CN108693256B - Analysis method for sulfur distribution in liquefied petroleum gas and sulfide qualitative database - Google Patents
Analysis method for sulfur distribution in liquefied petroleum gas and sulfide qualitative database Download PDFInfo
- Publication number
- CN108693256B CN108693256B CN201710224550.5A CN201710224550A CN108693256B CN 108693256 B CN108693256 B CN 108693256B CN 201710224550 A CN201710224550 A CN 201710224550A CN 108693256 B CN108693256 B CN 108693256B
- Authority
- CN
- China
- Prior art keywords
- sulfide
- gas
- retention time
- sulfur
- analysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention provides a method for analyzing sulfur distribution in liquefied petroleum gas. The method is based on a gas chromatography-sulfur chemiluminescence detector, and comprises the establishment of analysis conditions, qualitative analysis and quantitative analysis; wherein the chromatographic column is a capillary column of a porous layer open tube of bonding silica gel with weak polarity, and high-purity helium is used as carrier gas; the invention also sets a temperature-raising program of the column temperature. The invention provides a sulfide qualitative analysis database based on a gas chromatography/sulfur chemiluminescence detector, which comprises sulfides with retention time of 4-20 min. The method can accurately and rapidly analyze the sulfide structure and the content in the liquefied petroleum gas, thereby ensuring that a proper desulfurization means is adopted in real time in a production field and ensuring the stability of production and the quality of products.
Description
Technical Field
The invention relates to the field of analytical chemistry, in particular to an analysis method for analyzing the morphological distribution (sulfur distribution for short) of sulfides in liquefied petroleum gas by using a gas chromatography technology.
Background
With the development of world economy, the harm of environmental pollution to human beings is more and more serious, and SO discharged by gasoline, diesel oil and liquefied petroleum gas combustion 2 The acid rain caused by the pollution is the main source of air pollutionOne, the first step. In order to protect the atmospheric environment, countries have made more strict requirements on the sulfur content of oil products, so that the continuous improvement of the desulfurization technology to meet the requirements on product quality is the requirement of the production development of various oil refineries, and the improvement of the desulfurization technology has raised higher requirements on the analysis of the sulfide content, particularly the sulfide content in liquefied petroleum gas.
The main components of the liquefied petroleum gas are butylene, propylene, butane, propane and the like. The sulfide impurities in the liquefied petroleum gas are corrosive to equipment and have the functions of inhibiting and damaging a catalyst in a downstream processing process. For the deep processing of the liquefied petroleum gas, the reduction of the sulfur content in the liquefied petroleum gas is urgently needed. The liquefied petroleum gas contains various forms of sulfur compounds, including hydrogen sulfide, carbonyl sulfide, mercaptans, sulfides, etc., and carbon numbers of the sulfides are different, and they have different influences on the desulfurization of the apparatus. In order to effectively reduce the sulfur content of liquefied petroleum gas, the sulfur distribution of the liquefied petroleum gas needs to be mastered in time so as to adopt a proper desulfurization means.
Generally, a gas chromatography technology is used to separate various sulfides in the liquefied petroleum gas, and various detectors are used for identification and measurement, such as a Flame Photometric Detector (FPD), a Dual Flame Photometric Detector (DFPD), a flame ionization and flame photometric detector (FI-FPD), a mass spectrometry detector (MS), and the like. Although the detection technology in the prior art makes certain progress in qualitative aspect, the operation is complicated, the hydrocarbon chromatographic peak and the sulfide chromatographic peak interfere with each other, and the identification is difficult, so that higher requirements are provided for the separation performance of the chromatographic column.
The gas chromatography-pulsed flame photometric detection technology (GC-PFPD) is a new technology developed in recent years for analyzing and detecting sulfides. Compared with the traditional GC-FPD, the high-sensitivity and high-S/C selectivity (up to 10) are realized by adopting the pulse flame combustion technology, the sulfur filter filtering hydrocarbon light-emitting technology and adopting different delay time gate amplifiers to respectively receive the light emitted by sulfur (S) and carbon (C) 7 ) And no hydrocarbon quenching, etc. The Wenxingming, zhujianhua, liuhong Jiang, lizhong beam, etc. of China Petroleum university chemical industry institute and China petrochemical, jinnan division, etc. are performed on HP-6890 gas chromatograph by using pulsed flame lightDegree detector (PFPD) (Varian corporation, USA), GS-
Capillary chromatography column 30 m.times.0.32 mm (USA J)&W corporation), the morphology and the content of trace sulfides in liquefied petroleum gas were analyzed by GC-PFPD technique (morphometric identification of trace sulfides in liquefied gas, chemical industry of petroleum and natural gas, 10 months 2003). But the sulfide signals detected by the method can not be in equimolar linear response with sulfur in corresponding sulfides, so that the method is inconvenient to popularize and apply in production; in addition, the sample is directly injected through an injection valve on a chromatograph, so that the uniform gasification of the liquefied petroleum gas sample cannot be ensured, and the accuracy of the sulfide content analysis of the liquefied petroleum gas sample is influenced.
The gas chromatography-atomic emission spectrometry (GC-AED) is a trace sulfide detection method, has high sensitivity but low S/C selectivity of only 10 4 This places higher demands on the performance of the column. In addition, the detection needs long time for completing one detection, the price of the instrument is high, the operation cost is high, and the maintenance is difficult, so that the popularization and the application of the GC-AED are limited.
The gas chromatography-sulfur chemiluminescence detection technology (GC-SCD) is a new technology developed at present for analyzing and detecting sulfides. It uses the chemical luminescence generated by the reaction of the combustion product of sulfide and ozone under low pressure to make qualitative and quantitative detection. It has equimolar response to sulfur in sulfide with different structure and almost the same response factor to sulfur in sulfide with different concentration. Compared with GC-PFPD and GC-AED, the high-sensitivity high-selectivity high-cost performance liquid crystal has higher sensitivity and better selectivity.
