CN106770709A - A kind of method that gas chromatograph direct injected determines each Sulfur in coke-stove gas - Google Patents
A kind of method that gas chromatograph direct injected determines each Sulfur in coke-stove gas Download PDFInfo
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- CN106770709A CN106770709A CN201611039758.1A CN201611039758A CN106770709A CN 106770709 A CN106770709 A CN 106770709A CN 201611039758 A CN201611039758 A CN 201611039758A CN 106770709 A CN106770709 A CN 106770709A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
Abstract
The invention discloses a kind of method that gas chromatograph direct injected determines each Sulfur in coke-stove gas, the gas chromatograph uses flame photometric detector, auto linear data processor, quantity tube is set to 0.2~0.4ml, and signal amplifier resistor coupled in parallel resistance is 200~700K Ω resistance.The mass concentration that the method quantitative determination is applied to sulphur is 2.86~142.86mg/m3Coke-stove gas.Each form sulfur component in coke-stove gas is determined using this method, it is easy to operate, as a result accurately, it is to avoid error that troublesome operation is caused and may cause the incomplete problem of analyze data after dilute sample gas.For the application of coke oven gas desulfurization technology provides accurate and effective data, Instructing manufacture work.
Description
Technical field
The invention belongs to chemical analysis technical field, and in particular to a kind of gas chromatograph direct injected determines coke-stove gas
In each Sulfur method.
Background technology
It is accessory substance imflammable gas that coal for coking is obtained in coke oven after high-temperature retorting in coke-stove gas.Coke oven
The form sulfur component such as hydrogen sulfide, cos, mercaptan, thiophene has serious corrosion to equipment in coal gas, can also reduce catalyst work
Property, shorten catalyst life, while giving off sulfur dioxide severe contamination environment after burning.According to national standard《GB 16171-
2012 --- coking chemistry emission of industrial pollutants standard (water, air)》Specify existing crude benzene tubular furnace, semicoke drying and ammonia
The facility SO2 emissions that dore furnace etc. uses coke-stove gas are less than 100mg/m3, newly-built uses coke-stove gas device two
Sulfur oxide emissions amount is less than 50mg/m3.Require that the analysis method upper limit of detection of sulfide in coke oven thing component is not less than
100mg/m3。
At present, the detection and analysis to gaseous sulfide is main based on chemical analysis and gas chromatography.Iodine number
Method, lead acetate method, Coulomb equation etc. are used for the sulfide analysis of coke-stove gas, and these methods can only detect that total sulfur contains
Amount, and result is affected by many factors, it is impossible to for desulfurization technology provides accurate and effective data, Instructing manufacture.Gas-chromatography point
Analysis method is short because of analysis time, and sensitivity is high, it has also become be employed widest analysis method.The measure of red, orange, green, blue, yellow (ROGBY) sulfide
It is main to use flame photometric detector and sulfur chemiluminescent detector.Flame photometric detector have to sulfide high selectivity,
High sensitivity, and procurement price and maintenance cost are low compared with sulfur chemiluminescent detector, are widely used in vulcanizing analyte detection.
Using flame photometric detector, sulfide sample size is 2 × 10-7~1 × 10-4During mg, the content of sulfide and its
Concentration square is directly proportional.The matter of form sulfur component is detected using the chromatogram analysis method direct injected with flame photometric detector
Amount concentration is less than 71.43mg/m3.The analysis method of existing direct injected detection sulfide in coke oven thing component can not meet
National standard《GB 16171-2012 --- coking chemistry emission of industrial pollutants standard (water, air)》It is required that coke-stove gas
Facility SO2 emissions be less than 100mg/m3, but concentration is reduced in range ability by dilution.Work as coke-oven coal
When sulfide composition concentration difference is big in gas, part form sulfur component to be measured need to be made using the method for dilution dilution certain multiple
Concentration is in analysis range, in order to accurately to each form sulfur component quantitative analysis to be measured, need to be according to different shape sulphur component
Concentration dilute different multiples respectively and be analyzed one by one, cumbersome, analysis time is long, especially for relative in concentration
The quantitative analysis of relatively low form sulfur component, the form sulfur component concentration causes analysis to be tied less than test limit after dilution certain multiple
Fruit shows that the sulfide is not detected, and enriched sample can disturb low concentration sample peak if not diluting, and separating degree is poor, it is difficult to accurate
Qualitative and quantitative analysis, wherein concentration form sulfur component concentration high higher than analysis range, chromatographic column and detector may be polluted.
