CN111077258A - Sulfide analysis method - Google Patents
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- CN111077258A CN111077258A CN201811232258.9A CN201811232258A CN111077258A CN 111077258 A CN111077258 A CN 111077258A CN 201811232258 A CN201811232258 A CN 201811232258A CN 111077258 A CN111077258 A CN 111077258A
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000004458 analytical method Methods 0.000 title claims abstract description 38
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 88
- 239000007789 gas Substances 0.000 claims abstract description 71
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 230000009471 action Effects 0.000 claims abstract description 10
- 150000004763 sulfides Chemical class 0.000 claims description 80
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 32
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 20
- 238000001514 detection method Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000012159 carrier gas Substances 0.000 claims description 13
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 8
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- -1 polymethylsiloxane Polymers 0.000 claims description 5
- INBDPOJZYZJUDA-UHFFFAOYSA-N methanedithiol Chemical compound SCS INBDPOJZYZJUDA-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 abstract description 18
- 239000011593 sulfur Substances 0.000 abstract description 18
- 238000011084 recovery Methods 0.000 abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003345 natural gas Substances 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 150000003568 thioethers Chemical class 0.000 abstract 5
- 230000014759 maintenance of location Effects 0.000 description 21
- 238000009835 boiling Methods 0.000 description 17
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 238000004587 chromatography analysis Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/60—Construction of the column
- G01N30/6034—Construction of the column joining multiple columns
- G01N30/6039—Construction of the column joining multiple columns in series
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/52—Physical parameters
- G01N30/54—Temperature
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/66—Thermal conductivity detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N2030/685—Electrical detectors flame photometry
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses an analytical method of sulfides, and belongs to the field of chemical analysis of natural gas purification and sulfur recovery. The sulfide analysis method comprises the following steps: providing a gas chromatograph, enabling a sulfide mixture comprising hydrogen sulfide and other sulfides to enter a first chromatographic column, enabling the hydrogen sulfide to enter a second chromatographic column from the first chromatographic column firstly under the action of an electronic gas circuit control system, setting central cutting time aiming at a two-dimensional central cutting system, and enabling components in other sulfides to enter a third chromatographic column from the first chromatographic column sequentially under the action of the electronic gas circuit control system when the central cutting time is reached; and (3) carrying out programmed temperature rise on the third chromatographic column by using a programmed temperature rise controller, and sequentially detecting the types and the concentrations of the separated components by using a pulse type flame photometric detector. When the sulfide analysis method is used for detecting a sulfide mixture, the influence of hydrogen sulfide on other sulfides is eliminated first, and then the other sulfides are subjected to full-component analysis.
Description
Technical Field
The invention relates to an analytical method of sulfides, and belongs to the field of chemical analysis of natural gas purification and sulfur recovery.
Background
The sulfur recovery process is a chemical process for converting a sulfide mixture into elemental sulfur, thereby changing waste into valuable and protecting the environment. In the sulfur recovery hydrogenation process, hydrogen is adopted to completely hydrogenate other trace sulfides except hydrogen sulfide in the sulfide mixture in the tail gas of the sulfur recovery device to generate hydrogen sulfide. Wherein the sulfide mixture comprises hydrogen sulfide and other trace sulfides (such as sulfur dioxide, carbonyl sulfide, carbon disulfide, methyl mercaptan, ethyl mercaptan, etc.). The analysis and detection of other trace sulfide components in the sulfur recovery hydrogenation process play a vital technical support role in ensuring the safe, stable and clean operation of the device and developing more advanced sulfur recovery technology and catalysts with better performance.
In the prior art, sulfur dioxide is firstly introduced into a hydrogen sulfide absorption tube, the sulfur dioxide acidifies cadmium sulfate in the hydrogen sulfide absorption tube, and the acidified cadmium sulfate adsorbs hydrogen sulfide to generate cadmium sulfide precipitate after the introduced sulfur dioxide is saturated. Then, the total sulfur analysis of other trace sulfides is carried out by a micro coulometer.