The analytical method of sulfur content of each sulfide in liquefied petroleum gas (research on morphological distribution of sulfides in liquefied gas, petroleum refining and chemical industry, 2 months 2005) is established on an HP-6890 gas chromatograph by using a Sulfur Chemiluminescence Detector (SCD) and a VB-1 capillary chromatographic column of 60m multiplied by 0.53mm multiplied by 5.0 mu m and adopting an external standard method through optimization of chromatographic conditions. The hydrogen sulfide and the carbonyl sulfide are common sulfides in the liquefied gas, and when a VB-1 capillary chromatographic column is used, the carbonyl sulfide flows out from the tail part of the hydrogen sulfide, and when the concentration of the hydrogen sulfide is higher than that of the carbonyl sulfide, the carbonyl sulfide is difficult to detect. In addition, the sample is directly injected through an injection valve on a chromatograph, so that the uniform gasification of the liquefied petroleum gas sample cannot be ensured, and the accuracy of the sulfide content analysis is influenced.
Not only the above documents report, the national petrochemical industry standard NB/SH/T0919-2015 "gas chromatography and chemiluminescence detection method for measuring sulfur-containing compounds in gas fuel and natural gas" also stipulates that a nonpolar quartz capillary column of a methyl silicone stationary phase is used as a chromatographic column, and a sample is directly injected through an injection valve on a chromatograph. Therefore, in the prior art, the analysis of the sulfur distribution in the liquefied petroleum gas by means of GC-SCD still has more defects, and the analysis accuracy of the sulfide content is not high.
The inventors of the present invention previously proposed an invention patent application entitled "method for analyzing sulfur distribution in propylene feedstock and a qualitative database of sulfides", which describes qualitative and quantitative analysis of sulfides in propylene feedstock based on gas chromatography-sulfur chemiluminescence detection. The analysis conditions of the method are as follows: 1) Directly injecting a sample in a propylene raw material steel cylinder through a sample injection valve on a chromatograph; 2) Column temperature: the initial temperature is 35-40 ℃, the initial time is 0-4 min, the heating rate is 15-25 ℃/min, the final temperature is 200-250 ℃, and the temperature is kept for 4-8 min. According to the method, the sulfide qualitative analysis database only comprises carbonyl sulfide, hydrogen sulfide, carbon disulfide, sulfur dioxide, methyl mercaptan, ethanethiol, thiophene, dimethyl sulfide, isopropyl mercaptan, n-propyl mercaptan, ethyl methyl sulfide, dimethyl disulfide and diethyl sulfide. The sample feeding mode of the method can not ensure the uniform gasification of the liquefied petroleum gas sample, thereby influencing the accuracy of the analysis of the sulfide content of the liquefied petroleum gas sample; the analysis conditions and qualitative database of the method cannot analyze the higher content of the methyl ethyl disulfide and the diethyl disulfide in the liquefied petroleum gas, so the method is not suitable for analyzing the sulfur compounds in the liquefied petroleum gas.
Disclosure of Invention
The invention aims to provide an analysis method for analyzing the morphological distribution of sulfides in liquefied petroleum gas by using a gas chromatography-sulfur chemiluminescence detector, aiming at the defects of the prior art.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
the analysis method of the morphological distribution of the sulfide in the liquefied petroleum gas is based on a gas chromatography-sulfur chemiluminescence detector, comprises the establishment of analysis conditions, qualitative analysis and quantitative analysis, and comprises the following specific steps:
I. establishment of analysis conditions
And (3) chromatographic column: a capillary column with weak polarity, 60m multiplied by 0.32mm; preferably a low polarity bonded silica gel porous layer open tube PLOT column,
carrier gas: the high-purity helium is mixed with the nitrogen,
column head pressure of the chromatographic column: from 20psi to 30psi of the pressure vessel,
the split ratio is as follows: 4:1-6:1,
temperature of a sample injection valve: the temperature of 150-200 ℃,
gas sample introduction quantitative tube: 0.25mL to 1mL of the solution,
column temperature: the initial temperature is 35-45 ℃, the initial time is 0-4 min, the first-order heating rate is 10-20 ℃/min, the final temperature is 210-230 ℃, the temperature is kept for 5-10 min, the second-order heating rate is 30-35 ℃/min, the temperature is increased to 250-270 ℃, the temperature is kept for 8-15 min,
sulfur chemiluminescence detector pressure: the temperature of the mixture is 6Torr-12Torr,
dual ion controller pressure: the temperature of the mixture is between 350 and 400Torr,
combustor temperature: at a temperature of 800 c,
hydrogen gas: 40mL/min-50mL/min, air: 60mL/min-70mL/min,
background noise: 0.2mV-3.0mV,
qualitative analysis of
Connecting the liquid hydrocarbon flash evaporation gasification sampling injector with a sample valve of a chromatograph, so that a liquefied petroleum gas sample to be detected is gasified by the liquid hydrocarbon flash evaporation gasification sampling injector, enters a gas sample introduction quantitative tube through a gas sample introduction valve on the chromatograph, is subjected to sample introduction under the analysis condition, obtains a map, compares the map with a sulfide qualitative analysis database under the analysis condition, and determines a sulfide structure in the liquefied petroleum gas sample to be detected according to retention time; the temperature of the liquid hydrocarbon flash evaporation gasification sampling injector is controlled to be 80-150 ℃, and the flow rate of the gasified gas is controlled to be 150-250 mL/min;
quantitative analysis
Determining a sulfur quantitative response factor under the analysis condition by taking the gas organic sulfide as an external standard sample; connecting the liquid hydrocarbon flash evaporation gasification sampling injector with a sample valve of a chromatograph, so that a liquefied petroleum gas sample to be measured is firstly gasified by the liquid hydrocarbon flash evaporation gasification sampling injector, and then enters a gas sample injection quantitative tube for sample injection through a gas sample injection valve on the chromatograph, under the analysis condition, the peak area of each sulfide in the map is measured, and the sulfur content corresponding to the peak area of the sulfide is obtained by a sulfur quantitative response factor; the temperature of the liquid hydrocarbon flash evaporation gasification sampling injector is controlled to be 80-150 ℃, and the gas flow rate after gasification is controlled to be 150-250 mL/min.
Preferably, the external standard sample is carbonyl sulfide, helium or nitrogen is used as bottom gas, and the sulfur content prepared by the method is 5 x 10 -6 V/V-30×10 -6 And V/V external standard gas.
Preferably, the sulfide qualitative analysis database comprises sulfides with retention time of 4min-20min under the analysis conditions.
