner wall of the primary decompression box 21, the first heating membrane pressure reducer 23, the second heating membrane pressure reducer
  • the pressure regulator 28, the first pressure gauge 26 and the second pressure gauge 29 are all located in the first-stage decompression box 21, and the first heating membrane pressure reducer 23 and the second heating membrane pressure reducer 28 are provided with the first A communication pipe 27, one end of the first communication pipe 27 is communicated with the output port of the first heating membrane pressure reducer 23, and the other end is communicated with the input port of the second heating membrane type pressure reducer 28, and the first pressure gauge 26 is installed On the first communication pipe 27 and communicated with the first communication pipe 27, the other end of the first delivery pipe 5 penetrates into the primary decompression tank 21 and communicates with the input port of the
  • the decompression effect of the natural gas through the first heating membrane pressure reducer 23 is observed through the first pressure gauge 26, so as to obtain the real-time pressure of the natural gas.
  • the first heating membrane pressure reducer 23, the second heating membrane pressure reducer 28, the first pressure gauge 26 and the second pressure gauge 29 are all existing equipment.
  • the primary insulation layer 22 is made of polymer insulation material.
  • the secondary decompression component 10 includes a secondary decompression tank 30, a secondary insulation layer 31, a knob-type decompressor 34, a second communication pipe 35 and a third pressure Table 36, the secondary insulation layer 31 is laid on the inner wall of the secondary decompression box 30, the knob type pressure reducer 34, the second connecting pipe 35 and the third pressure gauge 36 are all arranged in the secondary decompression box 30,
  • the other end of the second delivery pipeline 9 penetrates the secondary decompression tank 30, and is communicated with the input port of the knob type decompressor 34, and one end of the second communication pipe 35 is communicated with the output port of the knob type decompressor 34, and the other One end communicates with one end of the third pressure gauge 36 , and one end of the third delivery pipeline 13 communicates with the other end of the third pressure gauge 36 .
  • the third pressure gauge 36 detects the pressure of the natural gas decompressed by the knob type pressure reducer 34, thereby controlling the flow rate of the natural gas, so that the detection of the content of sulfur compounds in the natural gas is more accurate.
  • the secondary insulation layer 31 is made of polymer material, wherein the third pressure gauge 36 and the knob type pressure reducer 34 are prior art.
  • an alarm 33 is also provided in the secondary decompression tank 30, through which the alarm 33 can detect whether there is a natural gas leakage, and can issue an alarm in time.
  • a circulating heat tracing pipe 7 is also included, and the circulating heat tracing pipe 7 is used to supply high-temperature gas.
  • One end of the primary heating pipe 11 communicates with the circulating heat tracing pipe 7, and the other end communicates with the inlet of the heat tracing assembly of the primary decompression component 8;
  • the other end of the primary discharge pipe 52 communicates with the circulating heating pipe 7; one end of the primary heating pipe 11 is respectively connected with the first hot gas pipe 24 and the second hot gas pipe 25, and the first hot gas pipe 24 and the first heating film
  • the inlet of the heating part of the pressure reducer 23 is communicated, and the second hot gas pipe 25 is connected with the inlet of the heating part of the second heating film pressure reducer 28, so that the first heating film pressure reducer 23 and the second heating film Type pressure reducer 28 is heated to prevent natural gas from condensing during the decompression process.
  • the primary discharge pipe 52 communicates with the outlet of the heating portion of the first heating membrane type pressure reducer 23 and the output of the second heating membrane type pressure reducer 28 respectively.
  • the outlet of the hot part is connected.
  • a secondary heating pipe 12 and a secondary discharge pipe 53 are arranged between the circulating heat tracing pipe 7 and the secondary decompression component 10; The inlet of the heat tracing component is communicated; one end of the secondary discharge pipe 53 communicates with the outlet of the heat tracing component of the secondary decompression component 10, and the other end of the secondary discharge pipe 53 communicates with the circulating heat tracing pipe 7; wherein the secondary decompression tank 30
  • the sampling probe, mounting base 3, first valve 6, first delivery pipeline 5, second delivery pipeline 9, and third delivery pipeline 13 etc. should be made of appropriate sulfur inert or passivated materials, the selected materials should be compatible with the gas and sampling method, the internal and external conditions of the sampling device should ensure that the composition of the gas being sampled is not degraded and does not change the composition of the gas .
  • the sampling probe is set on the natural gas pipeline 1, it should be located at the horizontal natural gas pipeline 1, and not at the corner or in the middle, so as to improve the detection accuracy of the content of sulfur compounds in natural gas.
  • the boiling point column 40 is a squalane chromatographic column, and the length of the boiling point column is 0.8 m;
  • the sulfur column 41 is an oxydipropionitrile chromatographic column, and the length of the sulfur column 41 is 1.7 m.
  • the basic parameters of the chromatographic column system 38 are as follows in Table 1:
  • the chromatographic column system is provided with a ten-way valve and a quantitative tube 54, and the on-off between the connecting parts in the chromatographic column is controlled through the ten-way valve;
  • the ten-way valve is provided with a first valve port 42, a second valve port 43, a third valve port 44, a fourth valve port 45, and a fifth valve port clockwise. 46.
  • the ten-way valve is an adjustable valve, through the ten-way valve gear control, it can realize Gear A (as shown in Figure 4A and Figure 4C) the first valve port 42 communicates with the second valve port 43, the third valve port 44 communicates with the fourth valve port 45, the fifth valve port 46 communicates with the sixth valve port 47 communication, the seventh valve port 48 communicates with the eighth valve port 49, the ninth valve port 50 communicates with the tenth valve port 51, and the B gear (as shown in Figure 4B and Figure 4D) the tenth valve port 51 communicates with the first valve port Port 42 communicates, the second valve port 43 communicates with the third valve port 44, the fourth valve port 45 communicates with the fifth valve port 46, the sixth valve port 47 communicates with the seventh valve port 48, the eighth valve port 48 communicates with the ninth valve port The valve port 49 is connected;
  • One of the tenth valve port 51 and the ninth valve port 50 of the ten-way valve communicates with the third delivery pipeline 13, the natural gas to be analyzed enters through the tenth valve port 51 or the ninth valve port 50 of the ten-way valve, and the first The other of the tenth valve port 51 and the ninth valve port 50 is used to discharge excess gas; wherein, as shown in Figure 4A and Figure 4B, the tenth valve port 51 of the ten-way valve communicates with the third delivery pipeline 13, and the natural gas to be analyzed The gas enters through the tenth valve port 51 of the ten-way valve, and the ninth valve port 50 of the ten-way valve is used to discharge excess gas; 13 is connected, the natural gas to be analyzed enters through the ninth valve port 50 of the ten-way valve, and the tenth valve port 51 of the ten-way valve is used to discharge excess gas;
  • a quantitative tube 54 is provided between the first valve port 42 of the ten-way valve and the eighth valve port 49 of the ten-way valve for temporarily storing the natural gas to be analyzed to realize the quantification of the natural gas to be analyzed.
  • the first valve port 42 of the ten-way valve passes the quantitative The pipe 54 communicates with the eighth valve port 49 of the ten-way valve;
  • the carrier gas input pipeline communicates with the second valve port 43 of the ten-way valve;
  • the boiling point column 40 is set at the fourth valve port 45 of the ten-way valve and the seventh valve port of the ten-way valve 48, so that the fourth valve port 45 of the ten-way valve communicates with the seventh valve port 48 through the boiling point column 40;
  • the sulfur column is arranged between the third valve port 44 of the ten-way valve and the sixth valve port 47 of the ten-way valve, so that The third valve port 44 of the ten-way valve communicates with the sixth valve port 47 of the ten-way valve through the sulfur column;
  • a standard gas substance storage bottle 15 is also included, a standard gas substance delivery pipe 16 is provided between the standard gas substance storage bottle 15 and the chromatographic column system 38, and one end of the standard gas substance delivery pipe 16 is connected to the chromatographic column The input port of the system 38 is communicated, and the other end is communicated with the output port of the standard gas substance storage bottle 15.
  • the standard gas substance delivery pipe 16 is provided with a second valve, and the standard gas substance delivery pipe 16 is opened or closed by the second valve.
  • the gas substance storage bottle 15 can transport standard gas substances, which is convenient to use standard gas substances for calibration in each batch or every day, thereby further improving the detection accuracy of sulfur compounds in natural gas.
  • the standard gas substance storage bottle 15 can be a container with a sulfur inert inner coating.
  • a display 39 is also included, the display 39 is fixedly connected to the flame photometric detector 14, the display 39 is electrically connected to the flame photometric detector 14, and the display 39 displays the detection result of the flame photometric detector 14.
  • an alarm linkage device 19 and a combustible gas detection and alarm instrument 18 are also included, and both the alarm linkage device 19 and the combustible gas detection and alarm instrument 18 are electrically connected to the flame photometric detector 14, and the alarm linkage device 19 is connected to the first Valve 6 is electrically connected.