Therefore it provides a kind of gas chromatography, each form sulfur component in energy direct injected detection coke-stove gas, it is to avoid cumbersome
The error that operation is caused, while also avoiding that after diluting identical multiple the incomplete problem of analyze data may be caused, becomes this
Art personnel's problem demanding prompt solution.
The content of the invention
The invention provides a kind of method that gas chromatograph direct injected determines each Sulfur in coke-stove gas, using this
Sample gas directly can be injected each form sulfur component in gas chromatograph for determination coke-stove gas by method, are solved troublesome operation and are caused
Error and dilute sample gas after may cause the incomplete problem of analyze data.
The technical solution adopted by the present invention is as follows：
A kind of gas chromatograph direct injected determines the method for each Sulfur in coke-stove gas, the detection of the gas chromatograph
Device is flame photometric detector, and data handling system is auto linear data processor, meets following equation：
In formula, x：Sulfur content, unit is mg/m3；hi:In the response of initial time, unit is mm to component i；Δt：When
Between increment, typically less than or equal to 10 milliseconds (ms), unit be millisecond (ms)；k：Coefficient；Quantity tube is set to 0.2~0.4ml,
Signal amplifier resistor coupled in parallel resistance is 200~700K Ω resistance；Photomultiplier tube voltage is set to 400~700V, chromatographic column
Column temperature be set to 50~70 DEG C, detector temperature is more than 100 DEG C；Methods described includes qualitative method and quantitative approach；
Methods described is comprised the following steps including qualitative method：The standard sample of each Sulfur is taken, institute is directly injected into
Gas chromatograph is stated, standard sample collection of illustrative plates is obtained；The coke-stove gas is taken, the gas chromatograph is directly injected into, sample collection of illustrative plates is obtained；Will
Each component retention time is determined compared with one pack system sulphur retention time in the standard diagram in the sample chromatogram figure
Property；
The quantitative approach is comprised the following steps：Set up the linear formula of each Sulfur, auto linear described in typing
Change data processor, verify each Sulfur linear formula；The coke-stove gas is directly injected into the gas chromatograph to survey
It is fixed, calculated according to each Sulfur linear formula by the auto linear data processor, obtain final product the coke-stove gas
Sulfur content to be measured.
Further, each Sulfur includes hydrogen sulfide, cos, methyl mercaptan, carbon disulfide, thiophene, the vulcanization
Hydrogen, chromatographic column used by the measure of cos are GDX-301 posts, the methyl mercaptan, carbon disulfide, chromatographic column used by the measure of thiophene
It is TCP posts.
Further, the linear formula of each Sulfur includes cos linear formula, carbon disulfide linear formula.
Further, the cos linear formula is set up to comprise the following steps：Configuration various concentrations and concentration be
2.86~14.29mg/3Or 14.29~142.86mg/m3Cos standard sample it is at least each 5, the chromatographic column be GDX-
301 posts, by the gas chromatograph for determination content, by the concentration of the cos standard sample and measured content with
2.86~14.29mg/m3With 14.29~142.86mg/m3Two interval linear fits respectively, obtain cos linear formula, by institute
State auto linear data processor described in cos linear formula typing.
Verify comprising the following steps for the cos linear formula：Cos standard sample is taken to the gas chromatograph
Carry out single point correction, configuration various concentrations and concentration is 2.86~14.29mg/m3Or 14.29~142.86mg/m3Carbonyl
Sulphur repetition measurement standard sample is at least each 5, injects the gas chromatograph for determination, is pressed by the auto linear data processor
Calculate content according to the cos linear formula, by the concentration of the cos repetition measurement standard sample and content obtained by repetition measurement with
2.86~14.29mg/m3With 14.29~142.86mg/m3Linear fits are distinguished in two intervals, such as linear, then the cos line
Property formula set up.