Preferably, the qualitative analysis database of sulfides includes part or all of carbonyl sulfide, hydrogen sulfide, carbon disulfide, sulfur dioxide, methyl mercaptan, ethanethiol, thiophene, dimethyl sulfide, isopropyl mercaptan, n-propyl mercaptan, t-butyl mercaptan, ethyl methyl sulfide, dimethyl disulfide, diethyl sulfide, methyl ethyl disulfide, and diethyl disulfide.
The preferred analysis conditions for the above analysis method are:
a chromatographic column: a PLOT column of a weak-polarity bonded silica gel porous open-cell tube, 60 mm multiplied by 0.32mm,
carrier gas: the high-purity helium is mixed with the nitrogen,
the split ratio is as follows: 5:1,
column head pressure of the chromatographic column: at a pressure of 25psi, and,
temperature of a sample injection valve: at a temperature of 200 c,
gas sample introduction quantitative tube: 1mL of the mixture is added into the reaction kettle,
column temperature: the initial temperature is 35 ℃, the initial time is 4min, the first-order heating rate is 20 ℃/min, the temperature is increased to 220 ℃, the temperature is kept for 6min, the second-order heating rate is 35 ℃/min, the temperature is increased to 260 ℃, the temperature is kept for 10min,
sulfur chemiluminescence detector pressure: the temperature of the molten iron was adjusted to 8Torr,
dual plasma controller pressure: the temperature of the molten steel is 360-375 Torr,
combustor temperature: at a temperature of 800 c,
hydrogen gas: 40mL/min, air: the concentration of the active carbon is 60mL/min,
background noise: 2.0mV.
The liquid hydrocarbon flash evaporation gasification sampling injector is connected with a sample valve of a chromatograph, the temperature of the liquid hydrocarbon flash evaporation gasification sampling injector is 100 ℃, and the gas flow rate after gasification is as follows: 200mL/min.
Under the above preferred analysis conditions, the sulfide qualitative analysis database includes:
carbonyl sulfide, retention time 4.851min; hydrogen sulfide, the retention time is 5.543min; carbon disulfide, retention time 8.806min; sulfur dioxide, retention time 8.962min; methyl mercaptan, retention time 10.603min; ethanethiol, retention time 12.169min; thiophene, retention time 13.123min; dimethyl sulfide, retention time 13.278min; isopropyl mercaptan, retention time 13.280min; n-propyl mercaptan, retention time 13.418min; tert-butyl mercaptan, retention time 14.096min; ethyl methyl sulfide, retention time 14.733min; dimethyl disulfide, retention time 14.980min; diethyl sulfide, retention time 16.535min; methyl ethyl disulfide, retention time 16.881min; diethyl disulfide, retention time 19.287min.
Preferably, in the assay method of the present invention, the minimum detectable concentration of sulfide is 25X 10 -9 V/V, the lowest detection limit of sulfur in sulfide is 0.5pg S/sec.
The invention also aims to provide the application of the analysis method in analysis of the sulfur distribution in the liquefied petroleum gas.
It is another object of the present invention to provide a qualitative analysis database of sulfides based on gas chromatography-sulfur chemiluminescence detector, wherein the database comprises sulfides with retention time of 4min-20min, and the analysis conditions of the gas chromatography-sulfur chemiluminescence detector are as described above.
Preferably, the qualitative analysis database of sulfides includes part or all of carbonyl sulfide, hydrogen sulfide, carbon disulfide, sulfur dioxide, methyl mercaptan, ethanethiol, thiophene, dimethyl sulfide, isopropyl mercaptan, n-propyl mercaptan, t-butyl mercaptan, ethyl methyl sulfide, dimethyl disulfide, diethyl sulfide, methyl ethyl disulfide, and diethyl disulfide.
More preferably, under the above preferred analysis conditions of the present invention, the retention time of the sulfide compounds included in the sulfide qualitative analysis database is:
carbonyl sulfide, retention time 4.851min; hydrogen sulfide, retention time 5.543min; carbon disulfide, retention time 8.806min; sulfur dioxide, retention time 8.962min; methyl mercaptan, retention time 10.603min; ethanethiol, retention time 12.169min; thiophene, retention time 13.123min; dimethyl sulfide, retention time 13.278min; isopropyl mercaptan, retention time 13.280min; n-propanethiol, retention time 13.418min; tert-butyl mercaptan, retention time 14.096min; ethyl methyl sulfide, retention time 14.733min; dimethyl disulfide, retention time 14.980min; diethyl sulfide, retention time 16.535min; methyl ethyl disulfide, retention time 16.881min; diethyl disulfide, retention time 19.287min.
In addition, the invention also aims to provide the application of the sulfide qualitative analysis database in analysis of sulfur distribution in liquefied petroleum gas based on a gas chromatography-sulfur chemiluminescence detector.
The gas chromatograph used in the present invention is equipped with a chemical workstation.
Under the preferred analytical conditions of the present invention, the retention time of each sulfur compound in the sulfide qualitative analysis database is substantially constant. The retention times will fluctuate only slightly with changes in the respective sulphide content and fluctuations in the column temperature, generally only in the second or third position after a fraction of the respective retention time. The chromatographic workstation will set the qualitative time window of the sulfide according to the absolute value range of the retention time.
The capillary column of the low-polarity bonded silica gel, preferably the porous layer open tubular chromatographic column (PLOT) of the low-sulfur selective low-polarity bonded silica gel, adopted by the invention has higher loading capacity and unique selectivity through tests, and can enable the sulfide component and the matrix component in the liquefied petroleum gas to achieve baseline separation. The inventors used a 60m long GS-on-a-gas chromatograph (equipped with an SCD detector) on an Agilent 7890 gas chromatograph in the United states
A capillary chromatographic column (belonging to a PLOT column) finds that carbonyl sulfide flows out before other sulfides, and solves the problem that the carbonyl sulfide in the prior art peaks at the tail of hydrogen sulfide and is difficult to separate.
The method for analyzing the sulfur distribution in the liquefied petroleum gas comprises the steps of optimizing analysis conditions, establishing a sulfide qualitative analysis database and establishing a quantitative analysis method. The present invention will be described in detail below from these aspects.
The gas chromatography-sulfur chemiluminescence detectors (GC-SCD) used in the following studies were 7890GC and 355SCD, agilent, usa.