  • the combustible gas detection and alarm device 18 is used to detect whether there is a combustible gas leakage near the flame photometric detector 14, thereby avoiding potential safety hazards, and the alarm linkage device 19 is a controller.
  • the first valve 6 will be closed in time, so that the natural gas will be stopped for detection. Avoid further security incidents.
  • an exhaust pipe 17 is provided on the side wall of the flame photometric detector 14 through which the combusted smoke is discharged from a long distance to avoid potential safety hazards.
  • a power supply box 20 is also included, and the power supply box 20 is electrically connected with the first valve 6, the flame photometer 14, the chromatographic column system 38 and the display 39 for power supply.
  • This embodiment also provides a method for flame photometric online detection of the content of sulfur-containing compounds in natural gas, wherein the method includes:
  • Step S1 Obtain the calibration curve spectrum:
  • Step S101 The six known sulfur-containing compounds stored in the standard gas substance storage bottle, specifically hydrogen sulfide, carbonyl sulfide, methyl mercaptan, ethanethiol, ethyl sulfide, and n-butanethiol, are prepared together with methane as a standard gas substance
  • a total of 5 groups of standard gas substances with different concentrations of sulfur-containing compounds are configured, respectively 1#, 2#, 3#, 4#, and 5#.
  • the concentration of each sulfur-containing compound in each group of standard gas substances is shown in Table 2-Table 7;
  • Step S102 pass it into the chromatographic column system 38 and the flame photometric detector 14, detect the standard gas substance obtained in step S101, detect the sulfur-containing compound content in the standard gas substance (ie, the natural gas standard sample), and obtain the natural gas standard sample spectrum (Proceed in the same way as step 3 below).
  • the standard gas substance ie, the natural gas standard sample
  • Step S103 Obtain the natural gas standard sample spectrum according to the display 39, obtain the response value of FPD according to the spectrum, obtain the corresponding response peak area value data, take the concentration of each standard substance as the vertical axis, and take the corresponding response peak area value of each standard substance as the horizontal axis Coordinates, draw the standard curve of the content of each sulfur-containing compound, the results are shown in Figure 6A- Figure 6F; the concentration of each standard and the corresponding response peak area data are as follows in Table 2-Table 7.
  • Table 2 is the corresponding value table of the concentration and response value of hydrogen sulfide components
  • Table 3 is the corresponding value table of the concentration and response value of carbonyl sulfide components
  • Table 4 is the corresponding value table of concentration and response value of diethyl sulfide component
  • Table 5 is the corresponding value table of the concentration and response value of n-butanthiol component
  • Table 6 is the corresponding value table of the concentration and response value of the methyl mercaptan component
  • Table 7 is the corresponding value table of the concentration and response value of ethanethiol component
  • step S3 The decompressed natural gas obtained in step S2 is transported to the chromatographic column system 38 through the third delivery pipeline 13 (the temperature control of the decompressed natural gas entering the chromatographic column system 38 is 45° C.), and the decompressed natural gas has a pressure of 0.24Mpa, Driven by nitrogen gas with a flow rate of 22ml/min, separation is carried out in the chromatographic column system 38, and the separated product is transported to the flame photometric detector 14 for combustion detection, and the detection spectrum is obtained (see Figure 5A- Figure 5J for the flow process):
  • step S301 Transport the decompressed natural gas obtained in step S2 to the chromatographic column system 38 through the third delivery pipeline 13.
  • the ten-way valve is in the B position (as shown in FIGS. 4B and 4D ).
  • the tenth valve port 51 and The first valve port 42 communicates
  • the second valve port 43 communicates with the third valve port 44
  • the fourth valve port 45 communicates with the fifth valve port 46
  • the sixth valve port 47 communicates with the seventh valve port 48
  • the eighth valve port 48 communicate with the ninth valve port 49;
  • the decompressed natural gas enters through the tenth valve port 51, then flows to the first valve port 42, and then enters the quantitative tube for temporary storage, and the excess decompressed natural gas is discharged from the ninth valve port 50; or; As shown in 4D, the decompressed natural gas enters through the ninth valve port 50 , then flows to the eighth valve port 48 , and then enters the metering tube for temporary storage, and the excess decompressed natural gas is discharged through the tenth valve port 51 .
  • Nitrogen gas with a pressure of 0.24MPa and a flow rate of 22ml/min is injected into the second valve port 3, enters the quantitative tube through the first valve port 42, drives the decompressed natural gas temporarily stored in the quantitative tube to flow, and passes through the The eighth valve port 49 and the seventh valve port 48 enter the boiling point column 40, and are separated in the boiling point column 40 at a temperature of 70°C.
  • Nitrogen gas with a pressure of 0.24MPa and a flow rate of 22ml/min is injected into the second valve port 3, enters into the sulfur column 41 through the third valve port 43, and drives the residual components of the natural gas in the sulfur column 41 to continue to be separated.
  • the residual components ethyl sulfide and n-butylmercaptan in the boiling point column 40 continue to separate and leave the boiling point column 40 successively; the methyl mercaptan and ethyl mercaptan components in the sulfur-containing compounds leave the sulfur column 41 successively and enter the boiling point The column 40 separates; finally leaves the boiling point column 40 in sequence according to ethyl sulfide, n-butyl mercaptan, methyl mercaptan, and ethanethiol; the components leaving the boiling point column 40 pass through the fourth valve port 45 and the fifth valve port 46 in sequence Enter flame photometric detector 14 and carry out combustion detection, obtain collection of illustrative plates;
  • the flame photometric detector 14 uses the flame photometric detector 14 to carry out combustion detection by the following way: in the flame photometric detector 14, the delivery pressure is 0.24MPa, the hydrogen gas with a flow velocity of 40ml/min and the air with a pressure of 0.24MPa and a flow velocity of 80ml/min , at 150° C., after combustion detection by the flame photometric detector 14, a detection spectrum is obtained; wherein the hydrogen is the gas, and the air is the supporting gas.
  • step S4 Obtain the response peak data according to the detection spectrum obtained in step S3, and bring the response peak data into the standard curve of each sulfur-containing compound content obtained in step S1, and read the content of sulfur-containing compounds in natural gas from the graph.
  • the total sulfur content in natural gas is the sum of the concentrations of various sulfur-containing compounds.
  • the error value of this online detection method is ⁇ 5%, which is within the error range, indicating that the flame photometric online detection system for the content of sulfur compounds in natural gas can effectively detect the content of sulfur compounds in natural gas online, and has high detection accuracy.