However, the hydrogen sulfide adsorption tube used in the method is complicated to manufacture, and the method can only perform total sulfur analysis on other trace sulfides and cannot perform full component analysis on other trace sulfides.
Disclosure of Invention
The embodiment of the invention provides a sulfide analysis method, which can solve the problem of analyzing the whole components of other sulfides in a sulfide mixture in the sulfur recovery hydrogenation process. The technical scheme is as follows:
a method of analyzing a sulfide, the method comprising:
providing a gas chromatograph which is provided with a two-dimensional central cutting system, an electronic gas circuit control system, a programmed temperature controller, a thermal conductivity detector and a pulse type flame photometric detector;
the sulfide mixture containing hydrogen sulfide and other sulfides enters a first chromatographic column and is separated according to the polarity and the boiling point;
under the action of the electronic gas circuit control system, the hydrogen sulfide enters a second chromatographic column from the first chromatographic column firstly, and the concentration of the hydrogen sulfide is detected by a thermal conductivity detector;
setting center cutting time for the two-dimensional center cutting system, and enabling components in other sulfides to sequentially enter a third chromatographic column from the first chromatographic column under the action of the electronic gas circuit control system when the center cutting time is reached;
carrying out programmed temperature rise on the third chromatographic column by using the programmed temperature rise controller, separating each component in other sulfides according to the polarity and the boiling point, and sequentially detecting the type and the concentration of each separated component by using a pulse type flame photometric detector;
wherein, the inner walls of the first chromatographic column, the second chromatographic column and the third chromatographic column are respectively coated with a polymethylsiloxane layer.
In one possible implementation, the electronic gas circuit control system performs valve switching under the control of the two-dimensional central cutting system.
In one possible implementation, the center cut time is 3.22min to 3.26 min.
In one possible implementation, the first, second, and third chromatography columns are capillary chromatography columns.
In one possible implementation, the other sulfides include: at least one of sulfur dioxide, carbonyl sulfur, dithiocarbon, methyl mercaptan and ethyl mercaptan.
In one possible implementation, for the gas chromatograph, the following chromatographic conditions are determined:
the temperature of a sample inlet is 100-150 ℃, the split ratio is 1: 50-1: 100, and the sample volume is 1.0-5.0 ml;
gradually increasing at a speed of 10-20 ℃ per minute from 50-70 ℃, carrying out the temperature programming, operating for 8min, and finally balancing for 6.5min at 80-120 ℃;
the flow rate of the second chromatographic column carrier gas He is 1.94ml/min, the flow rate of the third chromatographic column carrier gas He is 2.03ml/min, and the flow rate of the compensation gas He is 23-28 ml/min;
the detection temperature of the thermal conductivity detector is 80-120 ℃, the detection temperature of the pulse type flame photometric detector is 250-300 ℃, and H is2The flow rate was 14ml/min, the air flow rate of the second column was 17ml/min, and the air flow rate of the third column was 10 ml/min.