Further, the carbon disulfide linear formula is set up to comprise the following steps：Configuration various concentrations and concentration be
1.43~7.14mg/m3Or 7.14~71.43mg/m3Carbon disulfide standard sample it is at least each 5, the chromatographic column be TCP
Post, by the gas chromatograph for determination content, by 2 times of Carbon Disulfides and measured content with 2.86~
14.29mg/m3With 14.29~142.86mg/m3Two interval linear fits respectively, obtain carbon disulfide linear formula, by described two
Auto linear data processor described in nitric sulfid linear formula typing.
Verify that the carbon disulfide linear formula comprises the following steps：Configuration various concentrations and concentration be 1.43~
7.14mg/m3Or 7.14~71.43mg/m3Carbon disulfide repetition measurement standard sample it is at least each 5, by the auto linear
Data processor calculates content according to the carbon disulfide linear formula, by 2 times of carbon disulfide repetition measurement standard sample concentration
With the content obtained by repetition measurement with 2.86~14.29mg/m3With 14.29~142.86mg/m3Two interval linear fits respectively, such as into
Linearly, then carbon disulfide linear formula is set up.
Further, cos linear formula component to be measured suitable for the coke-stove gas is hydrogen sulfide and carbonyl
The quantitative determination of base sulphur；The mass concentration of sulphur is 2.86~142.86mg/m in the hydrogen sulfide, the cos3。
Carbon disulfide linear formula component to be measured suitable for the coke-stove gas is methyl mercaptan, carbon disulfide, thiophene
The quantitative determination of fen；The mass concentration of sulphur is 2.86~142.86mg/m in the methyl mercaptan, carbon disulfide, thiophene3。
Further, the carrier gas is nitrogen, and purity is not less than 99.999%, and the combustion gas is hydrogen, and purity is not less than
99.99%, the combustion-supporting gas is oxygen；The content of sulfide and ammonia is less than in the nitrogen, the hydrogen, the oxygen
0.01mg/m3, the hydrocarbon of sulfide and ammonia is less than 14.29mg/m3；The nitrogen flow rate is 52~57ml/min；It is described
Hydrogen flow rate is 60~65ml/min；The oxygen gas flow rate is 11~13ml/min.
The GDX-301 posts being previously mentioned in the present invention for 4 × 0.5mm of column length 1.5m, Ф polytetrafluoroethylene (PTFE) post, built-in 60~
The GDX-301 porous polymer bead carriers of 80 mesh.
The TCP posts being previously mentioned in the present invention are the polytetrafluoroethylene (PTFE) post of 4 × 0.5mm of column length 1.5m, Ф, built-in 60~80 mesh
White 101 carrier (white diatomite carrier) of coated 30wt% tricresyl phosphates (TCP).
With prior art will compared with, beneficial effects of the present invention：
The present invention has expanded the amount of analysis using form sulfur component in flame photometric detection direct injection analysis coke-stove gas
Journey, meets national standard《GB 16171-2012》It is required that coke-stove gas analysis indexes.
The data handling system of gas chromatograph is auto linear data processor in the present invention, can be carried out automatically linear
Change is processed, and most of sulfide can be quantified with a kind of standard sample.Quantity tube is decreased to 0.2~0.4ml by the present invention,
And by gas chromatograph signal amplifier resistor coupled in parallel resistance be 200~700K Ω resistance, it is ensured that use flame photometric detection
When device is measured to the sample gas of the coke-stove gas containing high concentration sulphur, sulfide content and its concentration square are directly proportional, from
And directly can be measured coke-stove gas injection gas chromatograph.Avoid sulfide in coke oven thing concentration of component difference
When big, part form sulfur component concentration to be measured need to be made to be in analysis range using the method for dilution dilution certain multiple, be
It is accurate to each form sulfur component quantitative analysis to be measured, need to respectively dilute different times according to the concentration of different shape sulphur component
Number is analyzed one by one, cumbersome, analysis time situation long, can particularly improve the relatively relatively low form sulfur component of concentration
Quantitative analysis when, dilution certain multiple after the form sulfur component concentration cause analysis result to show the sulfide less than test limit
Do not detect, enriched sample can disturb low concentration sample peak if not diluting, separating degree is poor, it is difficult to accurate qualitative, quantitative point
Analysis, wherein concentration form sulfur component concentration high may pollute the situation of chromatographic column and detector higher than analysis range.
