CN106770709B - A kind of method that gas chromatograph direct injected measures each Sulfur in coke-stove gas - Google Patents
A kind of method that gas chromatograph direct injected measures each Sulfur in coke-stove gas Download PDFInfo
- Publication number
- CN106770709B CN106770709B CN201611039758.1A CN201611039758A CN106770709B CN 106770709 B CN106770709 B CN 106770709B CN 201611039758 A CN201611039758 A CN 201611039758A CN 106770709 B CN106770709 B CN 106770709B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- gas
- linear
- coke
- concentration
- 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
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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses the methods of each Sulfur in a kind of gas chromatograph direct injected measurement coke-stove gas, the gas chromatograph uses flame photometric detector, auto linear data processor, quantity tube are set as 0.2~0.4ml, and signal amplifier resistor coupled in parallel resistance value is 200~700K Ω resistance.The mass concentration that this method quantitative detection is suitable for sulphur is 2.86~142.86mg/m3Coke-stove gas.It is easy to operate using each form sulfur component in this method measurement coke-stove gas, as a result accurately, it may cause the analysis incomplete problem of data after avoiding error caused by troublesome operation and dilute sample gas.Accurate and effective data, Instructing manufacture work are provided for the application of coke oven gas desulfurization technology.
Description
Technical field
The invention belongs to chemical analysis technical fields, and in particular to a kind of gas chromatograph direct injected measurement coke-stove gas
In each Sulfur method.
Background technique
It is the by-product imflammable gas that coal for coking obtains after high-temperature retorting in coke oven in coke-stove gas.Coke oven
The form sulfur components such as hydrogen sulfide, carbonyl sulfur, mercaptan, thiophene have serious corrosion to equipment in coal gas, and it is living also to reduce catalyst
Property, shorten catalyst life, while giving off sulfur dioxide after burning and seriously polluting environment.According to national standard " GB 16171-
2012 --- coking chemistry emission of industrial pollutants standard (water, atmosphere) " the existing crude benzene tubular furnace of regulation, 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.The analysis method upper limit of detection of sulfide in coke oven object component is required to be not less than
100mg/m3。
Currently, to the detection and analysis of gaseous sulfide mainly 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, these methods can only detect that total sulfur contains
Amount, and result is affected by many factors, and accurate and effective data, Instructing manufacture can not be provided for desulfurization technology.Gas-chromatography point
Analysis method is because analysis time is short, high sensitivity, it has also become by most widely used analysis method.The measurement of red, orange, green, blue, yellow (ROGBY) sulfide
Mainly use flame photometric detector and sulfur chemiluminescent detector.Flame photometric detector to sulfide have it is highly selective,
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 volume is 2 × 10-7~1 × 10-4When mg, the content of sulfide and its
Concentration it is square directly proportional.Using the matter of the chromatogram analysis method direct injected detection form sulfur component with flame photometric detector
It measures concentration and is lower than 71.43mg/m3.The analysis method of existing direct injected detection sulfide in coke oven object component is not able to satisfy
The coke-stove gas that national standard " GB 16171-2012 --- coking chemistry emission of industrial pollutants standard (water, atmosphere) " requires
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 diluted method dilution certain multiple
Concentration is in analysis range, need to be according to different shape sulphur component in order to accurately to each form sulfur component quantitative analysis to be measured
Concentration dilute different multiples respectively and analyzed one by one, cumbersome, analysis time is long, especially for opposite in concentration
The quantitative analysis of relatively low form sulfur component, dilute certain multiple after the form sulfur component concentration lower than detection limit cause analysis tie
Fruit shows that the sulfide is not detected, and enriched sample can interfere low concentration sample peak if not diluting, and separating degree is poor, it is difficult to accurate
Qualitative and quantitative analysis, wherein highly concentrated form sulfur component concentration be higher than analysis range, chromatographic column and detector may be polluted.
Therefore it provides a kind of gas chromatography, energy direct injected detects each form sulfur component in coke-stove gas, avoids cumbersome
Error caused by operation, while also avoiding may cause the analysis incomplete problem of data after diluting identical multiple, become this
Field technical staff's urgent problem to be solved.
Summary of the invention
The present invention provides the methods of each Sulfur in a kind of gas chromatograph direct injected measurement 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, solved troublesome operation and caused
Error and dilute sample gas after may cause analysis the incomplete problem of data.