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Abstract

一种天然气中含硫化合物含量的火焰光度在线检测的方法及系统。该系统包括：取样装置、减压系统、色谱柱系统和火焰光度检测仪（14）；色谱柱系统设有载气输入管路且内设有色谱柱，色谱柱包括沸点柱（40）和硫柱（41）；取样装置输出端口通过第一输送管道与减压系统输入端口连通，减压系统输出端口与沸点柱（40）输入端口通过可控制通断的连接管路连通，沸点柱（40）输入端口、硫柱（41）输入端口分别与载气输入管路通过可控制通断的连接管路连通，沸点柱（40）输出端口与硫柱（41）输入端口通过可控制通断的连接管路连通，硫柱（41）输出端口与沸点柱（40）输入端口通过可控制通断的连接管路连通，沸点柱（40）输出端口、硫柱（41）输出端口分别与火焰光度检测仪（14）输入端口通过可控制通断的连接管路连通。

Description

一种天然气中含硫化合物含量的火焰光度在线检测的方法及系统 技术领域
本发明属于天然气检测技术领域，具体涉及一种天然气中含硫化合物含量的火焰光度在线检测方法及系统。
背景技术
随着对能源需求的不断增长，提高天然气在能源结构中的比重对优化能源结构，有效解决能源供应安全和生态环境保护，实现经济和社会的可持续发展发挥重要作用。为了提高天然气产品质量，天然气工业的核心标准GB17820-2018《天然气》标准中关键技术指标作了进一步的提升，要求更加详细和严格，特别是天然气中总硫含量的技术指标由200mg/m 3提升为20mg/m 3，并提出了瞬时值要求。
目前，各净化厂净化气总硫含量大概从10mg/m 3到100mg/m 3不等，H 2S含量大部分小于6mg/m 3，硫含量降低的关键是降低净化气中氧硫化碳、硫醇等的含量。因此对天然气净化工艺又提出了新的要求，同时必须与之拥有配套快速、准确的测量手段。
目前净化气和管输天然气中总硫常用的检测方法仍然是现场取样、实验室采用氧化微库仑法和紫外荧光法进行检测的方法，但是此方法已不能满足现目前新的生产过程控制的需求，随着天然气总硫在线检测技术的逐步应用，紫外吸收光谱法和氢解-速率计比色法应用到天然气在线总硫的检测领域中，但由于仪器配置、技术参数和应用原理的特殊性，在线应用还存在着许多问题，不易全面应用到在线检测天然气中总硫和含硫化合物中。
发明内容
本发明的目的在于提供一种天然气中含硫化合物含量的火焰光度在线检测系统。该系统能够快速有效地实现对天然气中至少6种含硫化合物的含量进行在线分析测试。
为了实现上述目的，本发明提供了一种天然气中含硫化合物含量的火焰光度在线检测系统，其中，该系统包括：
取样装置、减压系统、色谱柱系统和火焰光度检测仪；
所述取样装置用于在线获取天然气管道中的待分析天然气气体；
所述火焰光度检测仪用以将输送进火焰光度检测仪的各个组分进行燃烧，检测透光率并转化为电信号从而检测出待分析天然气气体中含硫化合物的含量；
所述色谱柱系统设有载气输入管路且色谱柱系统内设有色谱柱，所述色谱柱包括沸点柱和硫柱(例如由沸点柱和硫柱组成)；
所述取样装置的输出端口通过第一输送管道与所述减压系统的输入端口连通，所述减压系统的输出端口与所述沸点柱的输入端口通过可控制通断的连接管路连通，所述沸点柱的输入端口、所述硫柱的输入端口分别与所述载气输入管路通过可控制通断的连接管路连通，所述沸点柱输出端口与所述硫柱输入端口通过可控制通断的连接管路连通，所述硫柱输出端口与所述沸点柱输入端口通过可控制通断的连接管路连通，所述沸点柱输出端口、所述硫柱输出端口分别与火焰光度检测仪的输入端口通过可控制通断的连接管路连通。
本发明提供的上述天然气中含硫化合物含量的火焰光度在线检测的系统能够很好的适用于在线分析天然气管道内天然气中含硫化合物的含量，能够实现至少6种含硫化合物的含量测试。本发明提供的上述天然气中含硫化合物含量的火焰光度在线检测的系统具备如下有益效果：
(1)通过设置的取样装置能够实时的将天然气管道中的天然气获取，并输送到减压系统，经过减压系统对天然气的压力降低，从而调整天然气的流速，使得天然气进入到色谱柱系统中的流速适中，利用载气将其带动在色谱柱中进行分离，通过设置的硫柱和沸点柱能够将天然气中含硫化合物分离效果更好，从而再采用火焰光度检测仪将各个组分进行燃烧，检测透光率，并转化为电信号，从而能够方便的检测出天然气中含硫化合物的含量；
(2)通过本发明色谱柱系统中各组件的独特连接方式，能够更快速准确的实现对天然气中至少6中不同含硫化合物的分离，从而提高天然气中含硫化合物的检测的效率和准确度；具体而言，通过本发明色谱柱系统中各组件的独特连接方式，能够实现基于天然气中不同组分的色谱分离特征，使天然气中的部分组分依次使用一次沸点柱和一次硫柱进行分离，部分组分使用两次沸点柱和一次硫柱具体为依次使用沸点柱、硫柱和沸点柱进行分离，部分组分仅使用一次沸点柱进行分离；
(3)通过本系统免去了现有的需要将天然气获取然后再移取到实验室中检测的繁琐步骤，使得对天然气中含硫化合物的检测更高效，也适用于目前对天然气开采的高要求；
(4)通过本系统能够减轻企业的检测成本，使得企业能够自主对天然气中含硫化合物进行检测，检测非常方便高效。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，所述取样 装置包括安装座和取样探头，所述取样探头固定连接在所述安装座上，所述取样探头与所述第一输送管道连通；通过所述安装座安装到天然气管道上能够实现将取样装置固定到天然气管道上从而通过置于所述天然气管道内的取样探头实现对天然气管道中的天然气进行在线获取。更优选地，所述取样探头上设有自伴热式减压器。该优选技术方案更有助于进行天然气管道内的天气燃气取样，取样效果好。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，所述第一输送管道上设有第一阀门，通过所述第一阀门打开或关闭所述第一输送管道。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，所述第一输送管道内设有过滤网。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，所述减压系统包括依次连接的一级减压部件和二级减压部件，所述二级减压部件的输入端口与所述一级减压部件的输出端口通过第二输送管道连通；所述一级减压部件的输入端口作为所述减压系统的输入端口与所述取样装置的输出端口通过所述第一输送管道连通；所述二级减压部件的输出端口作为所述减压系统的输出端口与所述沸点柱的输入端口通过可控制通断的连接管路连通；
上述优选技术方案，通过设置一级减压部件和二级减压部件对待分析天然气气体进行减压，能够更好的适用于在线分析天然气管道内天然气中含硫化合物，实现对从天然气管道中获取的天然气的压力降低的精准控制，更好的实现天然气流速的调整；
更优选地，所述一级减压部件包括一级减压箱、第一加热膜式减压器、第二加热膜式减压器、第一压力表和第二压力表，所述第一加热膜式减压器、所述第二加热膜式减压器、所述第一压力表和所述第二压力表均设在所述一级减压箱内；所述第一加热膜式减压器与所述第二加热膜式减压器之间设有第一连通管，所述第一连通管的一端与所述第一加热膜式减压器的输出端口连通，另一端与所述第二加热膜式减压器的输入端口连通；所述第一压力表安装在所述第一连通管上，并与所述第一连通管连通；所述第一输送管道的另一端穿入所述一级减压箱内，并与所述第一加热膜式减压器的输入端口连通；所述第二输送管道的一端穿入所述一级减压箱内，并与所述第二加热膜式减压器的输出端口连通，所述第二压力表安装到所述第二输送管道，并与所述第二输送管道连通；进一步优选地，所述一级减压部件进一步包括一级保温层，所述一级保温层铺贴在所述一级减压箱的内壁上；
上述优选技术方案，通过设置第一加热膜式减压器和第二加热膜式减压器，形成双重功能，使得降压效果显著高效，更有利于在进行在线分析天然气管道内天然气中含硫 化合物过程中对天然气进行降压操作；
更优选地，所述二级减压部件包括二级减压箱、旋钮式减压器、第二连通管和第三压力表，所述旋钮式减压器、所述第二连通管和所述第三压力表均设在所述二级减压箱内；所述第二输送管道的一端穿入所述二级减压箱，并与所述旋钮式减压器的输入端口连通，所述第二连通管的一端与所述旋钮式减压器的输出端口连通，另一端与所述第三压力表的一端连通，所述第三压力表另一端作为所述二级减压部件的输出端口与所述沸点柱的输入端口通过可控制通断的连接管路连通；进一步优选地，所述二级减压部件进一步包括二级保温层，所述二级保温层铺贴在所述二级减压箱的内壁上；