It is easy to operate using each form sulfur component in the inventive method measure coke-stove gas, as a result accurately.It is coke-stove gas
The application of desulfurization technology provides accurate and effective data, Instructing manufacture work.
Brief description of the drawings
Fig. 1 is to the collection of illustrative plates after hydrogen sulfide and carbonyl Sulfur Analysis
Fig. 2 is to the collection of illustrative plates after carbon disulfide analysis
Fig. 3 cos repetition measurement linear graphs
Fig. 4 carbon disulfide repetition measurement linear graphs
Sample gas GDX-301 posts analysis collection of illustrative plates before Fig. 5 Qian'ans coking saturator
Sample gas TCP posts analysis collection of illustrative plates before Fig. 6 Qian'ans coking saturator
Fig. 7 Qian'ans house steward sample gas GDX-301 post analysis collection of illustrative plates
Specific embodiment
The present invention is further illustrated below in conjunction with the accompanying drawings.
Gas chromatograph used by the embodiment of the present invention is WDL-94 Computerized multifunctional sulphur content analyzer, and detector is flame luminosity
Detector, detector temperature is more than 100 DEG C, and data handling system is auto linear data processor, meets following equation：
In formula, x：Sulfur content, unit is mg/m3；hi:In the response of initial time, unit is mm to component i；Δt：When
Between increment, typically less than or equal to 10 milliseconds (ms), unit be millisecond (ms)；k：Coefficient.
99.999% nitrogen is not less than as carrier gas using purity, purity is not less than 99.99% hydrogen as combustion gas,
Used as combustion-supporting gas, the content of sulfide and ammonia is less than 0.01mg/m to oxygen in nitrogen, hydrogen, oxygen3, hydrocarbon is less than
14.29mg/m3。
Embodiment 1
The foundation of cos linear formula
The quantity tube of gas chromatograph is set to 0.30ml, the column temperature of chromatographic column is set to 60 DEG C, photomultiplier electricity
Pressure is set to 530V, and signal amplifier resistor coupled in parallel resistance is 500K Ω resistance；Nitrogen flow rate is 55.4ml/min；Hydrogen flow rate
It is 60.2ml/min；Oxygen gas flow rate is 11.3ml/min.
It is 142.86mg/m by mass concentration3Cos standard sample be formulated as 2.86mg/m3、5.71mg/m3、
8.57mg/m3、11.43mg/m3、14.29mg/m3、28.57mg/m3、42.86mg/m3、71.43mg/m3、100.00mg/m3、
114.29mg/m3、142.86mg/m3Sample, using GDX-301 chromatographic columns, by gas chromatograph for determination content, gained carbonyl
Base sulphur data are listed in the table below 1：
Cos measurement result of the GDX-301 chromatographic columns of table 1 to various concentrations
Note：Relative error computing formula：
Relative error=(measured value-theoretical concentration)/theoretical concentration * 100%
Gas chromatography analysis sample quality concentration shown in table 1 is less than 28.57mg/m3When measured value it is inclined compared with theoretical concentration
Height, when sample quality concentration is more than 100.00mg/m3When measured value it is relatively low compared with theoretical concentration, in 2.86~142.86mg/m3Range
In the range of cannot linearly meet index of the relative error less than 10%, so gained cos measured value is divided into 2.86~
14.29mg/m3With 14.29~142.86mg/m3Two intervals carry out linear fit respectively, and with measured value as transverse axis, theoretical concentration is
The longitudinal axis, cos linear formula is after fitting：
Y=0.900X+0.073 (2.86≤X≤14.29)
Y=1.241X-9.623 (14.29 ＜ X≤142.86)
By gained linear formula typing auto linear data processor.With 71.43mg/m3Cos single point correction, adjusts
Whole instrument Photomultiplier tube voltage is 400~700V.
Embodiment 2
The confirmatory experiment of cos linear formula
Tested using the experiment condition in embodiment 1.
Configuration concentration is 2.86mg/m3、5.71mg/m3、8.57mg/m3、11.43mg/m3、14.29mg/m3、28.57mg/
m3、42.86mg/m3、71.43mg/m3、100.00mg/m3、142.86mg/m3Cos standard sample, according to embodiment 1
Method, repetition measurement is carried out using GDX-301 chromatographic columns to above-mentioned standard sample, by auto linear data processor using implementation
Cos linear formula is calculated in example 1.The data obtained is as shown in table 3.With theoretical concentration as transverse axis, it is vertical to determine average value
Axle represents that linearly dependent coefficient is more than 0.9997, and repetition measurement data are linearly good with Fig. 3.