The technical solution adopted by the invention is as follows:
A kind of method that gas chromatograph direct injected measures each Sulfur in coke-stove gas, the detection of the gas chromatograph
Device is flame photometric detector, and data processing system is auto linear data processor, meets following equation:
In formula, x: sulfur content, unit mg/m3；Hi: component i initial time response, unit mm；Δ t: when
Between increment, typically less than or equal to 10 milliseconds (ms), unit be millisecond (ms)；K: coefficient；Quantity tube is set as 0.2~0.4ml,
Signal amplifier resistor coupled in parallel resistance value is 200~700K Ω resistance；Photomultiplier tube voltage is set as 400~700V, chromatographic column
Column temperature be set as 50~70 DEG C, detector temperature is greater than 100 DEG C；The method includes qualitative methods and quantitative approach；
The method includes qualitative method the following steps are included: taking the standard sample of each Sulfur, it is directly injected into institute
Gas chromatograph is stated, standard sample map is obtained；The coke-stove gas is taken, the gas chromatograph is directly injected into, obtains sample map；It 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 the following steps are included: establish the linear formula of each Sulfur, auto linear described in typing
Change data processor, verifies each Sulfur linear formula；The coke-stove gas is directly injected into the gas chromatograph to survey
It is fixed, it is calculated by the auto linear data processor according to each Sulfur linear formula to get the coke-stove gas
Sulfur content to be measured.
Further, each Sulfur includes hydrogen sulfide, carbonyl sulfur, methyl mercaptan, carbon disulfide, thiophene, the vulcanization
Hydrogen, carbonyl sulfur measurement used in chromatographic column be GDX-301 column, the methyl mercaptan, carbon disulfide, thiophene measurement used in chromatographic column
For TCP column.
Further, the linear formula of each Sulfur includes carbonyl sulfur linear formula, carbon disulfide linear formula.
Further, establish the carbonyl sulfur linear formula include the following steps: configure various concentration and concentration be
2.86~14.29mg/3Or 14.29~142.86mg/m3Carbonyl sulfur standard sample it is 5 at least each, the chromatographic column be GDX-
301 columns, by the gas chromatograph for determination content, by the concentration of the carbonyl sulfur standard sample and measured content with
2.86~14.29mg/m3With 14.29~142.86mg/m3Linear fit is distinguished in two sections, carbonyl sulfur linear formula is obtained, by institute
State auto linear data processor described in carbonyl sulfur linear formula typing.
That verifies the carbonyl sulfur linear formula includes the following steps: to take carbonyl sulfur standard sample to the gas chromatograph
Carry out single point correction, configure various concentration and concentration be 2.86~14.29mg/m3Or 14.29~142.86mg/m3Carbonyl
Sulphur repetition measurement standard sample is 5 at least each, injects the gas chromatograph for determination, is pressed by the auto linear data processor
Calculate content according to the carbonyl sulfur linear formula, by the concentration of the carbonyl sulfur repetition measurement standard sample and the resulting content of repetition measurement with
2.86~14.29mg/m3With 14.29~142.86mg/m3Linear fit is distinguished in two sections, such as linear, then the carbonyl sulfur line
Property formula set up.
Further, establish the carbon disulfide linear formula include the following steps: configure various concentration and concentration be
1.43~7.14mg/m3Or 7.14~71.43mg/m3Carbon disulfide standard sample it is 5 at least each, the chromatographic column be TCP
Column, 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/m3Linear fit is distinguished in two sections, carbon disulfide linear formula is obtained, by described two
Auto linear data processor described in nitric sulfid linear formula typing.
Verify the carbon disulfide linear formula include the following steps: configure various concentration and concentration be 1.43~
7.14mg/m3Or 7.14~71.43mg/m3Carbon disulfide repetition measurement standard sample it is 5 at least each, pass through 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 resulting content of repetition measurement with 2.86~14.29mg/m3With 14.29~142.86mg/m3Two sections distinguish linear fit, such as at
Linearly, then carbon disulfide linear formula is set up.
Further, the carbonyl sulfur linear formula is divided into hydrogen sulfide and carbonyl for be measured group suitable for the coke-stove gas
The quantitative determination of base sulphur；The mass concentration of sulphur is 2.86~142.86mg/m in the hydrogen sulfide, the carbonyl sulfur3。
The carbon disulfide linear formula is divided into methyl mercaptan, carbon disulfide, thiophene for be measured group suitable for the coke-stove gas
The quantitative determination of pheno；The methyl mercaptan, carbon disulfide, the mass concentration of sulphur is 2.86~142.86mg/m in 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 nitrogen, the hydrogen, the content of sulfide and ammonia is less than in 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.
