CN109212047B - Analyzer for content of sulfur-containing compound in hydrocarbon gas - Google Patents
Analyzer for content of sulfur-containing compound in hydrocarbon gas Download PDFInfo
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Abstract
The invention relates to an analyzer for the content of sulfur-containing compounds in hydrocarbon gas, which comprises a first sample quantitative ring and a second sample quantitative ring which are connected in series, wherein the first sample quantitative ring is connected with a trace sulfur-containing compound detection unit, and the trace sulfur-containing compound detection unit comprises a first shunt sample inlet, a sulfur-containing compound analysis column, a current-limiting column and a sulfur selectivity detector which are sequentially connected in series; the second sample quantitative ring is connected with the high-concentration sulfur-containing compound detection unit, and the high-concentration sulfur-containing compound detection unit comprises a second shunt sample inlet, a nonpolar capillary chromatographic column, a flow path switching unit, a damping column, a thermal conductivity detector, a polar capillary chromatographic column and a hydrogen flame ionization detector. The analyzer can realize the qualitative result of the sulfur-containing compounds with wide concentration range in the gas by one-time sample introduction, and accordingly, the content of various sulfur-containing compounds can be obtained.
Description
Technical Field
The invention relates to a gas chromatographic analyzer, in particular to an analyzer for analyzing the content of sulfur-containing compounds in hydrocarbon gas.
Background
Sulfur compounds (hereinafter referred to as sulfides) in gas are usually the original poisons and deactivations of catalysts in the deep processing process, and the control and monitoring of sulfur content are very much concerned in various processes. The height of the device not only seriously affects the quality of subsequent products, but also has great harm to pipelines and storage containers. At present, when Liquefied Petroleum Gas (LPG) produced by various refineries is taken as civil fuel, the total sulfur content is required to be less than 343 multiplied by 10 according to the regulation of GB11174-2011 specification for LPG-6(volume fraction); when used as a polymer grade ethylene or propylene chemical material, the sulfur content (volume fraction) needs to be controlled at 1 x 10-6The following. In addition, with the continuous improvement of environmental protection regulations, the quality of petroleum products and the emission standard of the petroleum products in the production and use processes are strictly controlled, and after gasoline enters the national V era, the sulfur content of MTBE used as a gasoline additive is reduced to 10mg/kg from 50mg/kg of the national IV era. The product control indexes relate to the monitoring of sulfides in refinery gases, so that on one hand, from the viewpoints of safety, environmental protection and pipeline and equipment corrosion, the continuous improvement of the desulfurization technology is the subject of various refineries, and on the other hand, the improvement of the desulfurization technology depends on the progress of sulfide analysis methods to a great extent, which means that the development of deep research on the analysis methods of sulfides in various gases is increasingly important.
Currently, the gas chromatography/sulfur selectivity detector combined technology is mostly adopted for the analysis of the types of sulfur compounds in gas. This technique is widely used for trace amounts (single-component sulfide content less than 100X 10) in gas samples-6(volume fraction)) sulfide morphology detection.
Therefore, when the gas sample to be detected has a sample with high total sulfur content and widely distributed sulfide types, such as catalytic cracking process gas, coking process gas and other process gases, the method can perform qualitative analysis, but only can perform quantitative analysis on trace sulfur-containing compounds, and the sulfur content of a single component is more than 100 x 10-6(volume fraction) component, requiring flame ionization detectionChromatography with a detector (FID) or Thermal Conductivity Detector (TCD) results in a range of sulfur compound content from 10 in a sample-9About a few tens of percent, at least two instruments are needed to complete the analysis by sampling twice.
In summary, the conventional analysis apparatus and method cannot perform the type analysis of the sulfur-containing compounds in the gas sample with a wide concentration range on one chromatograph, and if a qualitative and quantitative analysis of one sample is required, at least two chromatographs are required for two sample injections.
Disclosure of Invention
The invention aims to provide an analyzer for content of sulfur-containing compounds in hydrocarbon gas, which can complete qualitative and quantitative analysis of volatile sulfur-containing compounds in gas only by one-time sample injection.