Cos measurement result of the GDX-301 chromatographic columns of table 3 to various concentrations
Note：Relative standard deviation computing formula：
It is general to illustrate that precision is good in the case of relative standard deviation ＜ 10%, the detection sample of direct injected shown in table 3
The measurement result of cos in product, relative standard deviation illustrates that the precision of determination sample reaches between 0.2~3.4%
It is required that.
If the carbon-based sulphur of repetition measurement data display is in 2.86~14.29mg/m3With 14.29~142.86mg/m3Two interval relations
Bad, then repeatedly embodiment 1 and the operation of embodiment 2, redefines the carbon-based sulphur range of linearity.
Embodiment 3
The foundation of carbon disulfide linear formula
Tested using the experiment condition in embodiment 1.
Switching chromatograph post is to TCP posts.It is 71.43mg/m by mass concentration3Carbon disulfide standard sample be formulated as
1.43mg/m3、2.14mg/m3、3.57mg/m3、4.29mg/m3、5.71mg/m3、7.14mg/m3、14.29mg/m3、21.43mg/
m3、35.71mg/m3、42.86mg/m3、57.14mg/m3、71.43mg/m3Sample, by gas chromatograph for determination content, two
Nitric sulfid analysis result is calculated with single sulphur, therefore analysis carbon disulfide theory measured value is equal to the twice of theoretical concentration, the sulphur of gained two
Change carbon number evidence and be shown in Table 2：
Carbon disulfide measurement result of the TCP chromatographic columns of table 2 to various concentrations
Gas chromatography is in 1.43~71.43mg/m shown in table 23As the increase of sample concentration is relative by mistake in range ability
Difference is gradually reduced, when carbon disulfide mass concentration is 71.43mg/m3When relative error be still+121%, so by the sulphur of gained two
Change carbon measured value and be divided into 2.86~14.29mg/m3With 14.29~142.86mg/m3Two intervals carry out linear fit respectively, to survey
Definite value is transverse axis, and theoretical concentration is the longitudinal axis, and carbon disulfide linear formula is after fitting：
Y=0.341X-1.528 (2.86≤X≤14.29)
Y=0.475X-12.628 (14.29 ＜ X≤142.86)
By gained carbon disulfide linear formula typing auto linear data processor.
Embodiment 4
The confirmatory experiment of carbon disulfide linear formula
Tested using the experiment condition in embodiment 1.
Configuration concentration is 1.43mg/m3、2.86mg/m3、4.29mg/m3、5.71mg/m3、7.14mg/m3、14.29mg/m3、
21.43mg/m3、35.71mg/m3、50.00mg/m3、71.43mg/m3Carbon disulfide standard sample, according to the side of embodiment 3
Method, repetition measurement is carried out using TCP chromatographic columns to above-mentioned standard sample, by auto linear data processor using in embodiment 3
Carbon disulfide linear formula calculated.Repetition measurement data are shown in Table 4.With theoretical concentration as transverse axis, determine average value be the longitudinal axis with
Fig. 4 represents that linearly dependent coefficient is more than 0.9987, and repetition measurement data are linearly good.
Carbon disulfide repetition measurement result of the TCP chromatographic columns of table 4 to various concentrations
To the measurement result of carbon disulfide in the sample of table 4, relative standard deviation between 0.3~2.9%, determination sample
Precision ＜ 10%, illustrates that determination sample precision has reached requirement.
If repetition measurement data display carbon disulfide is in 2.86~14.29mg/m3With 14.29~142.86mg/m3Two interval passes
It is bad, then repeatedly embodiment 3 and the operation of embodiment 4, redefines the carbon disulfide range of linearity.
Embodiment 5
Return the experiment of mark rate
The quantity tube of gas chromatograph is set to 0.40ml, the column temperature of chromatographic column is set to 55 DEG C, photomultiplier electricity
Pressure is set to 450V, and signal amplifier resistor coupled in parallel resistance is 430K Ω resistance；Nitrogen flow rate is 54.6ml/min；Hydrogen flow rate
It is 62.7ml/min；Oxygen gas flow rate is 12.5ml/min.