上述优选技术方案，通过旋钮式减压器进行二次降压，使得待分析天然气气体的压力进一步减小，更有利于在进行在线分析天然气管道内天然气中含硫化合物过程中对天然气的流速进行控制。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，该天然气中含硫化合物含量的火焰光度在线检测的系统进一步包括循环伴热管，所述减压系统进一步设有伴热组件，所述循环伴热管与所述减压系统的伴热组件连通，用以对减压系统中的待分析天然气气体进行加热；该优选技术方案能够防止在进行在线分析天然气管道内天然气中含硫化合物过程中在进行天然气降压时出现冷凝的情况；
更优选地，所述循环伴热管与所述一级减压部件之间设有一级加热管和一级排出管，所述一级加热管的一端与所述循环伴热管连通，另一端与所述一级减压部件的一端连通，所述一级排出管的一端与所述一级减压部件的另一端连通，所述一级排出管的另一端与所述循环伴热管连通，所述循环伴热管与所述二级减压部件之间设有二级加热管和二级排出管，所述二级加热管的一端与所述循环伴热管连通，另一端与所述二级减压部件的一端连通，所述二级排出管的一端与所述二级减压部件的另一端连通，所述二级排出管的另一端与所述循环伴热管连通；
在一具体实施方式中，一级加热管的一端与循环伴热管连通，一级加热管的另一端分别与第一加热膜式减压器的伴热部入口、与第二加热膜式减压器的伴热部入口连通，从而对第一加热膜式减压器和第二加热膜式减压器进行加热，从而防止待分析天然气气体减压过程产生冷凝；一级排出管的一端与循环伴热管连通，一级排出管的另一端分别与第一加热膜式减压器的伴热部出口、与第二加热膜式减压器的伴热部出口连通；
在一具体实施方式中，二级加热管的一端与循环伴热管连通，二级加热管的另一端与旋钮式减压器的伴热部入口连通，从而对旋钮式减压器进行加热，从而防止待分析天然气气体减压过程产生冷凝；二级排出管的一端与循环伴热管连通，二级排出管的另一 端与旋钮式减压器的伴热部出口连通。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，所述色谱柱系统内设有定量管，所述定量管用于暂时存放进入色谱柱系统的待分析天然气气体，实现对使用色谱柱系统进行含硫化合物分离的待分析天然气气体的定量化。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，所述色谱柱系统内设有十通阀，通过十通阀控制色谱柱中各部件之间可控制连通关系的通断；
更优选地，十通阀顺时针设有第一阀口、第二阀口、第三阀口、第四阀口、第五阀口、第六阀口、第七阀口、第八阀口、第九阀口和第十阀口；十通阀为可调节阀，通过十通阀档位控制，可实现其中一个档位第一阀口与第二阀口连通、第三阀口与第四阀口连通、第五阀口与第六阀口连通、第七阀口与第八阀口连通、第九阀口与第十阀口连通，其中另一个档位第十阀口与第一阀口连通、第二阀口第三阀口连通、第四阀口与第五阀口连通、第六阀口与第七阀口连通、第八阀口与第九阀口连通；十通阀第十阀口与第九阀口中的一个与减压系统的输出端口通过第三输送管道连通，待分析天然气气体经十通阀第十或第九阀口进入，十通阀第十阀口与第九阀口中的另一个用于排出多余气体；十通阀第一阀口与十通阀第八阀口之间设有定量管用于暂时存放待分析天然气气体实现待分析天然气气体定量化，十通阀第一阀口通过定量管与十通阀第八阀口连通；载气输入管路与十通阀第二阀口连通；沸点柱设在十通阀第四阀口与十通阀第七阀口之间，使得十通阀第四阀口通过沸点柱与十通阀第七阀口连通；硫柱设在十通阀第三阀口与十通阀第六阀口之间，使得十通阀第三阀口通过硫柱与十通阀第六阀口连通；十通阀第五阀口与火焰光度检测仪连通；
在一具体实施方式中，十通阀顺时针设有第一阀口、第二阀口、第三阀口、第四阀口、第五阀口、第六阀口、第七阀口、第八阀口、第九阀口和第十阀口；十通阀为可调节阀，通过十通阀档位控制，可实现其中一个档位第一阀口与第二阀口连通、第三阀口与第四阀口连通、第五阀口与第六阀口连通、第七阀口与第八阀口连通、第九阀口与第十阀口连通，其中另一个档位第十阀口与第一阀口连通、第二阀口第三阀口连通、第四阀口与第五阀口连通、第六阀口与第七阀口连通、第八阀口与第九阀口连通；减压系统的输出端口与十通阀第十阀口通过第三输送管道连通，待分析天然气气体经十通阀第十阀口进入；十通阀第九阀口用于排出多余气体；十通阀第一阀口与十通阀第八阀口之间设有定量管用于暂时存放待分析天然气气体实现待分析天然气气体定量化，十通阀第一阀口通过定量管与十通阀第八阀口连通；载气输入管路与十通阀第二阀口连通；沸点柱设在十通阀第四阀口与十通阀第七阀口之间，使得十通阀第四阀口通过沸点柱与十通阀 第七阀口连通；硫柱设在十通阀第三阀口与十通阀第六阀口之间，使得十通阀第三阀口通过硫柱与十通阀第六阀口连通；十通阀第五阀口与火焰光度检测仪连通；
在一具体实施方式中，十通阀顺时针设有第一阀口、第二阀口、第三阀口、第四阀口、第五阀口、第六阀口、第七阀口、第八阀口、第九阀口和第十阀口；十通阀为可调节阀，通过十通阀档位控制，可实现其中一个档位第一阀口与第二阀口连通、第三阀口与第四阀口连通、第五阀口与第六阀口连通、第七阀口与第八阀口连通、第九阀口与第十阀口连通，其中另一个档位第十阀口与第一阀口连通、第二阀口第三阀口连通、第四阀口与第五阀口连通、第六阀口与第七阀口连通、第八阀口与第九阀口连通；减压系统的输出端口与十通阀第九阀口通过第三输送管道连通，待分析天然气气体经十通阀第九阀口进入；十通阀第十阀口用于排出多余气体；十通阀第一阀口与十通阀第八阀口之间设有定量管用于暂时存放待分析天然气气体实现待分析天然气气体定量化，十通阀第一阀口通过定量管与十通阀第八阀口连通；载气输入管路与十通阀第二阀口连通；沸点柱设在十通阀第四阀口与十通阀第七阀口之间，使得十通阀第四阀口通过沸点柱与十通阀第七阀口连通；硫柱设在十通阀第三阀口与十通阀第六阀口之间，使得十通阀第三阀口通过硫柱与十通阀第六阀口连通；十通阀第五阀口与火焰光度检测仪连通。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，所述沸点柱选用角鲨烷色谱柱。更优选地，所述沸点柱的长度不低于0.8m，进一步优选为0.6m。该优选技术方案利于天然气中含硫化合物的分离。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，所述硫柱选用氧二丙腈色谱柱。更优选地，所述硫柱的长度不低于1.7m。该优选技术方案利于天然气中含硫化合物的分离。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，该天然气中含硫化合物含量的火焰光度在线检测的系统进一步包括显示器，所述显示器固定连接在所述火焰光度检测仪上，所述显示器与所述火焰光度检测仪电连接，所述显示器显示所述火焰光度检测仪的检测结果。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，该天然气中含硫化合物含量的火焰光度在线检测的系统进一步包括报警联动装置和可燃气体检测报警仪，所述报警联动装置和所述可燃气体检测报警仪均与所述火焰光度检测仪电连接，可燃气体检测报警仪用于检测火焰光度检测仪附近是否发生可燃气体泄漏，从而避免出现安全隐患；报警联动装置为控制器，当可燃气体检测报警仪检测到出现可燃气体泄漏时，将及时关闭第一输送管道使得待检测气体停止输送过来检测，避免进一步安全 事故；
采用上述进一步方案的有益效果是：避免出现可燃气体泄漏，避免出现安全事故。
在上述天然气中含硫化合物含量的火焰光度在线检测的系统中，优选地，该天然气中含硫化合物含量的火焰光度在线检测的系统进一步包括标准气体物质存储瓶，所述标准气体物质存储瓶与所述色谱柱系统之间设有标准气体物质输送管，所述标准气体物质输送管的一端与所述色谱柱系统的输入端口连通，另一端与所述标准气体物质存储瓶的输出端口连通，所述标准气体物质输送管上设有第二阀门，通过所述第二阀门打开或关闭所述标准气体物质输送管；
该优选技术方案便于在每批次或者每天采用标准气体物质进行校正，从而能够进一步提高对待分析天然气气体含硫化合物的检测准确率。
本发明提供了一种天然气中含硫化合物含量的火焰光度在线检测的方法，其中，该方法包括：
S1、取含硫化合物标准气体物质，检测含硫化合物标准气体物质中的含硫化合物含量，得到含硫化合物含量标准曲线；
S2、采用取样装置获取天然气管道中输送的天然气，将天然气输送至减压系统进行降压得到减压天然气；
S3、将步骤S2得到的减压天然气输送至色谱柱系统，在载气带动下减压天然气依次使用沸点柱和硫柱进行分离，分离得到的组分输送到火焰光度检测仪中经火焰光度检测仪燃烧检测，获得检测图谱；