GDX-301 column mentioned in the present invention be column length 1.5m, the polytetrafluoroethylene (PTFE) column of 4 × 0.5mm of Ф, built-in 60~
The GDX-301 porous polymer bead carrier of 80 mesh.
TCP column mentioned in the present invention is column length 1.5m, the polytetrafluoroethylene (PTFE) column of 4 × 0.5mm of Ф, built-in 60~80 mesh
101 carrier of white (white diatomite carrier) of coated 30wt% tricresyl phosphate (TCP).
With the 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 the coke-stove gas analysis indexes of national standard " GB 16171-2012 " requirement.
The data processing system of gas chromatograph is auto linear data processor in the present invention, can be carried out automatically linear
Change processing, can quantify most of sulfide 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 value be 200~700K Ω resistance, ensure that using flame photometric detection
When device is measured the sample gas of the coke-stove gas of the sulphur containing high concentration, sulfide content and its concentration it is square directly proportional, from
And directly coke-stove gas injection gas chromatograph can be measured.Avoid sulfide in coke oven object concentration of component difference
When big, part form sulfur component concentration to be measured need to be made to be in analysis range using diluted method dilution certain multiple, be
Accurately to each form sulfur component quantitative analysis to be measured, different times need to be diluted respectively according to the concentration of different shape sulphur component
Number is analyzed one by one, cumbersome, and the situation of analysis time length can especially improve the relatively relatively low form sulfur component of concentration
Quantitative analysis when, diluting after certain multiple the form sulfur component concentration lower than detection limit leads to the analysis sulfide as the result is shown
It is not detected, enriched sample can interfere low concentration sample peak if not diluting, and separating degree is poor, it is difficult to accurate qualitative, quantitative point
Analysis, wherein the case where highly concentrated form sulfur component concentration is higher than analyzing range, may pollute chromatographic column and detector.
It is easy to operate using each form sulfur component in the method for the present invention measurement coke-stove gas, as a result accurately.For coke-stove gas
The application of desulfurization technology provides accurate and effective data, Instructing manufacture work.
Detailed description of the invention
Fig. 1 is to the map after hydrogen sulfide and carbonyl Sulfur Analysis
Fig. 2 is to the map after carbon disulfide analysis
Fig. 3 carbonyl sulfur repetition measurement linear graph
Fig. 4 carbon disulfide repetition measurement linear graph
Sample gas GDX-301 column analyzes map before the Qian'an Fig. 5 coking saturator
Sample gas TCP column analyzes map before the Qian'an Fig. 6 coking saturator
The Qian'an Fig. 7 general pipeline sample gas GDX-301 column analyzes map
Specific embodiment
The present invention will be further described below with reference to the drawings.
Gas chromatograph used in the embodiment of the present invention is WDL-94 Computerized multifunctional sulphur content analyzer, and detector is flame luminosity
Detector, detector temperature are greater than 100 DEG C, and data processing system is auto linear data processor, meet following equation:
In formula, x: sulfur content, unit mg/m3；Hi: component i initial time response, unit mm；Δ t: when
Between increment, typically less than or equal to 10 milliseconds (ms), unit be millisecond (ms)；K: coefficient.
Nitrogen using purity not less than 99.999% is used as carrier gas, and purity is not less than 99.99% hydrogen as combustion gas,
Oxygen is as combustion-supporting gas, and nitrogen, hydrogen, the content of sulfide and ammonia is less than 0.01mg/m in oxygen3, hydrocarbon is less than
14.29mg/m3。
Embodiment 1
The foundation of carbonyl sulfur linear formula
0.30ml is set by the quantity tube of gas chromatograph, the column temperature of chromatographic column is set as 60 DEG C, photomultiplier tube electricity
Pressure is set as 530V, and signal amplifier resistor coupled in parallel resistance value is 500K Ω resistance；Nitrogen flow rate is 55.4ml/min；Hydrogen flow rate
For 60.2ml/min；Oxygen gas flow rate is 11.3ml/min.