The invention provides an analyzer for the content of sulfur-containing compounds in hydrocarbon gas, which comprises a first sample quantitative ring and a second sample quantitative ring which are connected in series, wherein the first sample quantitative ring is connected with a trace sulfur-containing compound detection unit, and the trace sulfur-containing compound detection unit comprises a first shunt sample inlet, a sulfur-containing compound analysis column, a current-limiting column and a sulfur selectivity detector which are sequentially connected in series; second sample ration ring links to each other with the high concentration sulphur compound detecting element that contains, the high concentration sulphur compound detecting element includes second reposition of redundant personnel introduction port, non-polarity capillary chromatographic column, flow path switching unit, damping column, thermal conductivity detector, polarity capillary chromatographic column and hydrogen flame ionization detector, the second reposition of redundant personnel introduction port with non-polarity capillary chromatographic column connects, non-polarity capillary chromatographic column with the central interface of flow path switching unit links to each other, the interface of flow path switching unit one end with the damping column with the thermal conductivity detector connects gradually, the interface of the other end with polarity capillary chromatographic column with the hydrogen flame ionization detector connects gradually.
In the analyzer, a gas sample to be analyzed is collected through two sample quantitative rings which are connected in series, and then the gas sample is divided into two paths, wherein one path can be used for qualitative analysis of all sulfur-containing compounds in the sample and quantitative analysis of trace sulfur-containing compounds, an analysis column and a current-limiting column are connected, trace carbonyl sulfur and sulfur dioxide can be analyzed through a sulfur selectivity detector, the other path enables high-concentration sulfur-containing compounds in the sample to enter different chromatographic columns through a flow path switching unit to separate different sulfur-containing compounds, so that the high-concentration sulfur-containing compounds are separated one by one and detected, and finally, the separation and detection of various sulfur-containing compounds in the gas can be completed through one-time sample injection.
The analyzer has wide content range of the sulfur-containing compounds, can detect the content of various trace sulfur-containing compounds in the gas, and can detect hydrogen sulfide, methyl mercaptan and ethanethiol with high gas concentration.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a schematic diagram of a compositional analyzer for sulfur compounds in a gas over a wide range of concentrations in accordance with the present invention;
FIGS. 2 to 4 are chromatograms of sulfur-containing compounds measured in example 1 of the present invention.
Description of the reference numerals
1 first six-way switching valve 2 second six-way switching valve
3-flow control switch 4 sulfur compound analysis column
5 current limiting column 6 damping column
7 nonpolar capillary chromatographic column 8 polar capillary chromatographic column
9 first split sample inlet 10 second split sample inlet
11 sulfur selectivity detector 12 thermal conductivity detector
13 hydrogen flame ionization detector 14 first sample quantitative ring
15 second sample quantitative ring 16 sample feeding pipeline
17 first carrier gas line 20 emptying line
21 second carrier gas line 18,19,22,24 line
23 microplate flow path center cutting system 25 center interface
26 first interface 27 second interface
111,112,113,114,115,116 interface of first six-way switching valve
221,222,223,224,225,226 interface of second six-way switching valve
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The instrument detection is divided into a trace sulfur compound detection unit and a high-concentration sulfur compound detection unit, wherein the single-component sulfide detection range of the trace sulfur compound detection unit is 20 multiplied by 10-9～100×10-6(volume fraction), the single-component sulfide detection range of the high-concentration sulfur-containing compound detection unit is 0.01-10% (volume fraction).