In one possible implementation, the injection port is an inert split/splitless injection port.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
the method for analyzing the sulfide provided by the embodiment of the invention comprises the steps of enabling a sulfide mixture of hydrogen sulfide and other sulfides to enter a first chromatographic column, and separating the hydrogen sulfide from the other sulfides according to the polarity and the boiling point. Through the effect of electron gas circuit control system, hydrogen sulfide enters the second chromatographic column at first, and the thermal conductivity detector detects the concentration of hydrogen sulfide. Meanwhile, the two-dimensional center cutting system controls the center cutting time, after the two-dimensional center cutting system determines that hydrogen sulfide completely enters the second chromatographic column, all components in other sulfides sequentially enter the third chromatographic column through the first chromatographic column under the action of the electronic gas circuit control system, the programmed temperature rise controller is used for carrying out programmed temperature rise on the third chromatographic column, all components in other sulfides are separated according to the polarity and the boiling point, and the pulse type flame photometric detector sequentially detects the types and the concentrations of all components in other separated sulfides. When the analysis method of the sulfide is used for detecting a sulfide mixture, the two-dimensional central cutting system can be used for setting central cutting time and controlling and valve switching of the electronic gas circuit control system, hydrogen sulfide can be cut out of the sulfide, the influence of the hydrogen sulfide on other sulfides can be eliminated, and then other sulfides can be separated by the process sequence heating controller, so that the other sulfides can be subjected to full-component analysis. The analytical method of the sulfide is quick and effective, simple to operate, low in detection limit, good in repeatability and high in stability, is suitable for qualitatively and quantitatively analyzing all components of trace sulfide in the sulfur recovery process, and can be widely applied to the fields of sulfur recovery analysis and test of petrochemical industry, natural gas purification plants, oil refineries, coal chemical industry and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a graph showing the retention time of a sulfide mixture in a second chromatographic column when the sulfide mixture is detected in a comparative example;
FIG. 2 is a graph showing the retention time of a part of other components in other sulfides in a third chromatographic column when a sulfide mixture is detected according to an embodiment of the present invention;
FIG. 3 is a graph comparing the retention time of hydrogen sulfide in the second column with the retention time of other sulfides in the third column when a mixture of sulfides is detected according to an embodiment of the present invention.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the following describes embodiments of the present invention in further detail.
The invention provides a sulfide analysis method, which comprises the following steps:
a gas chromatograph is provided, which is provided with a two-dimensional central cutting system, an electronic gas path control system, a programmed temperature controller, a thermal conductivity detector and a pulse type flame photometric detector.
The sulfide mixture containing hydrogen sulfide and other sulfides enters a first chromatographic column and is separated according to polarity and boiling point.
Under the action of the electronic gas circuit control system, hydrogen sulfide firstly enters the second chromatographic column from the first chromatographic column, and the concentration of the hydrogen sulfide is detected by the thermal conductivity detector.
And setting central cutting time aiming at the two-dimensional central cutting system, and enabling the components in the other sulfides to sequentially enter a third chromatographic column from the first chromatographic column under the action of the electronic gas circuit control system when the central cutting time is reached.
And (3) carrying out programmed temperature rise on the third chromatographic column by using a programmed temperature rise controller, separating each component in other sulfides according to the polarity and the boiling point, and sequentially detecting the composition and the concentration of each separated component by using a pulse type flame photometric detector.
In a possible implementation manner, when the thermal conductivity detector detects hydrogen sulfide, the concentration of hydrogen sulfide is calculated according to the chromatographic peak area of hydrogen sulfide and the peak area of a standard gas of hydrogen sulfide, that is, quantitative analysis is performed.
The specific calculation process is as follows: for example, when the sulfide mixture is introduced in an amount of 1ml, the chromatographic peak area of hydrogen sulfide is A. For example, when the standard gas sample amount of hydrogen sulfide may be 0.1ml, 0.5ml, 1ml, 1.5ml and 2ml, respectively, the corresponding standard peak areas of hydrogen sulfide are B, C, D, E and F, respectively. And (5) drawing according to the sampling amount of the hydrogen sulfide standard gas and the standard peak area to obtain a hydrogen sulfide standard working curve y which is ax + b. And (3) substituting the A into a hydrogen sulfide standard working curve y which is ax + b, and calculating to obtain x which is the concentration of the hydrogen sulfide in the target mixture.
When the pulse type flame photometric detector detects each component in other separated sulfides, the type of each component is determined according to the retention time of each component, and the concentration of each component is calculated according to the chromatographic peak area of each component and the standard gas peak area corresponding to each component.
The types of the components are different, the retention time of the components is different, and the types of the components, namely qualitative analysis, can be determined according to the retention time of the components.
The calculation process for calculating the concentration of each component according to the chromatographic peak area of each component and the standard gas peak area corresponding to each component is similar to the calculation process for calculating the concentration of hydrogen sulfide, and is not repeated here.