S4、步骤S2中直至天然气中的羰基硫(即氧硫化碳)组分离开硫柱后，载气转接至硫柱的输入端口，硫柱输出端口与沸点柱输入端口连通，沸点柱输出端口与火焰光度检测仪的输入端口连通，在载气的带动下剩余组分继续使用色谱柱系统进行分离，沸点柱输出端口分离得到的组分输送到火焰光度检测仪中经火焰光度检测仪燃烧检测，获得检测图谱；
S5、根据步骤S3、S4得到的检测图谱获取得到响应峰面积值数据，与步骤S1得到的含硫化合物含量标准曲线，得出天然气中含硫化合物含量。
本发明提供的天然气中含硫化合物含量的火焰光度在线检测的方法能够对天然气进行在线含硫化合物检测，检测操作简单，只需要简单计算即可得出天然气中含硫化合物的含量，使得企业可自行进行操作，不需要专门送检到实施室检测，减轻了企业的生产成本，同时加快了对天然气中含硫化合物的检测效率，提高了对天然气中含硫化合物的检测精度。
在上述天然气中含硫化合物含量的火焰光度在线检测的方法中，步骤S3中，在载气带动下减压天然气依次使用沸点柱和硫柱进行分离，含硫化合物中的硫化氢、羰基硫、甲硫醇、乙硫醇依次从沸点柱排出(其中硫化氢和羰基硫组分之间几乎时间差极小)进入硫柱进行分离进一步加大各组分之间的分离时间差，硫化氢、羰基硫依次从硫柱中排出后进入火焰光度检测仪中经火焰光度检测仪燃烧检测。步骤S4中，直至天然气中的羰基硫组分离开硫柱后(此时，乙硫醚组分即将排出沸点柱)，载气转接至硫柱的输入端口，硫柱输出端口与沸点柱输入端口连通，沸点柱输出端口与火焰光度检测仪的输入端口连通，在载气的带动下剩余组分继续使用色谱柱系统进行分离，乙硫醚、正丁硫醇、甲硫醇、乙硫醇组分依次从沸点柱中排出后进入火焰光度检测仪中经火焰光度检测仪燃烧检测。整个分离过程中，天然气中的部分组分如硫化氢、羰基硫组分依次使用一次沸点柱和一次硫柱进行分离，天然气中的部分组分如甲硫醇、乙硫醇组分使用两次沸点柱和一次硫柱进行分离具体为依次使用沸点柱、硫柱和沸点柱进行分离，天然气中的部分组分如乙硫醚、正丁硫醇组分仅使用一次沸点柱进行分离。
在上述天然气中含硫化合物含量的火焰光度在线检测的方法中，优选地，步骤S2得到的减压天然气的压力为0.18-0.25MPa(例如0.2MPa)。在一具体实施方式中，获取的天然气管道中输送的天然气经所述第一输送管道输送至一级减压部件，经所述一级减压部件将天然气的压力降至1.8-2.5MPa(例如2MPa)，再经所述第二输送管道输送至二级减压部件，经所述二级减压部件将天然气的压力降至0.18-0.25MPa(例如0.2MPa)，得到减压天然气。
在上述天然气中含硫化合物含量的火焰光度在线检测的方法中，优选地，使用硫柱进行分离时，硫柱的工作温度为55-65℃(例如62℃)。
在上述天然气中含硫化合物含量的火焰光度在线检测的方法中，优选地，使用沸点柱进行分离时，沸点柱的工作温度为65-75℃(例如70℃)。
在上述天然气中含硫化合物含量的火焰光度在线检测的方法中，优选地，载气使用氮气。
在上述天然气中含硫化合物含量的火焰光度在线检测的方法中，优选地，载气的流速为22ml/min。
在上述天然气中含硫化合物含量的火焰光度在线检测的方法中，优选地，分离得到的组分输送到火焰光度检测仪中经火焰光度检测仪燃烧检测通过下述方式实现：
分离得到的组分输送到火焰光度检测仪，充入压力为0.24MPa、流速为40ml/min的氢气以及压力为0.24MPa、流速为80ml/min的空气，在150℃下使用火焰光度检测仪 燃烧检测。
在上述天然气中含硫化合物含量的火焰光度在线检测的方法中，优选地，所述取含硫化合物标准气体物质，检测含硫化合物标准气体物质中的含硫化合物含量，得到含硫化合物含量标准曲线，包括以下步骤：
步骤S11：取硫化氢、羰基硫、甲硫醇、乙硫醇、乙硫醚和正丁硫醇与甲烷共同配置标准气体物质，至少取4组含硫化合物浓度不同的标准气体物质；
步骤S12：对步骤S11得到各标准气体物质检测，获得对应响应峰面积值数据，以各含硫化合物的浓度为纵坐标，以各含硫化合物的对应响应峰面积值为横坐标，绘制得到各含硫化合物含量标准曲线；
其中，标准气体物质中选用的含硫化合物基于待检测天然气中含硫化合物的种类进行确定即可；
标准气体物质一般有一个大量组分是作为底气的，天然气中硫化合物标准气体物质，在配置时是以天然气中实际组分为参照的；天然气中大量组分是甲烷，所以在配置硫化合物标准气体物质时，以甲烷作为底气或补充气获得特定含量的硫化合物标准气体物质；
采用该优选技术方案更有利于计算出天然气中含硫化合物含量。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单的介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图：
图1为本发明一实施例提供的天然气中含硫化合物含量的火焰光度在线检测的系统的结构示意图。
图2为本发明一实施例中一级减压部件的结构示意图。
图3为本发明一实施例中二级减压部件的结构示意图。
图4A为本发明一实施例中十通阀连接结构示意图。
图4B为本发明一实施例中十通阀连接结构示意图。
图4C为本发明一实施例中十通阀连接结构示意图。
图4D为本发明一实施例中十通阀连接结构示意图。
图5A-图5J为本发明一实施例中天然气中含硫化合物含量的火焰光度在线检测的 系统工作流程示意图。
图6A为本发明一实施例中硫化氢的标准曲线图。
图6B为本发明一实施例中氧硫化碳的标准曲线图。
图6C为本发明一实施例中甲硫醇的标准曲线图。
图6D为本发明一实施例中乙硫醇的标准曲线图。
图6E为本发明一实施例中乙硫醚的标准曲线图。
图6F为本发明一实施例中正丁硫醇的标准曲线图。
主要附图标号说明：
1天然气管道；2检测口；3安装座；4取样探头；5第一输送管道；6第一阀门；7循环伴热管；8一级减压部件；9第二输送管道；10二级减压部件；11一级加热管；12二级加热管；13第三输送管道；14火焰光度检测仪；15标准气体物质存储瓶；16标准气体物质输送管；17排气管；18可燃气体检测报警仪；19报警联动装置；20供电箱；21一级减压箱；22一级保温层；23第一加热膜式减压器；24第一热气管；25第二热气管；26第一压力表；27第一连通管；28第二加热膜式减压器；29第二压力表；30二级减压箱；31二级保温层；32第三热气管；33报警器；34旋钮式减压器；35第二连通管；36第三压力表；38色谱柱系统；39显示器；40沸点柱；41硫柱；42第一阀口；43第二阀口；44第三阀口；45第四阀口；46第五阀口；47第六阀口；48第七阀口；49第八阀口；50第九阀口；51第十阀口；52一级排出管；53二级排出管；54定量管。
具体实施方式
为使本发明实施例的目的技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚完整的描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明的保护范围。
下面参考本发明的若干代表性实施方式，详细阐述本发明的原理和精神。
实施例
如图1-图4D所示，本实施例提供天然气中含硫化合物含量的火焰光度在线检测的系统，该系统包括：取样装置、减压系统、色谱柱系统38和火焰光度检测仪(FPD) 14；期中色谱柱系统38设有载气输入管路且色谱柱系统38内设有色谱柱，色谱柱包括沸点柱40和硫柱41(例如，色谱柱由沸点柱40和硫柱41组成)。
取样装置的取样端置于天然气管道1中，在线获取天然气管道1中输送的天然气，天然气管道1中的天然气随着天然气输送动力部分进入到取样装置中。
取样装置与减压系统之间设有第一输送管道5，第一输送管道5的一端与取样装置的输出端口固定连接并连通，另一端与减压系统的输入端口固定连接并连通，从而取样装置获取的天然气经第一输送管道5进入到减压系统进行减压处理。
色谱柱系统38与减压系统之间设有第三输送管道13，第三输送管道13的一端与减压系统的输出端口固定连接并连通，另一端与色谱柱系统38的输入端口固定连接并连通，色谱柱系统38的输入端口与沸点柱40的输入端口通过可控制通断的连接管路连通，沸点柱40的输入端口、硫柱41的输入端口分别与载气输入管路通过可控制通断的连接管路连通，沸点柱40输出端口与硫柱41输入端口通过可控制通断的连接管路连通，硫柱41输出端口与沸点柱40输入端口通过可控制通断的连接管路连通，沸点柱40输出端口、硫柱41输出端口分别与火焰光度检测仪14的输入端口通过可控制通断的连接管路连通。经减压处理后的天然气进入到色谱柱系统38中，在色谱柱系统38中随着载气作用下进行分离。