As shown in fig. 1, the analyzer for content of sulfur-containing compounds in hydrocarbon gas according to the present invention includes a first sample quantitative ring 14 and a second sample quantitative ring 15 connected in series, where the first sample quantitative ring 14 is connected to a trace sulfur-containing compound detection unit, and the trace sulfur-containing compound detection unit includes a first split-flow sample inlet 9, a sulfur-containing compound analysis column 4, a current limiting column 5, and a sulfur selectivity detector 11 connected in series in sequence; second sample ration ring 15 links to each other with high concentration sulfur compound detecting element, high concentration sulfur compound detecting element includes that the second reposition of redundant personnel advances appearance mouth 10, nonpolar capillary chromatographic column 7, flow path switching unit, damping column 6, thermal conductivity detector 12, polarity capillary chromatographic column 8 and hydrogen flame ionization detector 13, second reposition of redundant personnel advances appearance mouth 10 with nonpolar capillary chromatographic column 7 is connected, nonpolar capillary chromatographic column 7 with flow path switching unit's central interface links to each other, flow path switching unit one end the interface with damping column 6 with thermal conductivity detector 12 connects gradually, the interface of the other end with polarity capillary chromatographic column 8 with hydrogen flame ionization detector 13 connects gradually.
In the invention, two sample quantitative rings are connected in series, so that the analysis of the sulfur-containing compounds in the gas is divided into two paths for carrying out, wherein the first path is a trace sulfur-containing compound detection unit, a sulfur-containing compound analysis column and a current limiting column are used, a sulfur selectivity detector is configured, and all the sulfur-containing compounds in the gas including hydrogen sulfide, carbonyl sulfide, sulfur dioxide and C are detected1-C5Thiol, C1-C7Thioether, thiophene, tetrahydrothiophene and the like, all sulfur-containing compounds can be characterized, and the detection range of a single sulfur-containing compound is 20 multiplied by 10-9-100×10-6(volume fraction), only qualitative but not quantitative results can be given for components above the upper limit of detection; the second path is a high-concentration sulfur-containing compound detection unit, the detection of hydrogen sulfide in the gas is completed by using a non-polar capillary chromatographic column and a damping column which are provided with a thermal conductivity detector, the detection of high-concentration methyl mercaptan and ethyl mercaptan is completed by using the non-polar capillary chromatographic column, a polar capillary chromatographic column and a hydrogen flame ionization detector, and the switching among the non-polar capillary chromatographic column, the damping column and the polar capillary chromatographic column is completed by using a flow path switching unit.
Preferably, the first sample quantification loop 14 and the second sample quantification loop 15 are connected in series by two six-way switching valves, and the series connection method is as follows: four interfaces of the first six-way switching valve 1 are connected into a first sample quantifying ring 14, the inlet end of the first sample quantifying ring 14 is connected with a sample feeding pipeline 16, the outlet end of the first sample quantifying ring 14 is connected with the second six-way switching valve 2 and serves as the inlet end of a second sample quantifying ring 15, four interfaces of the second six-way switching valve 2 are connected into the second sample quantifying ring 15, and the outlet end of the second sample quantifying ring 15 is connected with a vent pipeline 20. The invention uses six-way switching valve to divide the pipeline, the six-way switching valve only has two connection states of opening and closing, the gas passing through the valve can be divided into two paths, when the six-way valve is at one position, the gas flowing through the valve flows along one direction, the gas flows along the other direction by rotating the position of the valve, thereby the gas flowing into the valve can be divided into two working conditions by changing the position of the valve. One is used for feeding sample into the quantitative ring, and the other is used for introducing carrier gas carrying the sample for detection. The carrier gas is preferably helium.
In the invention, the trace sulfur compound detection unit and the high-concentration sulfur compound detection unit are both connected with a carrier gas pipeline, and a carrier gas carries a sample to flow, namely, the carrier gas pipeline is connected to the upstream of the sample quantification ring, so that the carrier gas enters the sample quantification ring, and the sample carried in the carrier gas flows through each analysis column and then enters the detector for detection.
The carrier gas inlet of the trace sulfur-containing compound detection unit is connected to the first six-way switching valve 1, the carrier gas outlet is sequentially connected in series with the first shunt sample inlet 9, the sulfur-containing compound analysis column 4 and the sulfur selectivity detector 11, and in order to analyze carbonyl sulfur and sulfur dioxide which cannot be separated by the sulfur-containing compound analysis column 4, the flow limiting column 5 is connected in series behind the sulfur-containing compound analysis column 4. In one embodiment, four ports of the first six-way switching valve 1 are connected to the first sample dosing ring 14, and the remaining two adjacent ports are connected, one port being connected to the first carrier gas line 17 and the other port being connected to the first split sample inlet 9.