Take air, add cos standard sample, using GDX-301 chromatographic columns by auto linear data processor according to
Cos linear formula is calculated in embodiment 1；Air is taken, carbon disulfide standard sample is added, transfer matic is passed through using TCP chromatographic columns
Property data processor is calculated according to carbon disulfide linear formula in embodiment 3, and acquired results are shown in Table 5.
The recovery test of table 5
Note：Recovery of standard addition computing formula：Recovery of standard addition=(measured value-original amount)/addition * 100%
It has been generally acknowledged that recovery of standard addition and 80~120% or close to 100%, that is, illustrate that quantitative analysis results are believable.
As shown in Table 5, this assay method recovery of standard addition is good.
Embodiment 6
The quantity tube of gas chromatograph is set to 0.26ml, the column temperature of chromatographic column is set to 58 DEG C, photomultiplier electricity
Pressure is set to 612V, and signal amplifier resistor coupled in parallel resistance is 620K Ω resistance；Nitrogen flow rate is 55.0ml/min；Hydrogen flow rate
It is 62.3ml/min；Oxygen gas flow rate is 11.8ml/min.
Configuration hybrid standard sample：Configuration concentration is 128.57mg/m3Hydrogen sulfide, 142.86mg/m3Cos and
71.43mg/m3The component hybrid standard sample of carbon disulfide three, is surveyed using GDX-301 chromatographic columns to the hybrid standard sample
It is fixed, calculated using cos linear formula in embodiment 1 by auto linear data processor.Gained chromatogram is as schemed
Shown in 1.Collection of illustrative plates shows that hydrogen sulfide and cos can obtain good separation, and hydrogen sulfide appearance time is 1 point of 34 seconds, measured concentration
It is 127.14mg/m3；Cos appearance time be 2 points 32 seconds, measured concentration is 148.57mg/m3, gained collection of illustrative plates shows the method
Suitable for hydrogen sulfide and the qualitative and quantitative determination of cos.
Embodiment 7
Using the experiment condition in embodiment 6, the hybrid standard sample of embodiment 6 is measured using TCP chromatographic columns,
Calculated using carbon disulfide linear formula in embodiment 3 by auto linear data processor.Gained chromatogram such as Fig. 2
It is shown.Collection of illustrative plates shows that carbon disulfide can obtain good separation, and hydrogen sulfide and cos cannot be separated.Because of gas-chromatography used
Instrument is calculated the analysis result of sulfide with single sulphur, therefore analysis carbon disulfide theory measured value is equal to the twice of theoretical concentration.Institute
With measured value as 150mg/m3, the concentration of carbon disulfide is 75mg/m3.Gained collection of illustrative plates shows that the method is applied to carbn disulfide
Qualitative and quantitative determination.
Embodiment 8
The quantity tube of gas chromatograph is set to 0.29ml, the column temperature of chromatographic column is set to 62 DEG C, photomultiplier electricity
Pressure is set to 520V, and signal amplifier resistor coupled in parallel resistance is 530K Ω resistance；Nitrogen flow rate is 53.8ml/min；Hydrogen flow rate
It is 61.5ml/min；Oxygen gas flow rate is 11.6ml/min.
Respectively in the difference position sampling of coke-stove gas production, using the different sampling point sample coke-oven coals of gas chromatograph detection
The component of each Sulfur in gas, using GDX-301 chromatographic columns by auto linear data processor according to carbonyl in embodiment 1
Sulphur linear formula is calculated；Pass through auto linear data processor according to curing carbon line in embodiment 3 with using TCP chromatographic columns
Property formula calculate, acquired results are shown in Table 6.
Fig. 5 is shown using sample gas before GDX-301 chromatogram column analysis Qian'an coking saturator, and analysis display cos go out
Peak time 2 point 26 seconds, actual measurement content is 27.14mg/m3。
Fig. 6 is shown using sample gas before TCP chromatogram column analysis Qian'an coking saturator, and analysis shows going out for carbon disulfide
Peak time is 3 minutes, and actual measurement content is 48.86mg/m3, actual measurement carbon disulfide mass concentration is 24.43mg/m3.Blowback appearance is
Thiophene, DMDS sulfides mixing peak.