The method for analyzing the sulfide provided by the embodiment of the invention comprises the steps of enabling a sulfide mixture of hydrogen sulfide and other sulfides to enter a first chromatographic column, and separating the hydrogen sulfide from the other sulfides according to the polarity and the boiling point. Through the effect of electron gas circuit control system, hydrogen sulfide enters the second chromatographic column at first, and the thermal conductivity detector detects the concentration of hydrogen sulfide. Meanwhile, the two-dimensional center cutting system controls the center cutting time, after the two-dimensional center cutting system determines that hydrogen sulfide completely enters the second chromatographic column, all components in other sulfides sequentially enter the third chromatographic column through the first chromatographic column under the action of the electronic gas circuit control system, the programmed temperature rise controller is used for carrying out programmed temperature rise on the third chromatographic column, all components in other sulfides are separated according to the polarity and the boiling point, and the pulse type flame photometric detector sequentially detects the types and the concentrations of all components in other separated sulfides. Therefore, when the sulfide analysis method is used for detecting a sulfide mixture, the two-dimensional central cutting system can be used for setting the central cutting time and controlling and valve switching by the electronic gas circuit control system, hydrogen sulfide can be cut out of sulfides, the influence of the hydrogen sulfide on other sulfides can be eliminated, and then other sulfides can be separated by the process sequence heating controller, so that the other sulfides can be subjected to full-component analysis. The analytical method of the sulfide is quick and effective, simple to operate, low in detection limit, good in repeatability and high in stability, is suitable for qualitatively and quantitatively analyzing all components of trace sulfide in the sulfur recovery process, and can be widely applied to the fields of sulfur recovery analysis and test of petrochemical industry, natural gas purification plants, oil refineries, coal chemical industry and the like.
In a possible implementation mode, the electronic gas circuit control system performs valve switching under the control of the two-dimensional central cutting system, and through the valve switching process, other sulfides can be switched into the third chromatographic column after hydrogen sulfide completely enters the second chromatographic column.
Based on the hydrogen sulfide component entering the second column, the center cut time can be made to be 3.22min to 3.26 min.
In a possible implementation mode, the electronic gas circuit control system is provided with a first control valve and a second control valve, after a sulfide mixture is separated in a first chromatographic column, the two-dimensional center cutting system controls the electronic gas circuit control system to open the first control valve, hydrogen sulfide in the sulfide mixture enters a second chromatographic column through the first control valve at first, center cutting time is set for the two-dimensional center cutting system, when the center cutting time is reached, the two-dimensional center cutting system controls the electronic gas circuit control system to close the first control valve, the second control valve is opened, and other sulfides enter a third chromatographic column through the second control valve by the first chromatographic column in sequence.
In another possible implementation, the first chromatography column, the second chromatography column, and the third chromatography column are capillary chromatography columns.
In another possible implementation, the inner walls of the first, second and third chromatography columns are coated with a polymethylsiloxane layer.
In one possible implementation, when the first, second and third chromatography columns are capillary chromatography columns, each capillary chromatography column has a length of 30m and an inner diameter of 0.32mm, and the inner wall of the capillary chromatography column is coated with a polymethylsiloxane layer having a thickness of 5 μm. Wherein, the capillary chromatographic column is subjected to inert treatment by covering the polymethylsiloxane layer, so that other sulfides are prevented from being attached to the capillary chromatographic column and influencing the detection of other sulfides.
TABLE 1
As shown in table 1, retention times for the other sulfides are for three different columns. As can be seen from Table 1, when the capillary column models are GS-GASPRO and SCION-1, the difference in retention times of sulfur dioxide and carbonyl sulfide is 0.17min and 0.09min, respectively, and the difference in retention times is small. And when the type of the capillary chromatographic column is BR-1, the retention time of sulfur dioxide is shortest, the separation process of other sulfides is also shortest, and the difference between the retention time of the sulfur dioxide and the retention time of carbonyl sulfide is 0.19 min. Therefore, compared with other two types of capillary chromatographic columns, the capillary chromatographic column with the BR-1 type can separate sulfur dioxide and carbonyl sulfide more effectively.