A carrier gas inlet in the high-concentration sulfur-containing compound detection unit is connected to the second six-way switching valve 2, a carrier gas outlet is sequentially connected in series with the second split-flow sample inlet 10, the nonpolar capillary chromatographic column 7 and the flow path switching unit, a gas path is divided into two paths through the flow path switching unit, one path is sequentially connected in series with the damping column 6 and the thermal conductivity detector 12 and is used for analyzing high-concentration hydrogen sulfide, and the other path is sequentially connected in series with the polar capillary chromatographic column 8 and the hydrogen flame ionization detector 13 and is used for analyzing high-concentration methyl mercaptan and ethanethiol. In one embodiment, four ports of the second six-way switching valve 2 are connected to the second sample quantification ring 15, and the remaining two adjacent ports are connected, one port is connected to the second carrier gas line 21, and the other port is connected to the second split sample inlet 10.
In the invention, the high-concentration sulfur-containing compound detection unit comprises three chromatographic columns and two detectors, wherein the non-polar capillary chromatographic column 7 and the other two chromatographic columns are connected and switched by adopting a flow path switching unit. The flow path switching unit can selectively connect the nonpolar capillary chromatographic column 7 with the damping column or the nonpolar capillary chromatographic column in sequence at different times, so that hydrogen sulfide, methyl mercaptan and ethanethiol in the gas are completely separated and detected by different detectors.
Preferably, the flow path switching unit is a microplate flow path center cutting system 23, the microplate flow path center cutting system 23 includes a center interface 25, and a first interface 26 and a second interface 27 located at two ends, and the flow control switch 3, the center interface 25 is connected to the nonpolar capillary chromatographic column 7, the first interface 26 is connected to the damping column 6, and the second interface 27 is connected to the polar capillary chromatographic column 8. When the current control switch 3 is in the open state, the central interface 25 is connected to the second interface 27. When the current control switch 3 is in the closed state, the central interface 25 is connected to the first interface 26.
In the trace sulfur compound detection unit, all the sulfur compounds can be separated, but the content of the sulfur compounds exceeds 100 x 10 for single component-6The components above (V/V) cannot be quantified.
In the high-concentration sulfur compound detection unit, when the hydrocarbon gas contains high concentrations of hydrogen sulfide, methyl mercaptan and ethyl mercaptan, C contained in the hydrocarbon gas3、C4The invention combines a flow path switching unit, analyzes hydrogen sulfide by utilizing a nonpolar capillary chromatographic column and a thermal conductivity detector, and then is connected in series by the flow path switching unit, and separates and detects methyl mercaptan and ethyl mercaptan by utilizing a polar capillary chromatographic column and a hydrogen flame ionization detector.
In the high-concentration sulfur-containing compound detection unit, a sample is injected through a shunt injection port 10, wherein high-concentration hydrogen sulfide is separated from other components on a nonpolar capillary chromatographic column 7, a flow control switch is in a closed state at the moment, the nonpolar capillary chromatographic column 7 is directly connected with a damping column 6, the high-concentration hydrogen sulfide is detected by a thermal conductivity detector 12, and after the hydrogen sulfide completely flows out, the flow control switch is switched to an open stateMethyl mercaptan and ethyl mercaptan in the sample flow out of the nonpolar capillary chromatographic column 7 in a mixed peak mode, enter the polar capillary chromatographic column 8 for separation, and are detected by a hydrogen flame ionization detector. After the ethanethiol completely flows out of the nonpolar capillary chromatographic column 7, the flow control switch 3 is switched to the off state again, and the boiling point of the ethanethiol flowing out of the nonpolar capillary chromatographic column 7 is higher than the rest C of the ethanethiol3、C4The hydrocarbons are again passed through the damping column and detected by the thermal conductivity detector 12.