Fig. 7 is shown using GDX-301 chromatogram column analysis house steward's sample gas, and the appearance time of analysis display hydrogen sulfide is 1
Divide 26 seconds, mass concentration is respectively 40.57mg/m3、42.43mg/m3, cos appearance time be 2 points 18 seconds, mass concentration point
Wei not 23.71mg/m3、25.43mg/m3, house steward's sample gas site-test analysis display hydrogen sulfide and cos good separation, and
It is repeated good.
Embodiment 9
Comparative example
Will in embodiment 8 obtain sample gas according to《Gas analysis vulcanizes the measure flame luminosity gas chromatography of method》
(National Standard of the People's Republic of China GB/T28727-2012) is determined, and the results are shown in Table 6.
Each form sulfur component testing result in the different sampling point sample coke-stove gas of table 6
As shown in Table 6, using the inventive method detection coke-stove gas in each Sulfur acquired results with use GB/
The result that the method for T28727-2012 is determined is consistent.
In sum, using each Sulfur in present invention detection coke-stove gas, coke-stove gas directly can be injected into gas phase
Chromatograph is measured, easy to operate using each form sulfur component in this method measure coke-stove gas, as a result accurately, can detect
Go out the component of low concentration.
The preferred embodiments of the present invention are the foregoing is only, is merely illustrative for the purpose of the present invention, and it is nonrestrictive；
Those of ordinary skill in the art understand that can carry out many to it in the spirit and scope that the claims in the present invention are limited changes
Become, modification, or even equivalent change, but fall within protection scope of the present invention.
Claims (10)
1. a kind of method that gas chromatograph direct injected determines each Sulfur in coke-stove gas, it is characterised in that：The gas phase
Chromatographic detector is flame photometric detector, and the data handling system of the gas chromatograph is at auto linear data
Reason device, meets following equation：
In formula, x：Sulfur content, unit is mg/m3；hi:In the response of initial time, unit is mm to component i；Δt：Time increases
Amount, typically less than or equal to 10 milliseconds (ms), unit is millisecond (ms)；k：Coefficient；The quantity tube of the gas chromatograph is set
It is 0.2~0.4ml, the signal amplifier resistor coupled in parallel resistance of the gas chromatograph is 200~700K Ω resistance；The gas phase
Chromatographic Photomultiplier tube voltage is set to 400~700V, and the column temperature of the chromatographic column of the gas chromatograph is set to 50~
70 DEG C, the detector temperature is more than 100 DEG C；Methods described includes qualitative method and quantitative approach；
Methods described is comprised the following steps including qualitative method：The standard sample of each Sulfur is taken, the gas is directly injected into
Chromatography, obtains standard sample collection of illustrative plates；The coke-stove gas is taken, the gas chromatograph is directly injected into, sample collection of illustrative plates is obtained；Will be described
Each component retention time is carried out qualitative compared with one pack system sulphur retention time in the standard diagram in sample chromatogram figure；
The quantitative approach is comprised the following steps：The linear formula of each Sulfur is set up, auto linear number described in typing
According to processor, each Sulfur linear formula is verified；The coke-stove gas is directly injected into the gas chromatograph for determination, is led to
Cross the auto linear data processor to be calculated according to each Sulfur linear formula, obtain final product coke-stove gas sulphur to be measured
Content.
2. the method that a kind of gas chromatograph direct injected according to claim 1 determines each Sulfur in coke-stove gas,
It is characterized in that：Each Sulfur includes hydrogen sulfide, cos, methyl mercaptan, carbon disulfide, thiophene, the hydrogen sulfide, carbonyl
Chromatographic column used by the measure of sulphur is GDX-301 posts, and the methyl mercaptan, carbon disulfide, chromatographic column used by the measure of thiophene are TCP
Post.
3. the method that a kind of gas chromatograph direct injected according to claim 2 determines each Sulfur in coke-stove gas,
It is characterized in that：The linear formula of each Sulfur includes cos linear formula, carbon disulfide linear formula.