9 standard gases were used, their sulphide composition is shown in Table 1, and the bottom gas was helium. The standard gas 1, the standard gas 2, the standard gas 3, the standard gas 5 and the standard gas 6 are standard gases of Huayuan gas chemical industry Co., ltd, beijing; standard gas 7, standard gas 8 and standard gas 9 are standard gases of Nanjing Tianze gas Limited liability company; the standard gas 4 is standard gas of Nanjing specialty gas plant Co.
Table 1 standard gaseous sulfur composition units: x 10 -6 V/V
(I) establishment and optimization of analysis conditions
Carrying out qualitative and quantitative analysis on sulfides in the liquefied petroleum gas, wherein except for the column temperature, the other conditions are as follows:
a chromatographic column: weak polarity bonded silica gel capillary column GS-
60m×0.32mm，
Carrier gas: the high-purity helium is obtained by using helium,
column head pressure of the chromatographic column: at a pressure of 25psi, and,
the split ratio is as follows: 5:1,
temperature of a sample injection valve: at a temperature of 200 c,
gas sample introduction quantifying pipe: 1mL of the mixture is added into the reaction kettle,
SCD detector pressure: the temperature of the molten iron was adjusted to 8Torr,
dual plasma controller pressure: 360Torr to 375Torr are used for carrying out the method,
combustor temperature: at the temperature of 800 ℃,
hydrogen gas: 40mL/min, air: the concentration of the active carbon is 60mL/min,
background noise: 2.0mV.
The liquid hydrocarbon flash evaporation gasification sampling injector is connected with a sample valve of a chromatograph, the temperature of the liquid hydrocarbon flash evaporation gasification sampling injector is 100 ℃, and the gas flow rate after gasification is as follows: 200mL/min.
The key point is the temperature setting before each sulfide peak in the liquefied petroleum gas to ensure that each sulfide in the liquefied petroleum gas has the highest response under the condition of good separation. The optimal column temperature condition is determined through an orthogonal test, three factors of initial temperature, initial time and heating rate are respectively taken, the bit levels of the established factors are shown in a table 2, the final temperature is set to be 220 ℃, the temperature is kept for 6min, the orthogonal test is carried out on the standard gas 2 under the conditions, and the height of the 5 th chromatographic peak (n-propyl mercaptan) is used as a measuring standard. According to the factor bit level table 2, selectL 9 (3 4 ) Orthogonal tables were used to determine the protocol, and the n-propanethiol peak in each test is shown in Table 3.
TABLE 2 bit-level table of three-factor three-level orthogonal test factors
TABLE 3 three-factor three-level orthogonal test protocol and test results
Directly reading: 9 out of 7A 1 B 3 C 3 Preferably, the analytical spectrum under these conditions is shown in FIG. 1. Through calculation: from the viewpoint of T value, A is preferred 3 B 3 C 3 The analysis spectrum under the conditions is shown in FIG. 2.
Further analysis of variance was performed:
(1) Calculating the sum of squares of the deviations
∑x 2 ＝1.08 2 +1.49 2 +2.48 2 +2.45 2 +3.73 2 +3.26 2 +4.05 2 +2.39 2 +3.20 2
＝72.43
S E ＝S General assembly -S A -S B -S C ＝7.73-0.40-4.48-2.48＝0.37
(2) Degree of freedom of calculation
ν General assembly ＝n-1＝9-1＝8
ν A ＝ν B ＝ν C ＝3-1＝2
(3) Column analysis of variance table (see Table 4)
TABLE 4 ANOVA TABLE
F 0.25 (2,2)＝3；F 0.10 (2,2)＝9；F 0.05 (2,2)＝19；F 0.01 (2,2)＝99
F 0.10 (2,2)<F B <F 0.05 (2, 2), significance of the factor, mark, significance level 0.10;
F 0.25 (2,2)<F C <F 0.10 (2, 2), indicating that this factor has some effect, mark (, significance level 0.25;
F 0.25 (2,2)>F A this factor is illustrated to have a small influence.
If the significance level is 0.10, the factor B is significant, and the factors C and A are not significant.
(4) Selecting the optimal bit level combination
The selection principle is as follows: the most obvious factors are selected from the best level, and the other factors can be selected by integrating the specific conditions of chromatographic peak separation, analysis time and the like.
The results of this experiment were subjected to varianceAfter analysis, the significance order of the obtained factors is as follows: and (6) BCA. The optimal bit-level combination is: a. The 1 B 3 C 3 I.e. orthogonal test 7 conditions: the initial temperature is 35 deg.C, the initial time is 4min, and the heating rate is 20 deg.C/min. The column temperature conditions for determining the sulfur distribution analysis in the liquefied petroleum gas are as follows: the initial temperature is 35 ℃, the initial time is 4min, the heating rate is 20 ℃/min, the final temperature is 220 ℃, and the temperature is kept for 6min. The analytical spectrum of the standard gas 2 under the analysis condition is shown in figure 3, and the chromatographic peaks are well separated and have high response.
Establishment of qualitative analysis database of (di) sulfide
As mentioned above, various types of sulfides are contained in the liquefied petroleum gas, but the retention times of various sulfides based on a weakly polar bonded silica gel PLOT column (60 m.times.0.32 mm) have not been reported, and the retention times are shifted depending on the analysis conditions (stationary phase, chromatography column, column temperature, etc.). Therefore, in order to perform accurate qualitative analysis, it is necessary to establish a sulfide qualitative analysis database including as many sulfides and their retention times as possible under the analysis conditions of the present invention.
For this reason, under the optimum analysis conditions for the analysis of sulfur distribution in the liquefied petroleum gas determined above, the standard gas 1, the standard gas 3, the standard gas 4, the standard gas 5, the standard gas 6, the standard gas 7 and the standard gas 8 were analyzed, and their analysis spectrograms are respectively shown in fig. 4, fig. 5, fig. 6, fig. 7, fig. 8, fig. 9 and fig. 10. The boiling point of hydrogen sulfide is-60.4 deg.C and that of carbonyl sulfide is-50.3 deg.C, and the hydrogen sulfide peak position should be before carbonyl sulfide according to the flow characteristics of weak polar column. However, in practical detection, the peak position of the hydrogen sulfide is unexpectedly found to be after carbonyl sulfide. This phenomenon may be caused by the fact that hydrogen sulfide has a dipole moment of 0.9 debyes and carbonyl sulfide has a dipole moment of 0.7debyes, and the polarity of hydrogen sulfide is greater than that of carbonyl sulfide, so that hydrogen sulfide and GS-
The chromatographic column has stronger action, which causes the hydrogen sulfide to flow out slowly. When standard gas 4 is analyzed, the peak is dimethyl disulfide after the retention time is 14.978min, and the figure shows that6, which is the result of the polymerization of the methanol component. The standard gas 5 was analyzed for sulfur dioxide as a severe tailing peak, see fig. 7, since sulfur dioxide is a polar molecular acid gas.