It should be noted that the other sulfides are: other sulfides, in trace amounts relative to hydrogen sulfide, include: at least one of sulfur dioxide, carbonyl sulfide, dithiocarbon, methyl mercaptan and ethyl mercaptan.
In one possible implementation, for a gas chromatograph, the following chromatographic conditions are determined:
the temperature of a sample inlet is 100-150 ℃, the split ratio is 1: 50-1: 100, and the sample volume is 1.0-5.0 ml.
Increasing the temperature from 50-70 ℃ at a speed of 10-20 ℃ per minute, carrying out temperature programming, operating for 8min, and finally balancing for 6.5min at 80-120 ℃.
The flow rate of the second chromatographic column carrier gas He is 1.94ml/min, the flow rate of the third chromatographic column carrier gas He is 2.03ml/min, and the flow rate of the compensation gas He is 23-28 ml/min.
The detection temperature of the thermal conductivity detector is 80-120 ℃, the detection temperature of the pulse type flame photometric detector is 250-300 ℃, and H is2The flow rate was 14ml/min, the air flow rate of the second column was 17ml/min, and the air flow rate of the third column was 10 ml/min.
The sample inlet is an inert shunt/non-shunt sample inlet, can be used for shunt sample injection and non-shunt sample injection, and can be freely selected according to requirements.
The method for analyzing the sulfide provided by the embodiment of the invention comprises the steps of enabling a sulfide mixture of hydrogen sulfide and other sulfides to enter a first chromatographic column, and separating the hydrogen sulfide from the other sulfides according to the polarity and the boiling point by adjusting the gas chromatography condition. The two-dimensional center cutting system controls the electronic gas circuit control system to open the first control valve, the hydrogen sulfide enters the second chromatographic column through the first control valve at the latest, and the thermal conductivity detector detects the concentration of the hydrogen sulfide. Meanwhile, the two-dimensional center cutting system controls the center cutting time, when the two-dimensional center cutting system determines that hydrogen sulfide completely enters the second chromatographic column, the electronic gas circuit control system is controlled to close the first control valve, the second control valve is opened, all components in other sulfides sequentially enter the third chromatographic column through the first chromatographic column through the second control valve, the temperature programming controller is used for conducting temperature programming on the third chromatographic column, all components in other sulfides are separated according to the polarity size and the boiling point height, and the pulse type flame photometric detector sequentially detects the types and the concentrations of all components in other separated sulfides. When the analysis method of the sulfide is used for detecting a sulfide mixture, the two-dimensional central cutting system can be used for setting central cutting time and controlling and valve switching of the electronic gas circuit control system, hydrogen sulfide can be cut out of the sulfide, the influence of the hydrogen sulfide on other sulfides can be eliminated, and then other sulfides can be separated by the process sequence heating controller, so that the other sulfides can be subjected to full-component analysis. The analytical method of the sulfide is quick and effective, simple to operate, good in repeatability and high in stability, is suitable for qualitatively and quantitatively analyzing all components of trace sulfide in the sulfur recovery process, and can be widely applied to the fields of sulfur recovery analysis and test of petrochemical industry, natural gas purification plants, oil refineries, coal chemical industry and the like.
The technical solution of the present invention will be described in detail by specific examples below.
Example 1
The sulfide mixture enters a gas chromatograph, the injection inlet temperature of the gas chromatograph is 100 ℃, the split ratio is 1:50, and the injection amount is 1.0 ml.
The sulfide mixture firstly enters a first chromatographic column, and is separated according to the polarity and the boiling point in the first chromatographic column; the two-dimensional center cutting system controls the electronic gas circuit control system to open the first control valve, and hydrogen sulfide enters the second chromatographic column through the first control valve firstly.
The flow rate of the carrier gas He of the second chromatographic column was 1.94ml/min, the air flow rate of the second chromatographic column was 17ml/min, and the flow rate of the compensation gas He was 28 ml/min.
The thermal conductivity detector detects the concentration of the hydrogen sulfide; the detection temperature of the thermal conductivity detector is 80 ℃.