It is 142.86mg/m by mass concentration3Carbonyl sulfur 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 gas chromatograph for determination content, gained carbonyl are passed through using GDX-301 chromatographic column
Base sulphur data are listed in the table below 1:
Carbonyl sulfur measurement result of the 1 GDX-301 chromatographic column of table to various concentration
Note: relative error calculation 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 greater than 100.00mg/m3When measured value it is relatively low compared with theoretical concentration, in 2.86~142.86mg/m3Range
The index that relative error is lower than 10% is linearly unable to satisfy in range, so gained carbonyl sulfur measured value is divided into 2.86~
14.29mg/m3With 14.29~142.86mg/m3Two sections carry out linear fit respectively, and using measured value as horizontal axis, theoretical concentration is
The longitudinal axis, carbonyl sulfur linear formula after fitting are as follows:
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/m3Carbonyl sulfur single point correction is adjusted
Whole instrument Photomultiplier tube voltage is 400~700V.
Embodiment 2
The confirmatory experiment of carbonyl sulfur linear formula
It is 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/m3Carbonyl sulfur standard sample, according to embodiment 1
Method carries out repetition measurement to above-mentioned standard sample using GDX-301 chromatographic column, by auto linear data processor using implementation
Carbonyl sulfur linear formula is calculated in example 1.The data obtained is as shown in table 3.Using theoretical concentration as horizontal axis, measurement average value is vertical
Axis indicates that linearly dependent coefficient is greater than 0.9997, and repetition measurement data are linearly good with Fig. 3.
Carbonyl sulfur measurement result of the 3 GDX-301 chromatographic column of table to various concentration
Note: relative standard deviation calculation formula:
Generally in the case where relative standard deviation < 10%, illustrate that precision is good, direct injected shown in table 3 detects sample
The measurement result of carbonyl sulfur in product, relative standard deviation illustrate that the precision for measuring sample reaches between 0.2~3.4%
It is required that.
If repetition measurement data show carbon-based sulphur in 2.86~14.29mg/m3With 14.29~142.86mg/m3Two section relationships
Bad, then the repeatedly operation of embodiment 1 and embodiment 2 redefines the carbon-based sulphur range of linearity.
Embodiment 3
The foundation of carbon disulfide linear formula
It is tested using the experiment condition in embodiment 1.
Switching chromatograph column is to TCP column.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 is analyzed twice that carbon disulfide theory measured value is equal to theoretical concentration, two sulphur of gained
Change carbon number evidence and be shown in Table 2:
Carbon disulfide measurement result of the 2 TCP chromatographic column of table to various concentration
Gas chromatography shown in table 2 is in 1.43~71.43mg/m3As the increase of sample concentration is opposite accidentally in range ability
Difference is gradually reduced, when carbon disulfide mass concentration is 71.43mg/m3When relative error be still+121%, so by two sulphur of gained
Change carbon measured value and is divided into 2.86~14.29mg/m3With 14.29~142.86mg/m3Two sections carry out linear fit respectively, to survey
Definite value is horizontal axis, and theoretical concentration is the longitudinal axis, carbon disulfide linear formula after fitting are as follows:
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
It is 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 carries out repetition measurement to above-mentioned standard sample using TCP chromatographic column, by auto linear data processor using in embodiment 3
Carbon disulfide linear formula calculated.Repetition measurement data are shown in Table 4.Using theoretical concentration as horizontal axis, measurement average value be the longitudinal axis with
Fig. 4 indicates that linearly dependent coefficient is greater than 0.9987, and repetition measurement data are linearly good.
Carbon disulfide repetition measurement result of the 4 TCP chromatographic column of table to various concentration
To the measurement result of carbon disulfide in 4 sample of table, relative standard deviation measures sample between 0.3~2.9%
Precision < 10% illustrates that measuring sample precision has reached requirement.
If repetition measurement data show carbon disulfide in 2.86~14.29mg/m3With 14.29~142.86mg/m3It closes in two sections
Be it is bad, then the repeatedly operation of embodiment 3 and embodiment 4, redefines the carbon disulfide range of linearity.
Embodiment 5
Return the test of mark rate
0.40ml is set by the quantity tube of gas chromatograph, the column temperature of chromatographic column is set as 55 DEG C, photomultiplier tube electricity
Pressure is set as 450V, and signal amplifier resistor coupled in parallel resistance value is 430K Ω resistance；Nitrogen flow rate is 54.6ml/min；Hydrogen flow rate
For 62.7ml/min；Oxygen gas flow rate is 12.5ml/min.