When standard gas 9 is analyzed, no peak is found in diethyl disulfide, in order to ensure that heavy sulfides in the liquefied petroleum gas are completely eluted, second-order heating is added on the basis of the preferred first-order heating, and the column temperature condition for analyzing the sulfur distribution in the liquefied petroleum gas is finally determined as follows: the initial temperature is 35 ℃, the initial time is 4min, the first-order heating rate is 20 ℃/min, the temperature is increased to 220 ℃, the temperature is kept for 6min, the second-order heating rate is 35 ℃/min, the temperature is increased to 260 ℃, and the temperature is kept for 10min. Under the condition of the second-order temperature rise, an analysis spectrum of the standard gas 9 is shown in FIG. 11, and carbonyl sulfide and diethyl disulfide all peak.
The established analysis method is utilized to monitor and analyze the liquefied petroleum gas before and after the site deodorization of the device of the Jiujiang division of the petrochemical industry so as to test the accuracy and the practicability of the method. On the site of a catalytic cracking production device set II of the division of Jiujiang, 5/11/2015, a 250mL steel cylinder is used for collecting deodorized liquefied petroleum gas for analysis, and the analysis spectrogram is shown in FIG. 12. The peak time of carbonyl sulfide (COS) is 4.223min, while the peak time of COS in standard gas is typically 4.851min. Theoretically, the bottom gas of the COS standard gas is helium, which is the same as the carrier gas used in the present invention. When analyzing liquefied petroleum gas, the column capacity is increased due to the liquefied petroleum gas entering the column, causing COS to peak ahead of time. The chromatographic peak with retention time of 14.096min is identified as tert-butylmercaptan by extensive literature search and from empirical data, its boiling point is 65.0 ℃.
The unknown peak with retention time of 16.881min in FIG. 12 was analyzed and judged: due to its retention time between the dimethyldisulfide chromatographic peak (14.970 min) and the diethyldisulfide chromatographic peak (19.287 min), this unknown peak can be inferred to be the chromatographic peak for methylethyldisulfide with the boiling point of 121.0 ℃ in the absence of the methylethyldisulfide standard by reference to the data in table 5, according to the separation characteristics of the less polar chromatographic column used in the present method, i.e. the characteristic of the various sulfides running out essentially in boiling point order. In view of the desulfurization mechanism of the liquefied petroleum gas catalytic oxidation sweetening device, the reaction of the process can be represented by the following reaction formula:
RSH+NaOH→RSNa+H 2 O
4RSNa+O 2 +2H 2 O→2RSSR+4NaOH
wherein R is CH 3 -or CH 3 CH 2 -, with CH 3 -is predominant. Part of the sodium methyl mercaptide may react with the sodium ethanethiol to generate methyl ethyl disulfide which is detected as recycled alkali liquor enters the liquefied petroleum gas, so that the principle proves that the methyl ethyl disulfide may appear in the liquefied petroleum gas. In conclusion, the unknown peak can be determined to be the chromatographic peak of methylethyldisulfide with a retention time of 16.881min.
The analysis of standard gas is integrated, according to the time position and area size of each sulfide peak, the molecular weight and boiling point of each sulfide are combined, the analysis of liquefied petroleum gas before and after deodorization in a production field is combined, and finally, a qualitative database of 16 sulfides during the analysis of the sulfur distribution in the liquefied petroleum gas is established according to the qualitative of empirical data, and the database is shown in table 5.
TABLE 5 qualitative data for the individual sulfides
(III) quantitative analysis
1. Determination of quantitative response factor for sulfur
The SCD detector responds to sulfur in different structures in equimolar mode, and response factors of sulfur in sulfides with different concentrations are almost the same. Because the content of carbonyl sulfide in the liquefied petroleum gas is high and stable, the carbonyl sulfide is preferably used as an external standard.
And establishing a sulfur quantitative working curve of the carbonyl sulfide by taking the sulfur content of the carbonyl sulfide as a horizontal ordinate and the peak area of the carbonyl sulfide as a vertical coordinate. Experimental data for gas dilution with standard gas 6 was used to establish a quantitative sulfur working curve through the origin, see fig. 13. This is a straight line through the origin with a slope of 33257 and a linear correlation coefficient R of 0.9995. An over-origin sulfur quantitative working curve is established by using experimental data of the standard gas 6, as shown in fig. 14, the slope of the line is 32954, which further indicates that the response factors of the SCD detector to sulfur with different concentrations are almost the same, and the measured sulfur quantitative response factor is 3.0 × 10 -5 。
TABLE 6 test data for carbonyl sulfide standard gas determination
2. Precision and accuracy of sulfur quantitation
The sulfur response factor is the sulfur content of the external standard sample divided by the chromatographic peak area of the external standard sample, so that the sulfur content of each sulfide in the liquefied petroleum gas is the chromatographic peak area of each sulfide multiplied by the sulfur response factor under the condition that the sulfur response factor is known.
The standard gas 1 is analyzed in parallel for 6 times, the sulfur response factor measured by the standard gas 6 is used for calculation, meanwhile, the standard gas 2, the standard gas 3, the standard gas 4, the standard gas 5, the standard gas 7, the standard gas 8 and the standard gas 9 are analyzed, the analysis results are shown in tables 7, 8, 9 and 10, the relative standard deviation of the sulfur quantification of each component is less than 10 percent, the absolute value of the relative error is less than 10 percent, and the sulfur quantitative analysis method has good precision and accuracy.