Meanwhile, the two-dimensional center cutting system controls the center cutting time, and the center cutting time is set to be 3.26 min.
And after the two-dimensional center cutting system determines that the hydrogen sulfide completely enters the second chromatographic column, the electronic gas circuit control system is controlled to close the first control valve, the second control valve is opened, and all components in other sulfides sequentially enter the third chromatographic column through the first chromatographic column through the second control valve.
The flow rate of carrier gas He of the third chromatographic column is 2.03ml/min, the air flow rate of the third chromatographic column is 10ml/min, and the flow rate of compensation gas He is 28 ml/min.
And utilizing a temperature programming controller to program temperature of the third chromatographic column.
The temperature is programmed to increase at a rate of 20 ℃ per minute from 50 ℃ and run for 8min, and finally equilibrate for 6.5min at 80 ℃.
The components of other sulfides are separated according to the polarity size and the boiling point height.
The pulsed flame photometric detector detects the types and the concentrations of the components in other separated sulfides in turn.
The detection temperature of the pulse type flame photometric detector is 250 ℃, and H2The flow rate was 14 ml/min.
And finally, calculating the concentration of the hydrogen sulfide through the peak area of the standard hydrogen sulfide gas and the chromatographic peak area of the hydrogen sulfide.
Determining the types of the components in other sulfides according to the retention time of the components, and calculating the concentration of each component according to the standard gas peak area of each component and the chromatographic peak area of each component.
Example 2
The sulfide mixture enters a gas chromatograph, the injection port temperature of the gas chromatograph is 120 ℃, the split ratio is 1:80, and the injection amount is 2.0 ml.
The sulfide mixture firstly enters a first chromatographic column, and is separated according to the polarity size and the boiling point height in the first chromatographic column. The two-dimensional center cutting system controls the electronic gas circuit control system to open the first control valve, and hydrogen sulfide enters the second chromatographic column through the first control valve firstly.
The flow rate of the carrier gas He of the second chromatographic column was 1.94ml/min, the air flow rate of the second chromatographic column was 17ml/min, and the flow rate of the compensation gas He was 25 ml/min.
The thermal conductivity detector detects the concentration of the hydrogen sulfide; the detection temperature of the thermal conductivity detector is 100 ℃.
Meanwhile, the two-dimensional center cutting system controls the center cutting time, and the center cutting time is set to be 3.24 min.
And after the two-dimensional center cutting system determines that the hydrogen sulfide completely enters the second chromatographic column, the electronic gas circuit control system is controlled to close the first control valve, the second control valve is opened, and all components in other sulfides sequentially enter the third chromatographic column through the first chromatographic column through the second control valve.
The flow rate of carrier gas He of the third chromatographic column is 2.03ml/min, the air flow rate of the third chromatographic column is 10ml/min, and the flow rate of compensation gas He is 25 ml/min.
And utilizing a temperature programming controller to program temperature of the third chromatographic column.
From 60 deg.C, increasing at a rate of 15 deg.C per minute, programming temperature, running for 8min, and balancing at 100 deg.C for 6.5 min.
The components of other sulfides are separated according to the polarity size and the boiling point height.
The pulsed flame photometric detector detects the types and the concentrations of the components in other separated sulfides in turn.
The detection temperature of the pulse type flame photometric detector is 280 ℃, and H is2The flow rate was 14 ml/min.
And finally, calculating the concentration of the hydrogen sulfide through the peak area of the standard hydrogen sulfide gas and the chromatographic peak area of the hydrogen sulfide.
Determining the types of the components in other sulfides according to the retention time of the components, and calculating the concentration of each component according to the standard gas peak area of each component and the chromatographic peak area of each component.
Example 3
The sulfide mixture enters a gas chromatograph, the injection port temperature of the gas chromatograph is 150 ℃, the split ratio is 1:100, and the injection amount is 5.0 ml.