火焰光度检测仪14用以将各个组分进行燃烧，检测透光率并转化为电信号从而检测出待分析天然气气体中含硫化合物的含量；天然气中分离出来的化合物在火焰光度检测仪14中燃烧检测。火焰光度检测仪14为已知的仪器，一种高灵敏度，仅对含硫、磷的有机物产生检测信号的高选择性检测器。其检测硫的原理：在富氢火焰中，含硫有机物燃烧后发出特征的蓝紫色光，波长为350nm-430nm，最大强度为394nm，经滤光片滤光，再由光电倍增管测量特征光的强度变化，转变成电信号，就可检测硫的含量。
优选地，本实施例中，取样装置包括安装座3和取样探头4，取样探头4固定连接在安装座3上，取样探头4上设有自伴热式减压器，取样探头4与第一输送管道5连通，安装座3安装到天然气管道1上，其中天然气管道1上设有检测口2，其中安装座3和检测口2设有连接法兰，通过连接法兰能够方便连接，取样探头4置于天然气管道1内，其中取样探头4与第一输送管道5连通，天然气管道1中的天然气自行进入到取样探头4中，再进入到第一输送管道5中。
优选地，本实施例中，第一输送管道5上内设有第一阀门6和过滤网；第一阀门6安装在第一输送管道5上，通过第一阀门6打开或关闭第一输送管道5，其中第一阀门6为电磁阀，能够通过电信号控制，从而操作更方便；过滤网为120目-160目过滤网， 能够过滤掉天然气中含有的颗粒杂质。
优选地，本实施例中，减压系统包括一级减压部件8和二级减压部件10；一级减压部件8与取样装置之间设有第一输送管道5，第一输送管道5的一端与取样装置的输出端口固定连接并连通，另一端与作为减压系统的输入端口的一级减压部件8的输入端口固定连接并连通，从而取样装置获取的天然气经第一输送管道5进入到一级减压部件8进行减压处理。二级减压部件10与一级减压部件8之间设有第二输送管道9，第二输送管道9的一端与一级减压部件8的输出端口固定连接并连通，另一端与二级减压部件10的输入端口固定连接并连通，天然气经一级减压部件8减压后再进入到二级减压部件10进行二次减压。
优选地，本实施例中，如图2所示，一级减压部件8包括一级减压箱21、一级保温层22、第一加热膜式减压器23、第二加热膜式减压器28、第一压力表26和第二压力表29，一级保温层22铺贴在一级减压箱21的内壁上，第一加热膜式减压器23、第二加热膜式减压器28、第一压力表26和第二压力表29均设在一级减压箱21内，第一加热膜式减压器23与第二加热膜式减压器28之间设有第一连通管27，第一连通管27的一端与第一加热膜式减压器23的输出端口连通，另一端与第二加热膜式减压器28的输入端口连通，第一压力表26安装在第一连通管27上，并与第一连通管27连通，第一输送管道5的另一端穿入一级减压箱21内，并与第一加热膜式减压器23的输入端口连通，第二输送管道9的一端穿入一级减压箱21内，并与第二加热膜式减压器28的输出端口连通，第二压力表29安装到第二输送管道9，并与第二输送管道9连通。通过第一压力表26观察经第一加热膜式减压器23对天然气的减压效果，从而得到实时天然气的压力。通过第二压力表29观察经第二加热膜式减压器28对天然气的减压效果，从而得到实时天然气的压力，调节减压效果，从而增加对天然气检测的准确度。其中第一加热膜式减压器23、第二加热膜式减压器28、第一压力表26和第二压力表29均为现有设备。其中一级保温层22为高分子保温材料制成。
优选地，本实施例中，如图3所示，二级减压部件10包括二级减压箱30、二级保温层31、旋钮式减压器34、第二连通管35和第三压力表36，二级保温层31铺贴在二级减压箱30的内壁上，旋钮式减压器34、第二连通管35和第三压力表36均设在二级减压箱30内，第二输送管道9的另一端穿入二级减压箱30，并与旋钮式减压器34的输入端口连通，第二连通管35的一端与旋钮式减压器34的输出端口连通，另一端与第三压力表36的一端连通，第三输送管道13的一端与第三压力表36另一端连通。其中通过第三压力表36检测经旋钮式减压器34减压后的天然气的压力，从而控制天然气的流 速，使得天然气中含硫化合物含量检测更准确。其中二级保温层31为高分子材料制成，其中第三压力表36和旋钮式减压器34为现有技术。
优选地，本实施例中，二级减压箱30内还设有报警器33，通过报警器33能够检测是否出现天然气泄漏的情况发生，能够及时发出警报。
优选地，本实施例中，还包括循环伴热管7，循环伴热管7用于供应高温气体，循环伴热管7与一级减压部件8之间设有一级加热管11和一级排出管52；一级加热管11的一端与循环伴热管7连通，另一端与一级减压部件8的伴热组件入口连通；一级排出管52的一端与一级减压部件8的伴热组件出口连通，一级排出管52的另一端与循环伴热管7连通；其中一级加热管11的一端分别连接有第一热气管24和第二热气管25，第一热气管24与第一加热膜式减压器23的伴热部入口连通，第二热气管25与第二加热膜式减压器28的伴热部入口连通，从而对第一加热膜式减压器23和第二加热膜式减压器28加热，从而防止天然气减压过程产生冷凝，一级排出管52分别与第一加热膜式减压器23的伴热部出口连通和第二加热膜式减压器28的伴热部出口连通。循环伴热管7与二级减压部件10之间设有二级加热管12和二级排出管53；二级加热管12的一端与循环伴热管7连通，另一端与二级减压部件10的伴热组件入口连通；二级排出管53的一端与二级减压部件10的伴热组件出口连通，二级排出管53的另一端与循环伴热管7连通；其中二级减压箱30内设有第三热气管32，第三热气管32的一端与二级加热管12连接并连通，第三热气管32的另一端与旋钮式减压器34的伴热部入口连通，防止天然气减压过程产生冷凝，二级排出管53与旋钮式减压器34的伴热部出口连通。
由于含含硫化合物极易吸附到各种材质上或与之发生化学反应，因此取样探头、安装座3、第一阀门6、第一输送管道5、第二输送管道9、第三输送管道13等都应由适当的硫惰性或钝化材料制成，选择的材料应与气体和取样方法相适应，取样装置的内部和外部条件应确保被取气体的组成不被降解和不改变气体的组成。其中取样探头设置在天然气管道1的位置应位于水平设置的天然气管道1处，同时不能处于拐角和中间部位，这样能够提高对天然气含硫化合物含量的检测准确率。
优选地，本实施例中，沸点柱40选用角鲨烷色谱柱，沸点柱的长度为0.8m；硫柱41选用氧二丙腈色谱柱，硫柱41的长度为1.7m。在一具体实施方式中，色谱柱系统38的基本参数如下表1：
表1色谱柱系统38配置参数
Figure PCTCN2022093508-appb-000001
Figure PCTCN2022093508-appb-000002
色谱柱系统内设有十通阀和定量管54，通过十通阀控制色谱柱中各连通部件之间的通断；
如图4A、图4B、图4C、图4D所示，十通阀顺时针设有第一阀口42、第二阀口43、第三阀口44、第四阀口45、第五阀口46、第六阀口47、第七阀口48、第八阀口49、第九阀口50和第十阀口51；十通阀为可调节阀，通过十通阀档位控制，可实现A档位(如图4A、图4C所示)第一阀口42与第二阀口43连通、第三阀口44与第四阀口45连通、第五阀口46与第六阀口47连通、第七阀口48与第八阀口49连通、第九阀口50与第十阀口51连通，B档位(如图4B、图4D所示)第十阀口51与第一阀口42连通、第二阀口43第三阀口44连通、第四阀口45与第五阀口46连通、第六阀口47与第七阀口48连通、第八阀口48与第九阀口49连通；
十通阀第十阀口51、第九阀口50中的一个与第三输送管道13连通，待分析天然气气体经十通阀第十阀口51或第九阀口50进入，十通阀第十阀口51与第九阀口50中的另一个用于排出多余气体；其中，如图4A、图4B所示，十通阀第十阀口51与第三输送管道13连通，待分析天然气气体经十通阀第十阀口51进入，十通阀第九阀口50用于排出多余气体；其中，如图4C、图4D所示，十通阀第九阀口50与第三输送管道13连通，待分析天然气气体经十通阀第九阀口50进入，十通阀第十阀口51用于排出多余气体；
十通阀第一阀口42与十通阀第八阀口49之间设有定量管54用于暂时存放待分析天然气气体实现待分析天然气气体定量化，十通阀第一阀口42通过定量管54与十通阀第八阀口49连通；载气输入管路与十通阀第二阀口43连通；沸点柱40设在十通阀第四阀口45与十通阀第七阀口48之间，使得十通阀第四阀口45通过沸点柱40与第七阀口48连通；硫柱设在十通阀第三阀口44与十通阀第六阀口47之间，使得十通阀第三阀口44通过硫柱与十通阀第六阀口47连通；十通阀第五阀口46与火焰光度检测仪14连通。