Take air, carbonyl sulfur standard sample be added, using GDX-301 chromatographic column by auto linear data processor according to
Carbonyl sulfur linear formula calculates in embodiment 1；Air is taken, carbon disulfide standard sample is added, transfer matic is passed through using TCP chromatographic column
Property data processor is calculated according to carbon disulfide linear formula in embodiment 3, and acquired results are shown in Table 5.
5 recovery test of table
Note: recovery of standard addition calculation formula: recovery of standard addition=(the original amount of measured value -)/additional amount * 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 measuring method recovery of standard addition is good.
Embodiment 6
0.26ml is set by the quantity tube of gas chromatograph, the column temperature of chromatographic column is set as 58 DEG C, photomultiplier tube electricity
Pressure is set as 612V, and signal amplifier resistor coupled in parallel resistance value is 620K Ω resistance；Nitrogen flow rate is 55.0ml/min；Hydrogen flow rate
For 62.3ml/min；Oxygen gas flow rate is 11.8ml/min.
Configure hybrid standard sample: configuration concentration 128.57mg/m3Hydrogen sulfide, 142.86mg/m3Carbonyl sulfur and
71.43mg/m3Three component hybrid standard sample of carbon disulfide surveys the hybrid standard sample using GDX-301 chromatographic column
It is fixed, it is calculated by auto linear data processor using carbonyl sulfur linear formula in embodiment 1.Gained chromatogram is as schemed
Shown in 1.Map shows, hydrogen sulfide and carbonyl sulfur can obtain good separation, hydrogen sulfide appearance time be 1 point 34 seconds, measured concentration
For 127.14mg/m3；Carbonyl sulfur appearance time be 2 points 32 seconds, measured concentration 148.57mg/m3, gained map shows this method
Qualitative and quantitative detection suitable for hydrogen sulfide and carbonyl sulfur.
Embodiment 7
Using the experiment condition in embodiment 6, it is measured using hybrid standard sample of the TCP chromatographic column to embodiment 6,
It is calculated by auto linear data processor using carbon disulfide linear formula in embodiment 3.Gained chromatogram such as Fig. 2
It is shown.Map shows that carbon disulfide can obtain good separation, and hydrogen sulfide and carbonyl sulfur can not separate.Because of gas-chromatography used
Instrument calculates the analysis result of sulfide with single sulphur, therefore analyzes twice that carbon disulfide theory measured value is equal to theoretical concentration.Institute
It is 150mg/m with measured value3, the concentration of carbon disulfide is 75mg/m3.Gained map shows that this method is suitable for carbn disulfide
Qualitative and quantitative detection.
Embodiment 8
0.29ml is set by the quantity tube of gas chromatograph, the column temperature of chromatographic column is set as 62 DEG C, photomultiplier tube electricity
Pressure is set as 520V, and signal amplifier resistor coupled in parallel resistance value is 530K Ω resistance；Nitrogen flow rate is 53.8ml/min；Hydrogen flow rate
For 61.5ml/min；Oxygen gas flow rate is 11.6ml/min.
Respectively in the different points sampling of coke-stove gas production, different sampling point sample coke-oven coals are detected using gas chromatograph
The component of each Sulfur in gas, using GDX-301 chromatographic column by auto linear data processor according to carbonyl in embodiment 1
Sulphur linear formula calculates；Pass through auto linear data processor according to curing carbon line in embodiment 3 with using TCP chromatographic column
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, analysis shows that carbonyl sulfur goes out
Peak time 2 divides 26 seconds, and actual measurement content is 27.14mg/m3。
Fig. 6 is shown using sample gas before TCP chromatogram column analysis Qian'an coking saturator, analysis shows that carbon disulfide goes out
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, dimethyl disulfide sulfides mixing peak.
Fig. 7 is shown using GDX-301 chromatogram column analysis general pipeline sample gas, analysis shows that the appearance time of hydrogen sulfide is 1
Divide 26 seconds, mass concentration is respectively 40.57mg/m3、42.43mg/m3, carbonyl sulfur appearance time be 2 points 18 seconds, mass concentration point
It Wei not 23.71mg/m3、25.43mg/m3, general pipeline sample gas site-test analysis shows hydrogen sulfide and carbonyl sulfur good separation, and
It is repeated good.