The sulfide mixture firstly enters a first chromatographic column, and is separated according to the polarity size and the boiling point height in the first chromatographic column. The two-dimensional center cutting system controls the electronic gas circuit control system to open the first control valve, and hydrogen sulfide enters the second chromatographic column through the first control valve firstly.
The flow rate of the carrier gas He of the second chromatographic column was 1.94ml/min, the air flow rate of the second chromatographic column was 17ml/min, and the flow rate of the compensation gas He was 23 ml/min.
The thermal conductivity detector detects the concentration of the hydrogen sulfide; the detection temperature of the thermal conductivity detector is 120 ℃.
Meanwhile, the two-dimensional center cutting system controls the center cutting time, and the center cutting time is set to be 3.22 min.
And after the two-dimensional center cutting system determines that the hydrogen sulfide completely enters the second chromatographic column, the electronic gas circuit control system is controlled to close the first control valve, the second control valve is opened, and all components in other sulfides sequentially enter the third chromatographic column through the first chromatographic column through the second control valve.
The flow rate of carrier gas He of the third chromatographic column is 2.03ml/min, the air flow rate of the third chromatographic column is 10ml/min, and the flow rate of compensation gas He is 23 ml/min.
And utilizing a temperature programming controller to program temperature of the third chromatographic column.
From 70 deg.C, increasing at a rate of 10 deg.C per minute, programming temperature, running for 8min, and balancing at 120 deg.C for 6.5 min.
The components of other sulfides are separated according to the polarity size and the boiling point height.
The pulsed flame photometric detector detects the types and the concentrations of the components in other separated sulfides in turn.
The detection temperature of the pulse type flame photometric detector is 300 ℃, and H is2The flow rate was 14 ml/min.
And finally, calculating the concentration of the hydrogen sulfide through the peak area of the standard hydrogen sulfide gas and the chromatographic peak area of the hydrogen sulfide.
Determining the types of the components in other sulfides according to the retention time of the components, and calculating the concentration of each component according to the standard gas peak area of each component and the chromatographic peak area of each component.
Comparative example
The sulfide mixture enters a gas chromatograph, the injection inlet temperature of the gas chromatograph is 100 ℃, the split ratio is 1:50, and the injection amount is 1.0 ml.
The sulfide mixture firstly enters a first chromatographic column, and is separated according to the polarity size and the boiling point height in the first chromatographic column.
And the hydrogen sulfide and other sulfides in the sulfide mixture enter a second chromatographic column in sequence.
The flow rate of the carrier gas He of the second chromatographic column was 1.94ml/min, the air flow rate of the second chromatographic column was 17ml/min, and the flow rate of the compensation gas He was 28 ml/min.
The thermal conductivity detector detects the concentration of hydrogen sulfide and the types and concentrations of all components in other sulfides; the detection temperature of the thermal conductivity detector is 80 ℃.
And finally, calculating the concentration of the hydrogen sulfide through the peak area of the standard hydrogen sulfide gas and the chromatographic peak area of the hydrogen sulfide.
Determining the types of the components in other sulfides according to the retention time of the components, and calculating the concentration of each component according to the standard gas peak area of each component and the chromatographic peak area of each component.
As shown in fig. 1, the retention time of the sulfide mixture in the second chromatographic column when the sulfide mixture was examined for comparative example. As can be seen from fig. 1, sulfur dioxide and carbonyl sulfide are not effectively separated due to the influence of hydrogen sulfide, and only hydrogen sulfide and sulfur dioxide are detected. And other components in other sulfides are not effectively separated, and the other components in other sulfides cannot be subjected to full component analysis.
Application examples
In this example, when the solution of example 1 is used to detect a sulfide mixture, as shown in fig. 2 and 3, fig. 2 shows the retention time of some of the other sulfide components, carbonyl sulfide and sulfur dioxide, in a third chromatographic column; FIG. 3 is a graph comparing the retention time of hydrogen sulfide in the second chromatographic column with the retention time of other sulfides in the third chromatographic column;
as can be seen from figure 2, the hydrogen sulfide cut is complete and the sulfur dioxide is effectively separated from the carbonyl sulfide.