4. the method that a kind of gas chromatograph direct injected according to claim 3 determines each Sulfur in coke-stove gas,
It is characterized in that：The cos linear formula is set up to comprise the following steps：Configuration various concentrations and concentration be 2.86~
14.29mg/m3Or 14.29~142.86mg/m3Cos standard sample it is at least each 5, the chromatographic column be GDX-301 posts,
By the gas chromatograph for determination content, by the concentration of the cos standard sample and measured content with 2.86~
14.29mg/m3With 14.29~142.86mg/m3Two interval linear fits respectively, obtain cos linear formula, by the carbonyl
Auto linear data processor described in sulphur linear formula typing.
5. the method that a kind of gas chromatograph direct injected according to claim 4 determines each Sulfur in coke-stove gas,
It is characterized in that：Verify comprising the following steps for the cos linear formula：Cos standard sample is taken to the gas phase color
Spectrometer carries out single point correction, configuration various concentrations and concentration is 2.86~14.29mg/m3Or 14.29~142.86mg/m3's
Cos repetition measurement standard sample is at least each 5, the gas chromatograph for determination is injected, by the auto linear data processing
Device calculates content according to the cos linear formula, by the concentration of the cos repetition measurement standard sample and containing obtained by repetition measurement
Amount is with 2.86~14.29mg/m3With 14.29~142.86mg/m3Linear fits are distinguished in two intervals, such as linear, then the carbonyl
Sulphur linear formula is set up.
6. the method that a kind of gas chromatograph direct injected according to claim 3 determines each Sulfur in coke-stove gas,
It is characterized in that：The carbon disulfide linear formula is set up to comprise the following steps：Configuration various concentrations and concentration be 1.43~
7.14mg/m3Or 7.14~71.43mg/m3Carbon disulfide standard sample it is at least each 5, the chromatographic column be TCP posts, pass through
The gas chromatograph for determination content, by 2 times of Carbon Disulfides with measured content with 2.86~14.29mg/m3
With 14.29~142.86mg/m3Two interval linear fits respectively, obtain carbon disulfide linear formula, by the curing carbon line
Property auto linear data processor described in formula typing.
7. the method that a kind of gas chromatograph direct injected according to claim 6 determines each Sulfur in coke-stove gas,
It is characterized in that：Verify that the carbon disulfide linear formula comprises the following steps：Configuration various concentrations and concentration be 1.43~
7.14mg/m3Or 7.14~71.43mg/m3Carbon disulfide repetition measurement standard sample it is at least each 5, by the auto linear
Data processor calculates content according to the carbon disulfide linear formula, by 2 times of carbon disulfide repetition measurement standard sample concentration
With the content obtained by repetition measurement with 2.86~14.29mg/m3With 14.29~142.86mg/m3Two interval linear fits respectively, such as into
Linearly, then carbon disulfide linear formula is set up.
8. a kind of gas chromatograph direct injected according to claim 4 or 5 determines the side of each Sulfur in coke-stove gas
Method, it is characterised in that：Cos linear formula component to be measured suitable for the coke-stove gas is hydrogen sulfide and cos
Quantitative determination；The mass concentration of sulphur is 2.86~142.86mg/m in the hydrogen sulfide, the cos3。
9. a kind of gas chromatograph direct injected according to claim 5 or 6 determines the side of each Sulfur in coke-stove gas
Method, it is characterised in that：Carbon disulfide linear formula component to be measured suitable for the coke-stove gas is methyl mercaptan, curing
The quantitative determination of carbon, thiophene；The mass concentration of sulphur is 2.86~142.86mg/m in the methyl mercaptan, carbon disulfide, thiophene3。
10. the method that a kind of gas chromatograph direct injected according to claim 9 determines each Sulfur in coke-stove gas,
It is characterized in that：The carrier gas is nitrogen, and purity is not less than 99.999%, and the combustion gas is hydrogen, and purity is not less than
99.99%, the combustion-supporting gas is oxygen；The content of sulfide and ammonia is less than in the nitrogen, the hydrogen, the oxygen
0.01mg/m3, the hydrocarbon of sulfide and ammonia is less than 14.29mg/m3；The nitrogen flow rate is 52~57ml/min；It is described
Hydrogen flow rate is 60~65ml/min；The oxygen gas flow rate is 11~13ml/min.
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