优选地，本实施例中，还包括标准气体物质存储瓶15，标准气体物质存储瓶15与色谱柱系统38之间设有标准气体物质输送管16，标准气体物质输送管16的一端与色谱柱系统38的输入端口连通，另一端与标准气体物质存储瓶15的输出端口连通，标准气 体物质输送管16上设有第二阀门，通过第二阀门打开或关闭标准气体物质输送管16，通过标准气体物质存储瓶15能够输送标准气体物质，便于在每批次或者每天采用标准气体物质进行校正，从而能够进一步提高对天然气含硫化合物的检测准确率。其中标准气体物质存储瓶15可为有硫惰性内涂层的容器。
优选地，本实施例中，还包括显示器39，显示器39固定连接在火焰光度检测仪14上，显示器39与火焰光度检测仪14电连接，显示器39显示火焰光度检测仪14的检测结果。
优选地，本实施例中，还包括报警联动装置19和可燃气体检测报警仪18，报警联动装置19和可燃气体检测报警仪18均与火焰光度检测仪14电连接，报警联动装置19与第一阀门6电连接。其中可燃气体检测报警仪18用于检测火焰光度检测仪14附近是否发生可燃气体泄漏，从而避免出现安全隐患，而报警联动装置19为控制器，当可燃气体检测报警仪18检测到出现可燃气体泄漏时，将及时关闭第一阀门6，使得天然气停止输送过来检测。避免进一步安全事故。
优选地，本实施例中，火焰光度检测仪14的侧壁上还设有排气管17，通过排气管17将燃烧后的烟气远距离排出，避免出现安全隐患。
优选地，本实施例中，还包括供电箱20，供电箱20与第一阀门6、火焰光度检测仪14、色谱柱系统38和显示器39电连接，用于供电。
本实施例还提供了一种天然气中含硫化合物含量的火焰光度在线检测的方法，其中，该方法包括：
步骤S1：获取校准曲线图谱：
步骤S101：将标准气体物质存储瓶储存的已知6种含硫化合物，具体为硫化氢、羰基硫、甲硫醇、乙硫醇、乙硫醚和正丁硫醇，与甲烷共同配置标准气体物质，共配置5组含硫化合物浓度不同的标准气体物质分别为1#、2#、3#、4#、5#，每组标准气体物质中各含硫化合物的浓度参见表2-表7；
步骤S102：通入到色谱柱系统38和火焰光度检测仪14中，对步骤S101得到标准气体物质进行检测，检测标准气体物质(即天然气标准样)中的含硫化合物含量，得到天然气标准样图谱(采用与下面步骤3相同的方式进行即可)。
步骤S103：根据显示器39获得天然气标准样图谱，根据图谱得到FPD的响应值，获得对应响应峰面积值数据，以各标准物的浓度为纵坐标，以各标准物的对应响应峰面积值为横坐标，绘制得到各含硫化合物含量标准曲线，结果参见图6A-图6F； 具体各标准物的浓度和对应响应峰面积值数据如下表2-表7。
表2为硫化氢组分的浓度与响应值对应值表
Figure PCTCN2022093508-appb-000003
表3为羰基硫组分的浓度与响应值对应值表
Figure PCTCN2022093508-appb-000004
表4为乙硫醚组分的浓度与响应值对应值表
Figure PCTCN2022093508-appb-000005
表5为正丁硫醇组分的浓度与响应值对应值表
Figure PCTCN2022093508-appb-000006
表6为甲硫醇组分的浓度与响应值对应值表
Figure PCTCN2022093508-appb-000007
表7为乙硫醇组分的浓度与响应值对应值表
Figure PCTCN2022093508-appb-000008
S2、采用取样探头获取天然气管道1中输送的天然气，经过过滤网过滤掉颗粒杂质后，经第一输送管道5输送至一级减压部件8，经一级减压部件8中的第一加热膜式减压器23和第二加热膜式减压器28双重降压作用下，将天然气的压力降至2MPa，再经第二输送管道9输送至二级减压部件10，经二级减压部件10中的旋钮式减压器34将天然气的压力降至0.2MPa，得到减压天然气。
S3、将步骤S2得到的减压天然气经第三输送管道13输送至色谱柱系统38中(减压天然气进入色谱柱系统38时的温度控制为45℃)，减压天然气在压力为0.24Mpa、流速为22ml/min的氮气带动下在色谱柱系统38中进行分离，将分离物输送到火焰光度检测仪14中进行燃烧检测，获得检测图谱(流程参见图5A-图5J)：
S301、将步骤S2得到的减压天然气经第三输送管道13输送至色谱柱系统38，此时十通阀处于B档(如图4B、图4D所示)，此时第十阀口51与第一阀口42连通、第二阀口43第三阀口44连通、第四阀口45与第五阀口46连通、第六阀口47与第七阀口48连通、第八阀口48与第九阀口49连通；
如图4B所示，减压天然气由第十阀口51进入，然后流动到第一阀口42，再进入定量管暂时存放，多余的减压天然气由第九阀口50排出；或者；如图4D所示，减压天 然气由第九阀口50进入，然后流动到第八阀口48，再进入定量管暂时存放，多余的减压天然气由第十阀口51排出。
S302、调节十通阀，使其处于A档(如图4A、图4C所示)，此时第一阀口42与第二阀口43连通、第三阀口44与第四阀口45连通、第五阀口46与第六阀口47连通、第七阀口48与第八阀口49连通、第九阀口50与第十阀口51连通；
采用压力为0.24MPa、流速为22ml/min的氮气注入到第二阀口3中，经第一阀口42进入到定量管中，将定量管中暂时存放的减压天然气带动流动，并依次经第八阀口49和第七阀口48后进入沸点柱40，在温度为70℃的沸点柱40中进行分离，由于各含硫化合物沸点不同，从而形成流速区别，不同的含硫化合物先后依次在载气氮气的作用下进入第四阀口45，并经第三阀口44进入到硫柱41中，在温度为68℃的硫柱41中进行再一次的分离，含硫化合物中的硫化氢、羰基硫组分依次离开硫柱，依次经过第六阀口47、第五阀口46进入火焰光度检测仪14中进行燃烧检测，获得图谱；其中天然气进入色谱柱系统38时的温度控制为45℃。
S303、当天然气中的羰基硫组分离开硫柱后，调节十通阀，使十通阀处于B档(如图4B、图4D所示)，此时第十阀口51与第一阀口42连通、第二阀口43第三阀口44连通、第四阀口45与第五阀口46连通、第六阀口47与第七阀口48连通、第八阀口48与第九阀口49连通；
采用压力为0.24MPa、流速为22ml/min的氮气注入到第二阀口3中，经第三阀口43进入到硫柱41中，带动硫柱41中天然气的残留组分继续进行分离，与此同时沸点柱40中的残留组分乙硫醚、正丁硫醇继续进行分离并依次离开沸点柱40；含硫化合物中的甲硫醇、乙硫醇组分依次离开硫柱41再次进入沸点柱40进行分离；最终按照乙硫醚、正丁硫醇、甲硫醇、乙硫醇顺序依次离开沸点柱40；离开沸点柱40的组分依次经过第四阀口45、第五阀口46进入火焰光度检测仪14中进行燃烧检测，获得图谱；
其中，使用火焰光度检测仪14进行燃烧检测通过下述方式实现：向火焰光度检测仪14中输送压力为0.24MPa、流速为40ml/min的氢气和压力为0.24MPa、流速为80ml/min的空气，在150℃下，经火焰光度检测仪14燃烧检测，获得检测图谱；其中氢气为燃气，空气为助燃气。
S4根据步骤S3到的检测图谱获取得到响应峰值数据，与步骤S1得到的各含硫化合物含量标准曲线，带入响应峰值数据，从图中读出天然气中含硫化合物含量。
从而获得天然气中含硫化合物含量。其中天然气中总硫含量为各个不同含硫化合物含量浓度的加和。
本在线检测方法误差值≤5％，符合误差范围内，说明本天然气中含硫化合物含量的火焰光度在线检测系统能够有效的在线检测天然气中含硫化合物含量，并且具有较高的检测精度。
本发明中应用了具体实施例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。

Claims (27)

  1. 一种天然气中含硫化合物含量的火焰光度在线检测的系统，其中，该系统包括：
    取样装置、减压系统、色谱柱系统和火焰光度检测仪；
    所述色谱柱系统设有载气输入管路且色谱柱系统内设有色谱柱，所述色谱柱包括沸点柱和硫柱；
    所述取样装置的输出端口通过第一输送管道与所述减压系统的输入端口连通，所述减压系统的输出端口与所述沸点柱的输入端口通过可控制通断的连接管路连通，所述沸点柱的输入端口、所述硫柱的输入端口分别与所述载气输入管路通过可控制通断的连接管路连通，所述沸点柱输出端口与所述硫柱输入端口通过可控制通断的连接管路连通，所述硫柱输出端口与所述沸点柱输入端口通过可控制通断的连接管路连通，所述沸点柱输出端口、所述硫柱输出端口分别与火焰光度检测仪的输入端口通过可控制通断的连接管路连通。
  2. 根据权利要求1所述的系统，其中，所述取样装置包括安装座和取样探头，所述取样探头固定连接在所述安装座上，所述取样探头与所述第一输送管道连通；通过所述安装座安装到天然气管道上能够实现将取样装置固定到天然气管道上从而通过置于所述天然气管道内的取样探头实现对天然气管道中的天然气进行在线获取。