Embodiment 9
Comparative example
By the sample gas obtained in embodiment 8 according to " the measurement flame luminosity gas chromatography of gas analysis vulcanization "
(National Standard of the People's Republic of China GB/T28727-2012) measurement, 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 each Sulfur acquired results in the method for the present invention detection coke-stove gas and using GB/
The result of the method measurement of T28727-2012 is consistent.
In conclusion coke-stove gas directly can be injected gas phase using each Sulfur in present invention detection coke-stove gas
Chromatograph is measured, easy to operate using each form sulfur component in this method measurement coke-stove gas, as a result accurately, can be detected
The component of low concentration out.
The above description is only a preferred embodiment of the present invention, is merely illustrative for the purpose of the present invention, and not restrictive；
Those of ordinary skill in the art understand, can carry out many to it in the spirit and scope defined by the claims in the present invention and change
Become, modification or even equivalent change, but falls in protection scope of the present invention.
Claims (8)
1. a kind of method of each Sulfur in gas chromatograph direct injected measurement coke-stove gas, it is characterised in that: the gas phase
Chromatographic detector is flame photometric detector, and the data processing system of the gas chromatograph is at auto linear data
Device is managed, following equation is met:
In formula, x: sulfur content, unit mg/m3；Hi: component i initial time response, unit mm；△ t: the time increases
Amount is less than or equal to 10 milliseconds, and unit is millisecond；K: coefficient；The parameter setting of the gas chromatograph are as follows: quantity tube 0.2
~0.4ml, signal amplifier resistor coupled in parallel resistance value are 200~700K Ω resistance；Photomultiplier tube voltage is 400~700V, color
The column temperature for composing column is 50~70 DEG C, and detector temperature is greater than 100 DEG C；The method includes qualitative methods and quantitative approach；
The qualitative method is directly injected into the gas chromatograph the following steps are included: take the standard sample of each Sulfur,
Obtain standard sample map；The coke-stove gas is taken, the gas chromatograph is directly injected into, obtains sample map；By the sample chromatogram
Each component retention time carries out qualitative compared with one pack system sulphur retention time in the standard diagram in figure；
The quantitative approach is the following steps are included: establish the linear formula of each Sulfur, 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
The auto linear data processor is crossed to calculate according to each Sulfur linear formula to get coke-stove gas sulphur to be measured
Content；
Each Sulfur includes hydrogen sulfide, carbonyl sulfur, methyl mercaptan, carbon disulfide, thiophene, the survey of the hydrogen sulfide, carbonyl sulfur
Fixed used chromatographic column is GDX-301 column, the methyl mercaptan, carbon disulfide, thiophene measurement used in chromatographic column be TCP column；
The linear formula of each Sulfur includes carbonyl sulfur linear formula, carbon disulfide linear formula；
The range of linearity of the carbonyl sulfur linear formula is 2.86~14.29mg/m3With 14.29~142.86mg/m3, described two
The range of linearity of nitric sulfid linear formula is 2.86~14.29mg/m3With 14.29~142.86mg/m3。
2. the method for each Sulfur in a kind of gas chromatograph direct injected measurement coke-stove gas according to claim 1,
It is characterized by: establish the carbonyl sulfur linear formula include the following steps: configure various concentration and concentration be 2.86~
14.29mg/m3Or 14.29~142.86mg/m3Carbonyl sulfur standard sample it is 5 at least each, the chromatographic column be GDX-301 column,
By the gas chromatograph for determination content, by the concentration of the carbonyl sulfur standard sample and measured content with 2.86~
14.29mg/m3With 14.29~142.86mg/m3Linear fit is distinguished in two sections, carbonyl sulfur linear formula is obtained, by the carbonyl
Auto linear data processor described in sulphur linear formula typing.
3. the method for each Sulfur in a kind of gas chromatograph direct injected measurement coke-stove gas according to claim 2,
It is characterized by: that verifies the carbonyl sulfur linear formula includes the following steps: to take carbonyl sulfur standard sample to the gas phase color
Spectrometer carries out single point correction, configure various concentration and concentration be 2.86~14.29mg/m3Or 14.29~142.86mg/m3's
Carbonyl sulfur repetition measurement standard sample is 5 at least each, injects the gas chromatograph for determination, passes through the auto linear data processing
Device calculates content according to the carbonyl sulfur linear formula, by the concentration of the carbonyl sulfur repetition measurement standard sample with repetition measurement is resulting contains
Amount is with 2.86~14.29mg/m3With 14.29~142.86mg/m3Linear fit is distinguished in two sections, such as linear, then the carbonyl
Sulphur linear formula is set up.