In the present invention, the sulfur compound-containing analytical column 4 may be a nonpolar capillary chromatographic column, preferably a capillary chromatographic column coated with a fixing solution of dimethylpolysiloxane, for example, a DB-1 capillary column.
In the present invention, the flow restriction column 5 is preferably a capillary chromatography column whose inner wall is deactivated.
In the present invention, the nonpolar capillary chromatographic column 7 may be a nonpolar capillary chromatographic column conventional in the art, preferably a capillary chromatographic column coated with a fixing solution of dimethylpolysiloxane, and may be, for example, a DB-1 capillary column.
In the present invention, the damping column 6 is preferably an inner wall deactivated quartz column, for example, an inner wall deactivated quartz column manufactured by Agilent corporation may be used.
In the present invention, the polar capillary column 8 is preferably a capillary column packed with a polar stationary phase, and may be, for example, a CP-LOWOX capillary column or a GS-OXYPLOT capillary column manufactured by Agilent.
The usage method of the analyzer can be as follows: the method comprises the steps of firstly introducing a sample into two sample quantification rings which are connected in series, then placing two six-way switching valves at a sample introduction position, wherein the sample in the first sample quantification ring 14 enters a first shunt sample inlet 9 under the carrying of carrier gas, then enters a sulfur compound analysis column 4 and a flow limiting column 5, and all sulfur compounds in the sample are detected by a sulfur selectivity detector.
Meanwhile, the carrier gas brings the sample in the second sample quantitative ring 15 into the second split sample inlet 10, the sample firstly enters the nonpolar capillary chromatographic column 7, the high-concentration hydrogen sulfide therein is separated on the nonpolar capillary chromatographic column 7, at this time, the flow control switch 3 of the microplate flow path center cutting system is in a closed state, the nonpolar capillary chromatographic column 7 is connected in series with the damping column 6, the hydrogen sulfide is sent to the thermal conductivity detector 12 for detection, after all the hydrogen sulfide flows out, the flow control switch 3 is adjusted to be in an open state, the high-concentration methyl mercaptan and the ethyl mercaptan in the sample enter the polar capillary chromatographic column 8 under the carrying of the carrier gas, the C1-C4 hydrocarbon compound firstly flows out due to weak retention, and the methyl mercaptan and the ethyl mercaptan with stronger polarity than the hydrocarbon component are separated from the hydrocarbon mixture and enter the hydrogen flame ionization detector 13 for detection. After all the ethanethiol flows out of the nonpolar capillary chromatographic column 7, the flow control switch 3 is turned off, and the rest of the hydrocarbon components still flow out of the nonpolar capillary chromatographic column 7 and are detected by the thermal conductivity detector 12.
After all the components in the gas sample are detected, the content of each sulfur-containing compound component in the gas sample can be calculated by an external standard method respectively. The gas to be measured is refinery gas, preferably liquefied petroleum gas containing C3 and C4 hydrocarbons as main components.
The analyzer for analyzing the composition of sulfur compounds in a gas with a wide concentration range according to the present invention will be described in detail with reference to FIG. 1.
The analyzer shown in fig. 1 includes a first six-way switching valve 1, a second six-way switching valve 2, a sulfur selectivity detector 11, a hydrogen flame ionization detector 13, a thermal conductivity detector 12, a first split sample inlet 9, a second split sample inlet 10, five capillary columns (i.e., a sulfur compound-containing analytical column 4, a flow restricting column 5, a damping column 6, a nonpolar capillary column 7, and a polar capillary column 8), and a flow path switching unit. The sample feeding pipeline 16 is connected with one interface 113 of the first six-way switching valve 1, the adjacent interface 112 is connected with the inlet end of the first sample quantitative ring 14, the outlet end of the first sample quantitative ring 14 is connected with the interface 115, the adjacent other interface 114 is connected with the pipeline 18, the other end of the pipeline 18 is connected with the interface 223 of the second six-way switching valve 2 and is connected with the inlet end of the second sample quantitative ring 15 through the other interface 222, the outlet end of the quantitative ring 15 is connected with the interface 225, and the interface 224 adjacent to the interface 225 is connected with the emptying pipeline 20. The above connection connects the first sample quantification loop 14 and the second sample quantification loop 15 in series through two six-way switching valves. Each switching valve is divided into two working conditions according to a dotted line and a solid line, wherein the dotted line indicates that the valve is in an 'open' state, and the solid line indicates that the valve is in a 'closed' state.