As can be seen from FIG. 3, hydrogen sulfide is completely separated from other sulfides, hydrogen sulfide is completely cut, sulfur dioxide and carbonyl sulfide are effectively separated, the influence of hydrogen sulfide on components in other sulfides is eliminated, components in other sulfides are also effectively separated, and the other sulfides are subjected to full-component analysis.
And, the analytical method of sulfide is to carry out the full component analysis of the sulfide mixture, the relative standard deviation<0.02, minimum detection limit<1ppm, linear correlation coefficient R2≥0.9999。
In summary, when the analysis method for sulfides provided by the embodiment of the present invention is used to detect a sulfide mixture, the analysis method can be used to perform full-component analysis on other sulfides in addition to detecting hydrogen sulfide. The analytical method of the sulfide is quick and effective, simple to operate, low in detection limit, good in repeatability and high in stability, is suitable for qualitatively and quantitatively analyzing all components of trace sulfide in the sulfur recovery process, and can be widely applied to the fields of sulfur recovery analysis and test of petrochemical industry, natural gas purification plants, oil refineries, coal chemical industry and the like.
The above description is only for facilitating the understanding of the technical solutions of the present invention by those skilled in the art, and is not intended to limit the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for analyzing a sulfide, comprising:
providing a gas chromatograph which is provided with a two-dimensional central cutting system, an electronic gas circuit control system, a programmed temperature controller, a thermal conductivity detector and a pulse type flame photometric detector;
the sulfide mixture containing hydrogen sulfide and other sulfides enters a first chromatographic column for separation;
under the action of the electronic gas circuit control system, the hydrogen sulfide enters a second chromatographic column from the first chromatographic column firstly, and the concentration of the hydrogen sulfide is detected by a thermal conductivity detector;
setting center cutting time for the two-dimensional center cutting system, and enabling components in other sulfides to sequentially enter a third chromatographic column from the first chromatographic column under the action of the electronic gas circuit control system when the center cutting time is reached;
carrying out programmed temperature rise on the third chromatographic column by using the programmed temperature rise controller so as to separate each component in other sulfides, and sequentially detecting the type and the concentration of each separated component by using a pulse type flame photometric detector;
wherein, the inner walls of the first chromatographic column, the second chromatographic column and the third chromatographic column are respectively coated with a polymethylsiloxane layer.
2. The analytical method for sulfides according to claim 1, wherein said electronic gas circuit control system performs valve switching under the control of said two-dimensional central cutting system.
3. The analytical method for sulfides according to claim 1, wherein the center cutting time is 3.22 to 3.26 min.
4. The method of analyzing sulfide according to claim 1, wherein the first column, the second column, and the third column are capillary columns.
5. The method for analyzing sulfide according to claim 1, wherein the other sulfide includes: at least one of sulfur dioxide, carbonyl sulfur, dithiocarbon, methyl mercaptan and ethyl mercaptan.
6. The method for analyzing sulfide according to any one of claims 1 to 5, wherein the following chromatographic conditions are determined for the gas chromatograph:
the temperature of a sample inlet is 100-150 ℃, the split ratio is 1: 50-1: 100, and the sample volume is 1.0-5.0 ml;
gradually increasing at a speed of 10-20 ℃ per minute from 50-70 ℃, carrying out the temperature programming, operating for 8min, and finally balancing for 6.5min at 80-120 ℃;
the flow rate of the second chromatographic column carrier gas He is 1.94ml/min, the flow rate of the third chromatographic column carrier gas He is 2.03ml/min, and the flow rate of the compensation gas He is 23-28 ml/min;
the detection temperature of the thermal conductivity detector is 80-120 ℃, the detection temperature of the pulse type flame photometric detector is 250-300 ℃, and H is2The flow rate was 14ml/min, the air flow rate of the second column was 17ml/min, and the air flow rate of the third column was 10 ml/min.
7. The method of analyzing sulfide according to claim 6, wherein the sample inlet is an inert split/splitless sample inlet.
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