4. the method for each Sulfur in a kind of gas chromatograph direct injected measurement coke-stove gas according to claim 3,
It is characterized by: establish the carbon disulfide linear formula include the following steps: configure various concentration and concentration be 1.43~
7.14mg/m3Or 7.14~71.43mg/m3Carbon disulfide standard sample it is 5 at least each, the chromatographic column be TCP column, pass through
The gas chromatograph for determination content, by 2 times of Carbon Disulfides and measured content with 2.86~14.29mg/m3
With 14.29~142.86mg/m3Linear fit is distinguished in two sections, carbon disulfide linear formula is obtained, by the curing carbon line
Auto linear data processor described in property formula typing.
5. the method for each Sulfur in a kind of gas chromatograph direct injected measurement coke-stove gas according to claim 4,
It is characterized by: verify the carbon disulfide linear formula include the following steps: configure various concentration and concentration be 1.43~
7.14mg/m3Or 7.14~71.43mg/m3Carbon disulfide repetition measurement standard sample it is 5 at least each, pass through 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 resulting content of repetition measurement with 2.86~14.29mg/m3With 14.29~142.86mg/m3Two sections distinguish linear fit, such as at
Linearly, then carbon disulfide linear formula is set up.
6. the side of each Sulfur in a kind of gas chromatograph direct injected measurement coke-stove gas according to claim 2 or 3
Method, it is characterised in that: the carbonyl sulfur linear formula is divided into hydrogen sulfide and carbonyl sulfur for be measured group suitable for the coke-stove gas
Quantitative determination；The mass concentration of sulphur is 2.86~142.86mg/m in the hydrogen sulfide, the carbonyl sulfur3。
7. the side of each Sulfur in a kind of gas chromatograph direct injected measurement coke-stove gas according to claim 4 or 5
Method, it is characterised in that: the carbon disulfide linear formula is divided into methyl mercaptan, curing for be measured group suitable for the coke-stove gas
The quantitative determination of carbon, thiophene；The methyl mercaptan, carbon disulfide, the mass concentration of sulphur is 2.86~142.86mg/m in thiophene3。
8. the method for each Sulfur in a kind of gas chromatograph direct injected measurement coke-stove gas according to claim 7,
It is characterized by: carrier gas is nitrogen, purity is not less than 99.999%；Combustion gas is hydrogen, and purity is not less than 99.99%；Combustion-supporting gas
For oxygen；The nitrogen, the hydrogen, the content of sulfide and ammonia is less than 0.01mg/m in the oxygen3, sulfide and ammonia
Hydrocarbon is less than 14.29mg/m3；The nitrogen flow rate is 52~57ml/min；The hydrogen flow rate is 60~65ml/
min；The oxygen gas flow rate is 11~13ml/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611039758.1A CN106770709B (en) | 2016-11-22 | 2016-11-22 | A kind of method that gas chromatograph direct injected measures each Sulfur in coke-stove gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611039758.1A CN106770709B (en) | 2016-11-22 | 2016-11-22 | A kind of method that gas chromatograph direct injected measures each Sulfur in coke-stove gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106770709A CN106770709A (en) | 2017-05-31 |
| CN106770709B true CN106770709B (en) | 2019-05-21 |
Family
ID=58974561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611039758.1A Active CN106770709B (en) | 2016-11-22 | 2016-11-22 | A kind of method that gas chromatograph direct injected measures each Sulfur in coke-stove gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106770709B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110554136A (en) * | 2018-06-04 | 2019-12-10 | 上海梅山钢铁股份有限公司 | Method for detecting sulfur content in blast furnace gas |
| CN111929369A (en) * | 2019-05-13 | 2020-11-13 | 定远县云森科技有限公司 | Method for measuring sulfur content in high-pressure sulfurized isobutylene by gas chromatography |
| CN110849984A (en) * | 2019-10-16 | 2020-02-28 | 夏云山 | Method for detecting sulfide in industrial gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85201771U (en) * | 1986-03-12 | 1987-12-12 | 化工部西南化工研究院 | Automatic chromatograph with microcomputer control and data processing |