The interface 111 of the first six-way switching valve 1 adjacent to the inlet end of the first sample quantitative ring 14 is connected with the gas carrying pipeline 17, the other interface 116 adjacent to the first six-way switching valve is connected with the sample inlet part of the first split-flow sample inlet 9, the outlet end of the first split-flow sample inlet 9 is connected with the sulfur compound analysis column 4, the sulfur compound analysis column 4 is connected with the flow limiting column 5, and the outlet end of the flow limiting column 5 is connected with the sulfur selectivity detector 11.
The inlet end of another gas carrying pipeline 21 is connected to the interface end 221 of the second six-way switching valve 2, the outlet end 226 thereof is connected to the second split sample inlet 10 through the pipeline 22, the outlet of the second split sample inlet 10 is connected to the nonpolar capillary chromatographic column 7, and the outlet of the nonpolar capillary chromatographic column 7 is connected to the central interface 25 of the microplate flow path center cutting system 23. The first port 26 at one end of the microplate flow path center cutting system 23 is connected to one end of the damping column 6, and the other end of the damping column 6 is connected to the thermal conductivity detector 12. The second interface 27 at the other end of the microplate flow path center cutting system 23 is connected to one end of the polar capillary column 8, and the other end of the polar capillary column 8 is connected to the hydrogen flame ionization detector 13. The flow control switch 3 of the microplate flow path center cutting system 23 is divided into two states of on and off, the solid line is the off state of the flow control switch, the dotted line is the on state of the flow control switch, and the driving of the flow control switch is controlled by the gas pipeline 24.
The operation method of the analyzer of the invention is as follows:
the two six-way switching valves of fig. 1 are positioned in a solid line connection, i.e., a "closed" state, to place the analyzer in a sampling state. Meanwhile, the microplate flow path center cutting system is in a solid line connection state, gas to be detected enters the first sample quantitative ring 14 through the sample injection pipeline 16, the interface 113 and the interface 112 of the first six-way switching valve, then flows through the pipeline 18 from the interface 115 and the interface 114, enters the second sample quantitative ring 15 through the interface 223 and the interface 222 of the second six-way switching valve 2, and is discharged through the discharge pipeline 20 through the interface 225 and the interface 224 for sample replacement sampling.
After sampling, starting a trace sulfur compound detection unit and a high-concentration sulfur compound detection unit, and specifically operating as follows:
detection unit of trace sulfur compound: the first six-way switching valve 1 and the second six-way switching valve 2 are simultaneously switched to a dotted line connection state, namely an 'open' state, the analysis instrument starts an analysis operation program, a gas sample in the first sample quantitative ring 14 is carried by carrier gas entering from a carrier gas pipeline 17 to enter a first shunt sample inlet 9 through a connecting pipeline 19, a gas sample to be detected enters a sulfur compound analysis column 4 (preferably a nonpolar capillary chromatographic column) and a flow limiting column 5 connected in series with the sulfur compound analysis column, all sulfur compounds are separated, the sulfur compounds are detected one by one through a sulfur selectivity detector 11 according to set conditions, and hydrocarbon components do not respond.
If high-concentration sulfur-containing compounds (hydrogen sulfide, methyl mercaptan and ethyl mercaptan) exist in the sample, the sulfur-containing compound analysis column 4 can separate the sulfur-containing compounds and detect the sulfur-containing compounds by a sulfur selectivity detector 11, but when the content exceeds a detection range, quantitative detection cannot be carried out, and the high-concentration sulfur-containing compound detection unit is adopted to detect the content.