TABLE 7 analysis results of Standard gas 1
TABLE 8 analysis results of Standard gas 2 and Standard gas 3
TABLE 9 analysis results of Standard gas 4 and Standard gas 5
TABLE 10 analysis results of standard gas 7, standard gas 8 and standard gas 9
3. Further examination of SCD response characteristics
In order to separate the three components well and obtain a fast peak, the following chromatographic conditions are adopted when the SCD response characteristics are examined:
a chromatographic column: DB-1 30m 0.32mm 1.0um nonpolar capillary column; column temperature: the initial temperature is 65 ℃, the temperature is kept for 1min, the temperature programming rate is 15 ℃/min, and the final temperature is 120 ℃; column head pressing: 12psi; the split ratio is as follows: 50; column flow rate: 2.4mL/min, line speed: 40.0cm/sec; sample inlet temperature: 250 ℃; sample introduction amount: 1uL.
Typical operating conditions for SCD are detector pressure: 8Torr; dual plasma controller pressure: 360Torr-375 Torr; combustor temperature: 800 ℃; hydrogen gas: 40mL/min, air: 60mL/min; background noise: 2mV.
Under the analysis conditions, the SCD debugging standard sample of the American agilent company is analyzed, and the analysis spectrogram is shown in figure 15, wherein: 1. peak No. 2 was dimethylsulfide, peak No. 2 was ethylmethylsulfide, peak No. 3 was thiophene, and the baseline noise intensity was 60 (40000 was 15 uV). The results of the calculation of the Minimum Detection Limit (MDL) for sulfur in each sulfide, when the signal to noise ratio was calculated as 3.3. The lowest detection limit is calculated as follows:
TABLE 11 lowest detection limit for sulfur in sulfides
Because the SCD can detect a plurality of sulfides with different structures, and the sulfur content of the sulfides is greatly changed, the inventor adopts a thiophene standard substance and a diethyl disulfide standard substance to prepare standard solutions with different concentrations to carry out quantitative experiments.
Weighing 0.0180g of thiophene on an electronic balance, putting the thiophene into a 100mL volumetric flask to prepare 180.0mg/L of thiophene standard solution, and sequentially diluting the thiophene standard solution into 90.00, 45.00, 9.00 and 0.90mg/L of thiophene standard solution. The sulfur content of the thiophene compound is 38.11 percent, and the sulfur contents of the standard sulfide solutions are 68.60, 34.30, 17.15, 3.43 and 0.34mg/L respectively. Under the analysis condition of examining SCD response characteristics, the thiophene standard solutions are sequentially analyzed, the analysis results are shown in a table 12, according to the analysis data, the sulfur content of thiophene is taken as a horizontal coordinate, the peak area of thiophene is taken as a vertical coordinate, a sulfur quantitative working curve of thiophene is established, Y =838.84X, and a linear correlation coefficient R 2 =0.9998, see fig. 16, which shows that the thiophene sulfur content correlates well with the thiophene peak area. In Table 12, the thiophene retention times are very close, with an average of 10.170min, a standard deviation of 0.004min, and a relative standard deviation of 0.04%, indicating that the chromatographic separation system has very stable performance.
TABLE 12 test data for thiophene standard solution determination
0.0180g of diethyl disulfide was weighed out on an electronic balance into a 100mL volumetric flask to prepare 180.0mg/L of diethyl disulfide standard solution, which was diluted in turn to 90.00, 45.00, 9.00, 0.90mg/L of diethyl disulfide standard solution. The sulfur content of diethyl disulfide was 52.46%, and the sulfur contents of these sulfide standard solutions were 94.43, 47.21, 23.61, 4.72, and 0.47mg/L, respectively. These diethyl disulfide standard solutions were analyzed in sequence, and the analysis results are shown in Table 13. From these analytical data, a sulfur quantitative working curve for diethyl disulfide was established with the sulfur content of diethyl disulfide as abscissa and the peak area of diethyl disulfide as ordinate, y =774.1x, and the linear correlation coefficient R =0.9995, see fig. 17. The diethyl disulfide retention times in Table 13 are very close, with an average of 21.599min, a standard deviation of 0.005min and a relative standard deviation of 0.02%, which also indicates that the chromatographic separation system is very stable.
The slope of the thiophene sulfur quantitation working curve is similar to that of diethyl disulfide, which illustrates the equimolar response of the SCD detector to sulfur in different structure sulfides. The two sulfur quantitative working curves pass through the original point, and the linear correlation coefficients R are 0.9999 and 0.9995 respectively, which indicates that the response factors of sulfur in sulfides with different concentrations are almost the same.
TABLE 13 Experimental data for the determination of the Diethyldisulfide Standard solution
Through the research, a qualitative and quantitative analysis method for the sulfur distribution in the liquefied petroleum gas by utilizing a gas chromatography/sulfur chemiluminescence detector is established. The method has the following advantages:
(1) high precision and good accuracy: the sulfur analysis relative standard deviation of each sulfide is less than 10%, and the absolute value of the relative error is less than 10%.
(2) The detection limit is low: the lowest detection concentration of sulfur in sulfide can completely reach 25 multiplied by 10 -9 V/V. The lowest detection limit of sulfur in the sulfide can completely reach 0.5pg S/sec.
(3) The quantification is quick and has no interference: under the analysis condition of the invention, the sulfide realizes baseline separation without interference. The analysis of one sample takes only about 30min to complete.
(4) The method is simple and convenient: the sample dosage is less, the sample injection amount is 0.25mL-1mL, and the sample is directly injected without pretreatment.
Drawings
The invention is described in further detail below with reference to the drawings and the detailed description.
FIG. 1 shows: a schematic diagram of the results of the orthogonal test; in the figure, the numerical value on the abscissa represents the test number, and the numerical value on the ordinate represents the peak height of n-propanethiol (10E + 3).
FIG. 2 shows: different bit level trend plots.
FIG. 3 shows: quadrature assay 7 analyses chromatograms.
FIG. 4 shows: standard gas 1 analysis chromatogram.
FIG. 5 shows: standard gas 3 analysis chromatogram.
FIG. 6 shows: standard gas 4 analysis chromatogram.
FIG. 7 shows: standard gas 5 analysis chromatogram.
FIG. 8 shows: standard gas 6 analysis chromatogram.
FIG. 9 shows: standard gas 7 analysis chromatogram.
FIG. 10 shows: standard gas 8 analysis chromatogram.
FIG. 11 shows: standard gas 9 analysis chromatogram.
FIG. 12 shows: and analyzing a chromatogram of the sample subjected to deodorization by the catalytic cracking liquefied petroleum gas.