| CN102914613A (en) * | 2012-10-15 | 2013-02-06 | 武汉钢铁(集团)公司 | Method for analyzing hydrogen sulfide in coke oven gas |
| CN103063790A (en) * | 2011-10-20 | 2013-04-24 | 攀钢集团西昌钢钒有限公司 | Method for detecting hydrogen sulfide content in coal gas |
| CN105911158A (en) * | 2016-04-08 | 2016-08-31 | 中国测试技术研究院化学研究所 | Gas chromatograph and detection method for determining total content of sulfides in natural gas |
-
2016
- 2016-11-22 CN CN201611039758.1A patent/CN106770709B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85201771U (en) * | 1986-03-12 | 1987-12-12 | 化工部西南化工研究院 | Automatic chromatograph with microcomputer control and data processing |
| CN103063790A (en) * | 2011-10-20 | 2013-04-24 | 攀钢集团西昌钢钒有限公司 | Method for detecting hydrogen sulfide content in coal gas |
| CN102914613A (en) * | 2012-10-15 | 2013-02-06 | 武汉钢铁(集团)公司 | Method for analyzing hydrogen sulfide in coke oven gas |
| CN105911158A (en) * | 2016-04-08 | 2016-08-31 | 中国测试技术研究院化学研究所 | Gas chromatograph and detection method for determining total content of sulfides in natural gas |
Non-Patent Citations (2)
| Title |
|---|
| 色谱反吹法快速检测天然气中硫化物;秦仲林等;《广西化工》;20001231;第131-133页 |
| 采用气相色谱仪分析焦炉煤气中硫化物的含量研究;张娟香;《建筑论坛》;20160615;第2709页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106770709A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106770709B (en) | A kind of method that gas chromatograph direct injected measures each Sulfur in coke-stove gas | |
| 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 | |
| CN105911158B (en) | The gas chromatograph and detection method of sulfide total content in a kind of measure natural gas | |
| CN103336070B (en) | The pick-up unit of sulfur-bearing failure gas component and method in a kind of quantitative detection sulfur hexafluoride electrical equipment | |
| CN102466636B (en) | Device for detecting marine volatile sulfur compounds with ultraviolet fluorescence method and manufacture method of device | |
| CN102253137B (en) | Detection method of trace volatile sulfide in gypsum board | |
| CN104020243A (en) | Detection method for solvent gasoline in air in working place | |
| CN110514755B (en) | Chromatographic detection device and method for detecting organic sulfur | |
| CN102507779B (en) | Method for measuring hydrogen sulfide content in desulfurized amine | |
| CN102914613A (en) | Method for analyzing hydrogen sulfide in coke oven gas | |
| CN105136917A (en) | Qualitative and quantitative analytic method of multiple sulfides in transformer oil | |
| CN101126749A (en) | Quantitative analysis method for all form sulfur component of light carbon and its fractional distillation product | |
| CN106153431A (en) | The detection method of a kind of quick mensuration raw gas composition and device thereof | |
| CN108693256B (en) | Analysis method for sulfur distribution in liquefied petroleum gas and sulfide qualitative database | |
| CN203405450U (en) | Detection device for quantitatively detecting sulfur-containing fault gas components in sulphur hexafluoride electrical equipment | |
| CN208721632U (en) | A kind of detection device of non-methane total hydrocarbons | |
| CN104267198B (en) | A kind of automatic calibration equipment for volatile organic matter analyzer and method | |
| Capelli et al. | Monitoring odour emisssions from an oil & gas plant: Electronic nose performance testing in the field | |
| CN107782807A (en) | The analysis method of sulphur content cloth and a kind of sulfide qualitative data storehouse in a kind of propylene feedstocks | |
| CN202583143U (en) | Chromatographic analyzer | |
| CN109709219A (en) | Detect the method for polar substances structure and/or content in non-polar substrate | |
| CN211348073U (en) | Analysis device for measuring contents of hydrogen sulfide and phosphine | |
| CN111024828B (en) | Online detection device and detection method for nitrogen content of air foam flooding oil well | |
| CN203758975U (en) | Analyzing device for simulating cigarette burning absorption based on controllable equivalent-ratio method | |
| CN110895266A (en) | Analysis device and method for measuring contents of hydrogen sulfide and phosphine |
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 |