High concentration sulfur compound detection unit: the second six-way switching valve 2 is in a dotted line connection state, and the other carrier gas flows through the interface 221 and the interface 222 through the carrier gas line 21, enters the second sample quantifying ring 15, carries the gas sample therein through the interface 225 and the interface 226, enters the second split sample inlet 10 through the connecting pipeline 22, the sample enters the nonpolar capillary chromatographic column 7 after being split, because the boiling point of the hydrogen sulfide is lowest and the retention is weaker, the hydrogen sulfide flows out of the nonpolar capillary chromatographic column 7 firstly, when the flow control switch 3 of the microplate flow path center cutting system 23 is in a solid line connection state, the high concentration hydrogen sulfide separated by the nonpolar capillary chromatographic column 7 enters the thermal conductivity detector 12 through the damping column 6, when the hydrogen sulfide completely flows out of the chromatographic column 7, the flow control switch 3 of the microplate flow control center cutting system 23 is switched to a dotted line connection state, and the boiling point of the hydrogen sulfide flowing out of the nonpolar capillary chromatographic column 7 in a peak mixing mode is lower than that of ethanethiol.3The hydrocarbons, methyl mercaptan, ethyl mercaptan, etc. are transferred to a polar capillary chromatographic column 8, and high concentration sulfides are separated from the hydrocarbon matrix and enter a hydrogen flame ionization detector 13 for detection. When the ethanethiol completely flows out of the nonpolar capillary chromatographic column 7, the flow control switch 3 of the microplate flow path center cutting system 23 is adjusted to be switched to a solid line connection state, and C with a boiling point higher than that of the ethanethiol in the sample to be detected3、C4The hydrocarbon components continue to separate on the non-polar capillary chromatographic column 7 and are detected by the thermal conductivity detector 12.
The present invention is further illustrated by the following examples, but is not limited thereto.
Example 1
Connecting a chromatographic column and a detector according to the figure 1, wherein a sulfur-containing compound analysis column 4 in a trace sulfur-containing compound detection unit adopts a DB-1 capillary column, the length of the column is 60m, and the inner diameter of the column is 0.53 mm; the flow limiting column 5 is a capillary chromatographic column with deactivated inner wall, the length of the column is 1m, and the inner diameter of the column is 0.18 mm. The nonpolar capillary chromatographic column 7 in the high-concentration sulfur-containing compound detection unit adopts a DB-1 capillary column, the length of the column is 30m, and the inner diameter of the column is 0.32 mm; the polar capillary chromatographic column 8 is a CP-LOWOX capillary column produced by Agilent, the length of the column is 10m, and the inner diameter of the column is 0.53 mm; the damping column 6 is a quartz column with a deactivated inner wall, which is produced by Agilent company, the length of the column is 0.62m, and the inner diameter of the column is 0.25 mm.
Connecting pipes between interfaces in the two six-way switching valves are made of 1/16-inch stainless steel pipes, and joints between pipe diameters are 1/16 inches.
After the six-way switching valve, the microplate flow path control center cutting system, the chromatographic column and the pipeline were connected as shown in fig. 1, the gas sample, which was a liquefied petroleum gas sample containing high concentrations of hydrogen sulfide, methyl mercaptan and ethyl mercaptan, was analyzed under the conditions listed in table 1, and the chromatograms obtained were as shown in fig. 2 to 4, and the analysis results were as shown in table 2.
TABLE 1
Note that, in table 1, the "open" state of each valve is that the lines that the valve takes are connected by a broken line, and the "closed" state is that the lines that the valve takes are connected by a solid line.