FIG. 13 shows: a sulfur quantitative working curve of carbonyl sulfide is established according to experimental data of standard gas 6 diluent gas; in the drawing, the horizontalThe numerical value of the coordinates represents the sulfur content of carbonyl sulfide (unit:. Times.10) -6 V/V), the numerical value of the ordinate represents the carbonyl sulfide peak area (unit: μ V × s). The regression equation for the working curve is:
Y＝33257X(R 2 ＝0.9991)。
FIG. 14 shows: sulfur response factor determination of carbonyl sulfide established with experimental data of standard gas 6; in the figure, the numerical value on the abscissa represents the sulfur content (unit:. Times.10) of carbonyl sulfide -6 V/V), the numerical value of the ordinate represents the carbonyl sulfide peak area (unit: μ V × s). The regression equation for the working curve is:
Y＝32954X(R 2 ＝1)。
FIG. 15 shows: SCD standard sample analysis chromatogram
FIG. 16 shows: sulfur quantitative working curve of thiophene; in the figure, the horizontal axis represents the sulfur content (unit: mg/L) of carbonyl sulfide, and the vertical axis represents the area of the carbonyl sulfide peak (unit: μ V × s). The regression equation for the working curve is:
Y＝838.84X(R 2 ＝0.9998)。
FIG. 17 shows: sulfur quantitative working curve for diethyl disulfide; in the figure, the horizontal axis represents the sulfur content (unit: mg/L) of carbonyl sulfide, and the vertical axis represents the area of the carbonyl sulfide peak (unit: μ V × s). The regression equation for the working curve is:
Y＝774.1X(R 2 ＝0.9995)。
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
The gas chromatography-sulfur chemiluminescence detectors (GC-SCD) used in the examples were 7890GC and 355SCD, agilent, usa. Unless otherwise specified, the standard gases used in the following examples are all commercially available.
The samples before and after deodorization of the first and second sets of catalytically cracked liquefied petroleum gas of Jiujiang division 10/22/2015 were analyzed, and the analysis results are shown in Table 14, and it can be seen from the analysis results that the disulfide sulfur content in the liquefied petroleum gas sample after deodorization was increased, while the sulfur content of other sulfides was decreased.
TABLE 14 analysis of sulfur distribution in LPG on site
In a word, the method for qualitatively/quantitatively analyzing the sulfide in the liquefied petroleum gas by using the gas chromatography/sulfur chemiluminescence detector, which is established by the invention, can identify various sulfur compounds with different structure types in the liquefied petroleum gas at one time and quantitatively analyze the sulfur compounds by depending on the sulfide qualitative analysis database; the analysis of one sample is completed only within about 30min, thereby ensuring that a proper desulfurization means is adopted in real time in a production field and ensuring the production stability and the product quality.
Claims (5)
1. The analysis method of the morphological distribution of the sulfide in the liquefied petroleum gas is based on a gas chromatography-sulfur chemiluminescence detector, comprises the establishment of analysis conditions, qualitative analysis and quantitative analysis, and comprises the following specific steps:
I. establishment of analysis conditions
A chromatographic column: a PLOT column of a weak-polarity bonded silica gel porous open-cell tube, 60 mm multiplied by 0.32mm,
carrier gas: the high-purity helium is mixed with the nitrogen,
the split ratio is as follows: 5:1,
column head pressure of the chromatographic column: at a pressure of 25psi, and,
temperature of a sample injection valve: at a temperature of 200 c,
gas sample introduction quantitative tube: 1mL of the mixture is added into the reaction kettle,
column temperature: the initial temperature is 35 ℃, the initial time is 4min, the first-order heating rate is 20 ℃/min, the temperature is increased to 220 ℃, the temperature is kept for 6min, the second-order heating rate is 35 ℃/min, the temperature is increased to 260 ℃, the temperature is kept for 10min,
sulfur chemiluminescence detector pressure: the temperature of the molten iron was adjusted to 8Torr,
dual plasma controller pressure: the temperature of the molten steel is 360-375 Torr,
combustor temperature: at a temperature of 800 c,
hydrogen gas: 40mL/min, air: the concentration of the active carbon is 60mL/min,
background noise: 2.0mV of the total weight of the alloy,
the liquid hydrocarbon flash evaporation gasification sampling injector is connected with a sample valve of a chromatograph, the temperature of the liquid hydrocarbon flash evaporation gasification sampling injector is 100 ℃, and the flow rate of the gasified gas is as follows: 200mL/min;
qualitative analysis of
Connecting the liquid hydrocarbon flash evaporation gasification sampling injector with a sample valve of a chromatograph, so that a liquefied petroleum gas sample to be detected is gasified through the liquid hydrocarbon flash evaporation gasification sampling injector firstly, then enters a gas sample introduction quantitative tube through a gas sample introduction valve on the chromatograph for sample introduction, a map is obtained under the analysis condition, then the map is compared with a sulfide qualitative analysis database under the analysis condition, and a sulfide structure in the liquefied petroleum gas sample to be detected is determined according to retention time;
the sulfide qualitative analysis database includes all of carbonyl sulfide, hydrogen sulfide, carbon disulfide, sulfur dioxide, methyl mercaptan, ethanethiol, thiophene, dimethyl sulfide, isopropyl mercaptan, n-propyl mercaptan, t-butyl mercaptan, ethyl methyl sulfide, dimethyl disulfide, diethyl sulfide, methyl ethyl disulfide, diethyl disulfide;
quantitative analysis
Determining a sulfur quantitative response factor under the analysis condition by taking the gas organic sulfide as an external standard sample; and connecting the liquid hydrocarbon flash evaporation gasification sampling injector with a sample injection valve of a chromatograph, so that the liquefied petroleum gas sample to be detected is gasified by the liquid hydrocarbon flash evaporation gasification sampling injector firstly, and then enters a gas sample injection quantitative tube for sample injection through the gas sample injection valve on the chromatograph, under the analysis condition, the peak area of each sulfide in the spectrum is determined, and the sulfur content corresponding to the peak area of the sulfide is obtained by a sulfur quantitative response factor.
2. The method of claim 1, wherein the external standard is carbonyl sulfide, and the external standard is prepared to have a sulfur content of 5 x 10 using helium or nitrogen as a base gas -6 V/V-30×10 -6 And V/V external standard gas.