  3. 根据权利要求2所述的系统，其中，所述取样探头上设有自伴热式减压器。
  4. 根据权利要求1-3任一项所述的系统，其中，所述第一输送管道上设有第一阀门，通过所述第一阀门打开或关闭所述第一输送管道。
  5. 根据权利要求1-3任一项所述的系统，其中，所述第一输送管道内设有过滤网。
  6. 根据权利要求1所述的系统，其中，所述减压系统包括依次连接的一级减压部件和二级减压部件，所述二级减压部件的输入端口与所述一级减压部件的输出端口通过第二输送管道连通；所述一级减压部件的输入端口作为所述减压系统的输入端口与所述取样装置的输出端口通过所述第一输送管道连通；所述二级减压部件的输出端口作为所述减压系统的输出端口与所述沸点柱的输入端口通过可控制通断的连接管路连通。
  7. 根据权利要求6所述的系统，其中，所述一级减压部件包括一级减压箱、第一加热膜式减压器、第二加热膜式减压器、第一压力表和第二压力表，所述第一加热膜式减压器、所述第二加热膜式减压器、所述第一压力表和所述第二压力表均设在所述一级减压箱内；所述第一加热膜式减压器与所述第二加热膜式减压器之间设有第一连通管，所述第一连通管的一端与所述第一加热膜式减压器的输出端口连通，另一端与所述第二加热膜式减压器的输入端口连通；所述第一压力表安装在所述第一连通管上，并与所述第 一连通管连通；所述第一输送管道的另一端穿入所述一级减压箱内，并与所述第一加热膜式减压器的输入端口连通；所述第二输送管道的一端穿入所述一级减压箱内，并与所述第二加热膜式减压器的输出端口连通，所述第二压力表安装到所述第二输送管道，并与所述第二输送管道连通。
  8. 根据权利要求7所述的系统，其中，所述一级减压部件进一步包括一级保温层，所述一级保温层铺贴在所述一级减压箱的内壁上。
  9. 根据权利要求6所述的系统，其中，所述二级减压部件包括二级减压箱、旋钮式减压器、第二连通管和第三压力表，所述旋钮式减压器、所述第二连通管和所述第三压力表均设在所述二级减压箱内；所述第二输送管道的一端穿入所述二级减压箱，并与所述旋钮式减压器的输入端口连通，所述第二连通管的一端与所述旋钮式减压器的输出端口连通，另一端与所述第三压力表的一端连通，所述第三压力表另一端作为所述二级减压部件的输出端口与所述沸点柱的输入端口通过可控制通断的连接管路连通。
  10. 根据权利要求9所述的系统，其中，所述二级减压部件进一步包括二级保温层，所述二级保温层铺贴在所述二级减压箱的内壁上。
  11. 根据权利要求1、6-10中任一项所述的系统，其中，该天然气中含硫化合物含量的火焰光度在线检测的系统进一步包括循环伴热管，所述减压系统进一步设有伴热组件，所述循环伴热管与所述减压系统的伴热组件连通，用以对减压系统中的待分析天然气气体进行加热。
  12. 根据权利要求1所述的系统，其中，所述色谱柱系统内设有定量管，所述定量管用于暂时存放进入色谱柱系统的待分析天然气气体，实现对使用色谱柱系统进行含硫化合物分离的待分析天然气气体的定量化。
  13. 根据权利要求12所述的系统，其中，所述色谱柱系统内设有十通阀，通过十通阀控制色谱柱中各部件之间可控制连通关系的通断。
  14. 根据权利要求13所述的系统，其中，十通阀顺时针设有第一阀口、第二阀口、第三阀口、第四阀口、第五阀口、第六阀口、第七阀口、第八阀口、第九阀口和第十阀口；十通阀为可调节阀，通过十通阀档位控制，可实现其中一个档位第一阀口与第二阀口连通、第三阀口与第四阀口连通、第五阀口与第六阀口连通、第七阀口与第八阀口连通、第九阀口与第十阀口连通，其中另一个档位第十阀口与第一阀口连通、第二阀口第三阀口连通、第四阀口与第五阀口连通、第六阀口与第七阀口连通、第八阀口与第九阀口连通；十通阀第十阀口与第九阀口中的一个与减压系统的输出端口通过第三输送管道连通，十通阀第十阀口与第九阀口中的另一个用于排出多余气体；十通阀第一阀口与十 通阀第八阀口之间设有定量管用于暂时存放待分析天然气气体实现待分析天然气气体定量化，十通阀第一阀口通过定量管与十通阀第八阀口连通；载气输入管路与十通阀第二阀口连通；沸点柱设在十通阀第四阀口与十通阀第七阀口之间，使得十通阀第四阀口通过沸点柱与十通阀第七阀口连通；硫柱设在十通阀第三阀口与十通阀第六阀口之间，使得十通阀第三阀口通过硫柱与十通阀第六阀口连通；十通阀第五阀口与火焰光度检测仪连通。
  15. 根据权利要求1、12-14中任一项所述的系统，其中，所述沸点柱选用角鲨烷色谱柱。
  16. 根据权利要求15所述的系统，其中，所述沸点柱的长度不低于0.8m。
  17. 根据权利要求1、12-14中任一项所述的系统，其中，所述硫柱选用氧二丙腈色谱柱。
  18. 根据权利要求17所述的系统，其中，所述硫柱的长度不低于1.7m。
  19. 根据权利要求1所述的系统，其中，天然气中含硫化合物含量的火焰光度在线检测的系统进一步包括显示器，所述显示器固定连接在所述火焰光度检测仪上，所述显示器与所述火焰光度检测仪电连接，所述显示器显示所述火焰光度检测仪的检测结果。
  20. 根据权利要求1所述的系统，其中，天然气中含硫化合物含量的火焰光度在线检测的系统进一步包括报警联动装置和可燃气体检测报警仪，所述报警联动装置和所述可燃气体检测报警仪均与所述火焰光度检测仪电连接，可燃气体检测报警仪用于检测火焰光度检测仪附近是否发生可燃气体泄漏；报警联动装置为控制器，当可燃气体检测报警仪检测到出现可燃气体泄漏时，将及时关闭第一输送管道使得待检测气体停止输送过来检测。
  21. 根据权利要求1所述的系统，其中，天然气中含硫化合物含量的火焰光度在线检测的系统进一步包括标准气体物质存储瓶，所述标准气体物质存储瓶与所述色谱柱系统之间设有标准气体物质输送管，所述标准气体物质输送管的一端与所述色谱柱系统的输入端口连通，另一端与所述标准气体物质存储瓶的输出端口连通，所述标准气体物质输送管上设有第二阀门，通过所述第二阀门打开或关闭所述标准气体物质输送管。
  22. 一种天然气中含硫化合物含量的火焰光度在线检测的方法，该方法采用如权利要求1-21任一项所述的天然气中含硫化合物含量的火焰光度在线检测的系统进行，其中，该方法包括：
    S1、取含硫化合物标准气体物质，检测含硫化合物标准气体物质中的含硫化合物含量，得到含硫化合物含量标准曲线；
    S2、采用取样装置获取天然气管道中输送的天然气，将天然气输送至减压系统进行降压得到减压天然气；
    S3、将步骤S2得到的减压天然气输送至色谱柱系统，在载气带动下减压天然气依次使用沸点柱和硫柱进行分离，分离得到的组分输送到火焰光度检测仪中经火焰光度检测仪燃烧检测，获得检测图谱；
    S4、步骤S2中直至天然气中的羰基硫组分离开硫柱后，载气转接至硫柱的输入端口，硫柱输出端口与沸点柱输入端口连通，沸点柱输出端口与火焰光度检测仪的输入端口连通，在载气的带动下剩余组分继续使用色谱柱系统进行分离，沸点柱输出端口分离得到的组分输送到火焰光度检测仪中经火焰光度检测仪燃烧检测，获得检测图谱；
    S5、根据步骤S3、S4得到的检测图谱获取得到响应峰面积值数据，与步骤S1得到的含硫化合物含量标准曲线，得出天然气中含硫化合物含量。
  23. 根据权利要求22所述的方法，其中，使用硫柱进行分离时，硫柱的工作温度为55-65℃。
  24. 根据权利要求23所述的方法，其中，使用硫柱进行分离时，硫柱的工作温度为62℃。
  25. 根据权利要求22所述的方法，其中，使用沸点柱进行分离时，沸点柱的工作温度为65-75℃。
  26. 根据权利要求25所述的方法，其中，使用沸点柱进行分离时，沸点柱的工作温度为70℃。
  27. 根据权利要求22所述的方法，其中，所述取含硫化合物标准气体物质，检测含硫化合物标准气体物质中的含硫化合物含量，得到含硫化合物含量标准曲线，包括以下步骤：
    步骤S11：取硫化氢、羰基硫、甲硫醇、乙硫醇、乙硫醚和正丁硫醇与甲烷共同配置标准气体物质，至少取4组含硫化合物浓度不同的标准气体物质；
    步骤S12：对步骤S11得到各标准气体物质检测，获得对应响应峰面积值数据，以各含硫化合物的浓度为纵坐标，以各含硫化合物的对应响应峰面积值为横坐标，绘制得到各含硫化合物含量标准曲线。
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DE112022002640T5 (de) 2024-02-29
JP2024519902A (ja) 2024-05-21
CN115372485B (zh) 2024-01-12

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