TABLE 2
| Component name | Content, volume fraction x 10-6 |
| Hydrogen sulfide | 5000 |
| Methyl mercaptan | 4900 |
| Ethanethiol | 4800 |
| Dimethyl disulfide | 5 |
| |
10 |
| |
8 |
| Diethyl disulfide | 3 |
| Dimethyl trisulfide | 2 |
| Methyl ethyl trisulfide | 1 |
Therefore, the analyzer can achieve the qualitative result of the sulfur-containing compounds with wide concentration range in the gas by one-time sample injection, and obtain the content of various sulfur-containing compounds according to the result.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (9)
1. An analyzer for content of sulfur-containing compounds in hydrocarbon gas comprises a first sample quantitative ring (14) and a second sample quantitative ring (15) which are connected in series, wherein the first sample quantitative ring (14) is connected with a trace sulfur-containing compound detection unit, and the trace sulfur-containing compound detection unit comprises a first shunt sample inlet (9), a sulfur-containing compound analysis column (4), a current limiting column (5) and a sulfur selectivity detector (11) which are sequentially connected in series; the second sample quantitative ring (15) is connected with the high-concentration sulfur-containing compound detection unit, the high-concentration sulfur-containing compound detection unit comprises a second shunt sample inlet (10), a nonpolar capillary chromatographic column (7), a flow path switching unit, a damping column (6), a thermal conductivity detector (12), a polar capillary chromatographic column (8) and a hydrogen flame ionization detector (13), the second shunt sample inlet (10) is connected with the nonpolar capillary chromatographic column (7), the nonpolar capillary chromatographic column (7) is connected with a central interface of the flow path switching unit, an interface at one end of the flow path switching unit is sequentially connected with the damping column (6) and the thermal conductivity detector (12), an interface at the other end is sequentially connected with the polar capillary chromatographic column (8) and the hydrogen flame ionization detector (13), the sulfur-containing compound analysis column (4) is a nonpolar capillary chromatographic column, the first sample quantification loop (14) and the second sample quantification loop (15) are connected in series by two six-way switching valves.
2. The analyzer according to claim 1, wherein four ports of the first six-way switching valve (1) are connected to a first sample quantitative ring (14), an inlet end of the first sample quantitative ring (14) is connected to a sample feeding line (16), an outlet end of the first six-way switching valve is connected to a second six-way switching valve (2) as an inlet end of a second sample quantitative ring (15), four ports of the second six-way switching valve (2) are connected to the second sample quantitative ring (15), and an outlet end of the second sample quantitative ring (15) is connected to a vent line (20).
3. Analyser according to claim 1, wherein two adjacent ports of the first six-way switching valve (1) are connected, one port being connected to the first carrier gas line (17) and the other port being connected to the first split sample inlet (9);
two adjacent interfaces of the second six-way switching valve (2) are connected, one interface is connected to the second carrier gas pipeline (21), and the other interface is connected with the second shunt sample inlet (10).
4. The analyzer according to claim 1, wherein the flow path switching unit is a microplate flow path center cutting system (23), the microplate flow path center cutting system (23) comprises a center interface (25), a first interface (26) and a second interface (27) at two ends, and a flow control switch (3), the center interface (25) is connected with the nonpolar capillary chromatography column (7), the first interface (26) is connected with the damping column (6), the second interface (27) is connected with the polar capillary chromatography column (8),
when the flow control switch (3) is in an open state, the central interface (25) is connected with the second interface (27);
when the flow control switch (3) is in a closed state, the central interface (25) is connected with the first interface (26).
5. The analyzer according to any one of claims 1 to 4, wherein the sulfur compound-containing analytical column (4) is a capillary chromatographic column coated with a fixing liquid of dimethylpolysiloxane.
6. The analyzer according to any one of claims 1 to 4, wherein the flow restricting column (5) is a capillary chromatography column having an inner wall which has been subjected to a deactivation treatment.
7. The analyzer according to any one of claims 1 to 4, wherein the non-polar capillary chromatographic column (7) is a capillary chromatographic column coated with a fixing fluid of dimethylpolysiloxane.
8. The analyser according to any one of claims 1 to 4 wherein the damping columns (6) are inner wall deactivated quartz columns.
9. The analyzer according to any one of claims 1-4, wherein the polar capillary column (8) is a capillary column packed with a polar stationary phase.
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| CN113203801A (en) * | 2020-11-20 | 2021-08-03 | 济南海能仪器股份有限公司 | Gas shunting detection device |
| CN115236247A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | System and method for measuring concentration of trace impurities in hydrogen gas |
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