3. The analytical method of claim 1, wherein the sulfide qualitative analysis database comprises: carbonyl sulfide, retention time 4.851min; hydrogen sulfide, retention time 5.543min; carbon disulfide, retention time 8.806min; sulfur dioxide, retention time 8.962min; methyl mercaptan, retention time 10.603min; ethanethiol, retention time 12.169min; thiophene, the retention time is 13.123min; dimethyl sulfide, retention time 13.278min; isopropyl mercaptan, retention time 13.280min; n-propyl mercaptan, retention time 13.418min; tert-butyl mercaptan, retention time 14.096min; ethyl methyl sulfide, retention time 14.733min; dimethyl disulfide, retention time 14.980min; diethyl sulfide, retention time 16.535min; methyl ethyl disulfide, retention time 16.881min; diethyl disulfide, retention time 19.287min.
4. The assay of any one of claims 1 to 3, wherein the minimum detectable concentration of sulfide is 25 x 10 -9 V/V, the lowest detection limit of sulfur in sulfide is 0.5pg S/sec.
5. Use of the analytical method according to any one of claims 1 to 4 for analysis of sulfur distribution in liquefied petroleum gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710224550.5A CN108693256B (en) | 2017-04-07 | 2017-04-07 | Analysis method for sulfur distribution in liquefied petroleum gas and sulfide qualitative database |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710224550.5A CN108693256B (en) | 2017-04-07 | 2017-04-07 | Analysis method for sulfur distribution in liquefied petroleum gas and sulfide qualitative database |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108693256A CN108693256A (en) | 2018-10-23 |
| CN108693256B true CN108693256B (en) | 2023-03-17 |
Family
ID=63842186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710224550.5A Active CN108693256B (en) | 2017-04-07 | 2017-04-07 | Analysis method for sulfur distribution in liquefied petroleum gas and sulfide qualitative database |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108693256B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109613173A (en) * | 2018-12-21 | 2019-04-12 | 陕西延长石油（集团）有限责任公司延安石油化工厂 | A kind of method that constant-current titration measures mercaptan sulfur in gas |
| CN111829867B (en) * | 2020-07-17 | 2022-10-21 | 贵州理工学院 | Method for rapidly determining sulfur species in solid-phase minerals by using infrared-temperature programming oxidation combination method |
| CN114836245B (en) * | 2021-02-01 | 2023-06-30 | 中国石油天然气集团有限公司 | Pilot-scale treatment process for crude gas |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1085075A1 (en) * | 1999-09-16 | 2001-03-21 | Abb Research Ltd. | Treatment of hydrogen sulfide-containing gaseous compositions |
| CN104807895B (en) * | 2014-01-27 | 2019-07-09 | 中国石油化工股份有限公司 | The analysis method of sulphur content cloth, the sulfide qualitative analysis database utilized and application thereof in a kind of methyl tert-butyl ether product |
| CA2983156C (en) * | 2015-04-17 | 2020-04-07 | Cabot Corporation | Sulfur removal from petroleum fluids |
| CN106290660A (en) * | 2016-11-10 | 2017-01-04 | 同济大学 | A kind of fast, the method for sulfurous gas in accurate quantitative analysis biogas |
-
2017
- 2017-04-07 CN CN201710224550.5A patent/CN108693256B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108693256A (en) | 2018-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104807895B (en) | The analysis method of sulphur content cloth, the sulfide qualitative analysis database utilized and application thereof in a kind of methyl tert-butyl ether product | |
| CN108693256B (en) | Analysis method for sulfur distribution in liquefied petroleum gas and sulfide qualitative database | |
| Hernández-Fernández | Quantification of oxygenates, sulphides, thiols and permanent gases in propylene. A multiple linear regression model to predict the loss of efficiency in polypropylene production on an industrial scale | |
| US20110263034A1 (en) | Method and device for fast sulfur characterization and quantification in sedimentary rocks and petroleum products | |
| CN103336070B (en) | The pick-up unit of sulfur-bearing failure gas component and method in a kind of quantitative detection sulfur hexafluoride electrical equipment | |
| Djokic et al. | Quantitative on-line analysis of sulfur compounds in complex hydrocarbon matrices | |
| CN105911158A (en) | Gas chromatograph and detection method for determining total content of sulfides in natural gas | |
| CN110514755B (en) | Chromatographic detection device and method for detecting organic sulfur | |
| CN102043021B (en) | Qualitative and quantitative analysis method of elemental sulfur in light petroleum fractions and light petroleum products | |
| CN102507779B (en) | Method for measuring hydrogen sulfide content in desulfurized amine | |
| CN102788856B (en) | The analytical approach of elementary sulfur quantitative and qualitative analysis in liquefied petroleum gas (LPG) | |
| Firor et al. | A comparison of sulfur selective detectors for low level analysis in gaseous streams | |
| JP2014507660A (en) | Method for measuring the content of hydrogen sulfide in crude oil and residual oil | |
| Bouyssiere et al. | Determination of mercury in organic solvents and gas condensates by μflow-injection—inductively coupled plasma mass spectrometry using a modified total consumption micronebulizer fitted with single pass spray chamber | |
| CN109709219B (en) | Method for detecting structure and/or content of polar substance in non-polar matrix | |
| Pauls | Determination of elemental sulfur in gasoline by gas chromatography with on-column injection and flame ionization detection following derivatization with triphenylphosphine | |
| CN102749390B (en) | Method for determining contents of microscale allene and acetylene in MTO (methanol to olefin) products through gas chromatography | |
| CN105259156A (en) | Sulfur testing device and method | |
| CN107782807A (en) | The analysis method of sulphur content cloth and a kind of sulfide qualitative data storehouse in a kind of propylene feedstocks | |
| CN105424866A (en) | Method for quickly analyzing gas mixture by determining hydrogen and carbon monoxide | |
| CN109212047B (en) | Analyzer for content of sulfur-containing compound in hydrocarbon gas | |
| Pavlova et al. | Determination of total nitrogen content by different approaches in petroleum matrices | |
| Field et al. | Conversion of Organic Sulfur to Hydrogen Sulfide for Analysis | |
| Pavlova et al. | Sulfur compounds in petroleum hydrocarbon streams | |
| CN111650324A (en) | Online detection method for hydrocarbon content |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |