CN110514755A - The method of chromatographic detection apparatus and detection organic sulfur - Google Patents
The method of chromatographic detection apparatus and detection organic sulfur Download PDFInfo
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- CN110514755A CN110514755A CN201910757460.1A CN201910757460A CN110514755A CN 110514755 A CN110514755 A CN 110514755A CN 201910757460 A CN201910757460 A CN 201910757460A CN 110514755 A CN110514755 A CN 110514755A
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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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
Abstract
The present invention relates to organic sulfur analysis field, the method for disclosing chromatographic detection apparatus and detecting organic sulfur.The device includes: ten-way valve, the first chromatographic column, the second chromatographic column, FPD detector and work station, the first chromatographic column by sample hydrogen sulfide and organic sulfur separate；Second chromatographic column is used to organic sulfur importing FPD detector；Ten-way valve communication with carrier gas source, sample source, the first chromatographic column and the second chromatographic column；Ten-way valve is controlled by work station, for carrying out blowback and emptying by sample delivery to the first chromatographic column, by hydrogen sulfide, and organic sulfur is passed through the second chromatographic column；FPD detector is used to detect the content of organic sulfur.The organic sulfur content in high hydrogen sulfide can be analyzed using apparatus and method of the present invention, detection accuracy is high, while can preferably protect flame photometric detector, reduces the loss of device.
Description
Technical field
The present invention relates to organic sulfur analysis fields, and in particular to the method for chromatographic detection apparatus and detection organic sulfur.
Background technique
Coal oil project is that various product is synthesized using the indirect liquefaction of coal, and main process is coal dust burn incompletely
It generates raw gas (gasified raw material gas), raw gas is transformed, is sent after purification to products such as each factory production methanol, oil products.Unstripped gas
Middle sulfur-bearing, will cause the poisoning of Fischer-Tropsch catalyst, therefore Fiscber-Tropscb synthesis has strict requirements to unstripped gas (sulphur is less than
It 50ppb), will be by the sulphuring treatment of decarbonylation base (it is required that carbonyl sulfur be less than 10ppm) before process gas carries out low-temp methanol elution sulphur.
The method of Determination of Trace Sulfur mainly has a two major classes in country's detection desulfurizer gas, i.e. chemical analysis (including electricity
Method, spectrophotometer method etc.) and instrumental method (predominantly chromatography), the former is longer analysis time, is chiefly used in research unit
Research and analyse, the latter by the chemical companies such as oil plant be widely used in device production analyze, but this class standard use more FPD,
The detection of PFPD or SCD detector is micro or trace sample suitable for content.
When being greater than 0.1 mole of % for hydrogen sulfide content in sample, or even required in 0.5 mole of % or so, analysis
Particularity is to be not concerned with hydrogen sulfide content, only norm controlling requirement is done to carbonyl sulfur, methyl mercaptan, methyl sulfide, in gas
Any traces of carbonyl sulfide, methyl mercaptan, methyl sulfide analytical equipment predominantly configure thermal conductivity detector (TCD) (TCD) and sulfur chemiluminescent detector
(SCD), the gas chromatograph of flame photometric detector (FPD), pulsed flame photometric detector (PFPD), such device are total to
It is all to use photomultiplier tube with feature, if using above method to such gas (sample of 0.5 mole of % of hydrogen sulfide or so
Gas) directly detection will cause the pollution of micro system and the damage of photomultiplier tube, and thermal conductivity detector (TCD) (TCD) detection limits and spirit
The index of process requirements is not achieved in sensitivity, can not analyze 10ppm organic sulfur below.
CN104407075A disclose it is a kind of analysis gas in micro sulfur-containing compound gas-chromatography detection system and side
Method specifically discloses: the gas-chromatography detection system includes ten-way valve (1), six-way valve (2), quantitative loop I (3), quantitative loop II
(4), gas chromatographic column I (5), gas chromatographic column II (6), flame photometric detector I (7), flame photometric detector II (8), institute
The interface I (1.1) for stating ten-way valve (1) is sample holes, and the interface II (1.2) of the ten-way valve (1) is relieving device, the ten-way valve
(1) interface III (1.3) is connect by quantitative loop I (3) with the interface VI (1.6) of ten-way valve (1), and ten-way valve (1) connects
IV (1.4) of mouth are connect with gas-carrier pipeline I, and the interface V (1.5) of the ten-way valve (1) and the interface V (2.5) of six-way valve (2) connect
It connects, the interface VII (1.7) of the ten-way valve (1) is connect by quantitative loop II (4) with the interface Ⅹ (1.10) of ten-way valve (1), institute
The interface VIII (1.8) for stating ten-way valve (1) is connect by gas chromatographic column II (6) with flame photometric detector II (8), and described ten is logical
The interface Ⅸ (1.9) of valve (1) is connect with gas-carrier pipeline II, and the interface I (2.1) of the six-way valve (2) passes through pipeline and six-way valve
(2) interface III (2.3) connection, the interface II (2.2) of the six-way valve (2) is connect with flame photometric detector I (7), described
The interface IV (2.4) of six-way valve (2) is connect by gas chromatographic column I (5) with the interface VI (2.6) of six-way valve (2).But it uses
When the device detects hydrogen sulfide content higher sample, the damage of the photomultiplier tube of flame photometric detector is relatively easily caused, is filled
It sets and is easier to be lost, improve analysis cost.
Summary of the invention
The purpose of the invention is to overcome sample higher for hydrogen sulfide content of the existing technology, it is more difficult to realize
The problem of analysis of organic sulfur, device is easily lost, the method that chromatographic detection apparatus is provided and detects organic sulfur, using the device energy
Organic sulfur content in enough accurate analysis high hydrogen sulfides, and reduce the loss of device.
The present inventor by by carbonyl sulfur, hydrogen sulfide, methyl mercaptan, ethyl mercaptan, 6 kinds of substances of thiophene and methyl sulfide into
Row mixing is made each content of material standard sample known, is then detected, and obtains the appearance time of each substance, and carbonyl sulfur is first
It is first separated, followed by hydrogen sulfide, is then successively methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide, and determine the appearance of each substance
Time.According to peak sequence and time, hydrogen sulfide is blown out and is vented, large content of hydrogen sulfide is not allowed to enter FPD detector, only
Micro organic sulfur is analyzed, adopts to realize the organic sulfur content in analysis high hydrogen sulfide.
To achieve the goals above, first aspect present invention provides a kind of chromatographic detection apparatus, which includes: ten logical
Valve, the first chromatographic column, the second chromatographic column, FPD detector and work station, wherein
First chromatographic column by sample hydrogen sulfide and organic sulfur separate；
Second chromatographic column is used to organic sulfur importing FPD detector；
The ten-way valve communication with carrier gas source, sample source, first chromatographic column and second chromatographic column；
The ten-way valve is controlled by the work station, for by the sample delivery to the first chromatographic column, by the vulcanization
Hydrogen carries out blowback and emptying, and the organic sulfur is passed through the second chromatographic column；
The FPD detector is used to detect the content of organic sulfur.
Second aspect of the present invention provides a kind of method for detecting organic sulfur, comprising:
(A) sample is separated:
Carrier gas and sample containing hydrogen sulfide and organic sulfur are passed through ten-way valve, and are delivered to the first chromatographic column, pass through
One chromatographic column by sample hydrogen sulfide and organic sulfur separate, then by the switching of ten-way valve, by the hydrogen sulfide into
Row blowback and emptying, and the organic sulfur is passed through the second chromatographic column；
(B) it sample introduction and detects:
The organic sulfur is imported FPD detector and detects the content of organic sulfur by FPD detector by the second chromatographic column；
Ten-way valve sample introduction is controlled by work station, collects the voltage signal data of FPD detector, and calculates containing for organic sulfur
Amount.
Preferably, the process of step (A) the separation sample includes:
(a) sample introduction:
Ten-way valve is switched into first interface and the tenth orifice, second interface and third orifice, the 4th interface
With the 5th orifice, the 6th interface and the 7th orifice, the 8th interface and the 9th orifice；
First carrier gas enters ten-way valve by the 7th interface, and the sample containing hydrogen sulfide and organic sulfur is logical by the tenth interface
Enter, and full of the quantitative loop being connected with first interface and the 8th interface, sample is expelled to waste liquid collection vessel from the 9th interface；
(b) carbonyl sulfur is detected:
By ten-way valve switch to first interface be connected to second interface, third interface and the 4th orifice, the 5th interface
With the 6th orifice, the 7th interface and the 8th orifice, the 9th interface and the tenth orifice；
First carrier gas enters ten-way valve by the 7th interface, pushes in the quantitative loop being connected to the 8th interface and first interface
Sample from second interface enter the first chromatographic column, by the first chromatographic column by sample hydrogen sulfide and organic sulfur divided
From the carbonyl sulfur in organic sulfur is separated first, flow to the 6th interface by the 5th interface, and flow to the second chromatographic column；
(c) hydrogen sulfide is vented:
Ten-way valve is switched into first interface and the tenth orifice, second interface and third orifice, the 4th interface
With the 5th orifice, the 6th interface and the 7th orifice, the 8th interface and the 9th orifice；
Second carrier gas enters ten-way valve by third interface, enters the first chromatographic column from second interface, blowback step (b)
The isolated hydrogen sulfide of first chromatographic column flow to the 4th interface by the 5th interface, flows out and is vented from the 4th interface；
(d) one of methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide or a variety of are detected:
By ten-way valve switch to first interface be connected to second interface, third interface and the 4th orifice, the 5th interface
With the 6th orifice, the 7th interface and the 8th orifice, the 9th interface and the tenth orifice；
First carrier gas enters ten-way valve by the 7th interface, enters the first chromatographic column from second interface, pushes step (b)
Successively isolated the second organic sulfur flow to the 6th interface by the 5th interface to first chromatographic column, and flow to the second chromatographic column,
Wherein, second organic sulfur is one of methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide or a variety of.
Through the above technical solutions, big content of hydrogen sulphide can be cut off, does not allow it to enter detector, only analyze micro
Organic sulfur, to realize the organic sulfur content in analysis high hydrogen sulfide, detection accuracy is high, can achieve process requirement index,
Flame photometric detector can also be preferably protected, avoids detector contaminated, reduces the loss of device, improve device
Service life.
Detailed description of the invention
Fig. 1 is a kind of chromatographic detection apparatus of specific embodiment provided by the invention.
Description of symbols
I, ten-way valve II, the first chromatographic column III, the second chromatographic column
IV, FPD detector 1, first interface 2, second interface
3, third interface 4, the 4th interface 5, the 5th interface
6, the 6th interface 7, the 7th interface 8, the 8th interface
9, the 9th interface 10, the tenth interface
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In the present invention, FPD detector refers to flame photometric detector.
In the present invention,Refer to internal diameter.
In the present invention, Balance Air refers to the gas in sample to be tested gas except sulfur-containing compound and hydrogen sulfide.Such as table 2
In Balance Air refer to the gas other than carbonyl sulfur, methyl mercaptan, ethyl mercaptan, thiophene, methyl sulfide and hydrogen sulfide, generally
The gas that FPD is not responding to, such as nitrogen.
First aspect present invention provides a kind of chromatographic detection apparatus, as shown in Figure 1, the device includes: ten-way valve I,
One chromatographic column II, the second chromatographic column III, FPD detector IV and work station, wherein
The first chromatographic column II by sample hydrogen sulfide and organic sulfur separate；
The second chromatographic column III is used to organic sulfur importing FPD detector IV；
The ten-way valve I communication with carrier gas source, sample source, the first chromatographic column II and the second chromatographic column III；
The ten-way valve I is controlled by the work station, for by the sample delivery to the first chromatographic column II, by the sulphur
Change hydrogen and carry out blowback and emptying, and the organic sulfur is passed through the second chromatographic column III；
The FPD detector IV is used to detect the content of organic sulfur.
In the present invention, there are four working conditions for ten-way valve tool:
First working condition are as follows: first interface 1 is connected to the tenth interface 10, second interface 2 is connected to third interface 3,
Four interfaces 4 are connected to the 5th interface 5, the 6th interface 6 is connected to the 7th interface 7, the 8th interface 8 is connected to the 9th interface 9；
First carrier gas enters ten-way valve I by the 7th interface 7, and the sample containing hydrogen sulfide and organic sulfur passes through the tenth interface
10 are passed through, and full of the quantitative loop being connected with first interface 1 and the 8th interface 8, sample is expelled to waste liquid from the 9th interface 9 and receives
Collect container.
Second working condition are as follows: first interface 1 is connected to second interface 2, third interface 3 is connected to the 4th interface 4, the 5th
Interface 5 is connected to the 6th interface 6, the 7th interface 7 is connected to the 8th interface 8, the 9th interface 9 is connected to the tenth interface 10；
First carrier gas enters ten-way valve I by the 7th interface 7, and promotion is quantified with what the 8th interface 8 and first interface 1 were connected to
Sample in ring enters the first chromatographic column II from second interface 2, by the first chromatographic column II by hydrogen sulfide in sample and organic
Sulphur is separated, and the carbonyl sulfur in organic sulfur is separated first, flow to the 6th interface 6 by the 5th interface 5, and flow to the second color
Compose column III.
Third working condition are as follows: first interface 1 is connected to the tenth interface 10, second interface 2 is connected to third interface 3,
Four interfaces 4 are connected to the 5th interface 5, the 6th interface 6 is connected to the 7th interface 7, the 8th interface 8 is connected to the 9th interface 9；
Second carrier gas enters ten-way valve I by third interface 3, enters the first chromatographic column II, blowback first from second interface 2
Chromatographic column II isolated hydrogen sulfide flow to the 4th interface 4 by the 5th interface 5, flows out and is vented from the 4th interface 4.
4th working condition are as follows: first interface 1 is connected to second interface 2, third interface 3 is connected to the 4th interface 4, the 5th
Interface 5 is connected to the 6th interface 6, the 7th interface 7 is connected to the 8th interface 8, the 9th interface 9 is connected to the tenth interface 10；
First carrier gas enters ten-way valve I by the 7th interface 7, enters the first chromatographic column II from second interface 2, pushes first
Successively isolated the second organic sulfur by the 5th interface 5 flow to the 6th interface 6 to chromatographic column II, and flow to the second chromatographic column
III, wherein second organic sulfur is one of methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide or a variety of.
Chromatographic detection apparatus of the invention can cut off big content of hydrogen sulphide, it is not allowed to enter detector, realize FPD only
Analyze micro organic sulfur.The content of other organic sulfurs mixed in high hydrogen sulfide gas can be accurately analyzed using the device,
And flame photometric detector is preferably protected, the loss of device is reduced, the service life of device is improved, saves analysis cost.
In the present invention, work station is mainly used for controlling ten-way valve sample introduction, control analysis condition, and collects data-signal
And analyzed, to measure the content of organic sulfur.
In the present invention, it is preferred to which as shown in Figure 1, the first interface 1 and the 8th interface 8 of shown ten-way valve I are respectively and fixed
Measure the both ends connection of ring；Second interface 2 and the 5th interface 5 are connected to the both ends of the first chromatographic column II respectively；Third interface 2 and
The connection of two carrier gas sources of supply；4th interface 4 is connected to blow-down pipe；6th interface 6 is connected to the second chromatographic column III；7th connects
Mouth 7 is connected to the first carrier gas source of supply；Tenth interface 10 is connected to sample source of supply；9th interface 9 connects with waste liquid collection vessel
It is logical.
In the present invention, the first chromatographic column is main analytical column.Preferably, first chromatographic column is GAS-pro chromatographic column,
PreferablyGAS-pro chromatographic column.
In the present invention, it is preferred to which second chromatographic column is empty tube column, it is highly preferred that second chromatographic column is interior
Diameter is less than 5 μm, further preferably 0.1-0.18 μm；It is further preferred that second chromatographic column is's
Empty tube column.Second chromatographic column by determinand (organic sulfur) import FPD detector, and can regime flow, enable a device to
Even running.
Second aspect of the present invention provides a kind of method for detecting organic sulfur, comprising:
(A) sample is separated:
Carrier gas and sample containing hydrogen sulfide and organic sulfur are passed through ten-way valve I, and are delivered to the first chromatographic column II, pass through
First chromatographic column II by sample hydrogen sulfide and organic sulfur separate, then by the switching of ten-way valve I, by the vulcanization
Hydrogen carries out blowback and emptying, and the organic sulfur is passed through the second chromatographic column III；
(B) it sample introduction and detects:
The organic sulfur is imported FPD detector IV and detects organic sulfur by FPD detector IV by the second chromatographic column III
Content；
Ten-way valve I sample introduction is controlled by work station, collects the voltage signal data of FPD detector IV, and calculates organic sulfur
Content.
Method in accordance with the invention it is preferred that the organic sulfur is carbonyl sulfur, and it is selected from methyl mercaptan, ethyl mercaptan, thiophene
With one of methyl sulfide or a variety of.
By mixing the standard substance of carbonyl sulfur, hydrogen sulfide, methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide, it is made
The sample of each content of material known, is then detected, and the appearance time of each substance is obtained, and carbonyl sulfur is separated first, secondly
It is hydrogen sulfide, is then successively methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide, and determine the appearance time of each substance.
According to the method for the present invention, method of the invention is directed to containing the organic sulfur sample compared with hydrogen polysulfide, can be carried out
High-precision measurement, but the organic sulfur sample less for hydrogen sulfide content, equally can detecte.Preferably, the sample
In hydrogen sulfide content be greater than 0.1 mole of %, more preferably 0.2-5 moles of %, further preferably 0.5-1 moles of %.
Method in accordance with the invention it is preferred that the process of step (A) the separation sample includes:
(a) sample introduction:
By ten-way valve I switch to first interface 1 is connected to the tenth interface 10, second interface 2 is connected to third interface 3,
Four interfaces 4 are connected to the 5th interface 5, the 6th interface 6 is connected to the 7th interface 7, the 8th interface 8 is connected to the 9th interface 9；
First carrier gas enters ten-way valve I by the 7th interface 7, and the sample containing hydrogen sulfide and organic sulfur passes through the tenth interface
10 are passed through, and full of the quantitative loop being connected with first interface 1 and the 8th interface 8, sample is expelled to waste liquid from the 9th interface 9 and receives
Collect container；
(b) carbonyl sulfur is detected:
By ten-way valve I switch to first interface 1 is connected to second interface 2, third interface 3 is connected to the 4th interface 4, the 5th
Interface 5 is connected to the 6th interface 6, the 7th interface 7 is connected to the 8th interface 8, the 9th interface 9 is connected to the tenth interface 10；
First carrier gas enters ten-way valve I by the 7th interface 7, and promotion is quantified with what the 8th interface 8 and first interface 1 were connected to
Sample in ring enters the first chromatographic column II from second interface 2, by the first chromatographic column II by hydrogen sulfide in sample and organic
Sulphur is separated, and the carbonyl sulfur in organic sulfur is separated first, flow to the 6th interface 6 by the 5th interface 5, and flow to the second color
Compose column III；
(c) hydrogen sulfide is vented:
By ten-way valve I switch to first interface 1 is connected to the tenth interface 10, second interface 2 is connected to third interface 3,
Four interfaces 4 are connected to the 5th interface 5, the 6th interface 6 is connected to the 7th interface 7, the 8th interface 8 is connected to the 9th interface 9；
Second carrier gas enters ten-way valve I by third interface 3, enters the first chromatographic column II, blowback step from second interface 2
(b) the first chromatographic column II isolated hydrogen sulfide flow to the 4th interface 4 by the 5th interface 5, simultaneously from the outflow of the 4th interface 4
Emptying；
(d) one of methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide or a variety of are detected:
By ten-way valve I switch to first interface 1 is connected to second interface 2, third interface 3 is connected to the 4th interface 4, the 5th
Interface 5 is connected to the 6th interface 6, the 7th interface 7 is connected to the 8th interface 8, the 9th interface 9 is connected to the tenth interface 10；
First carrier gas enters ten-way valve I by the 7th interface 7, enters the first chromatographic column II from second interface 2, pushes step
(b) successively isolated the second organic sulfur by the 5th interface 5 flow to the 6th interface 6 to the first chromatographic column II, and flow to the
Two chromatographic column III, wherein second organic sulfur is one of methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide or a variety of.
Method in accordance with the invention it is preferred that the determined volume of the quantitative loop is 0.1-1mL, preferably 0.2-
0.3mL.Such as any number in the range that constitutes of 0.2mL, 0.25mL, 0.3mL and above-mentioned any two numerical value.
Method in accordance with the invention it is preferred that first carrier gas and the second carrier gas be each independently helium, nitrogen or
Argon gas, preferably helium or nitrogen.
Method in accordance with the invention it is preferred that first chromatographic column is GAS-pro chromatographic column, preferablyGAS-pro chromatographic column.First chromatographic column is main analytical column.
Method in accordance with the invention it is preferred that second chromatographic column is empty tube column, it is highly preferred that second chromatography
The internal diameter of column is less than 5 μm, further preferably 0.1-0.18 μm；It is further preferred that second chromatographic column isEmpty tube column.Determinand (organic sulfur) is imported FPD detector by the second chromatographic column, and being capable of stationary flow
Amount, enables a device to even running.
Method in accordance with the invention it is preferred that the temperature-programmed mode of the column temperature are as follows: setting initial temperature is 40-60 DEG C, and
Then constant temperature 5-10min rises to 160-200 DEG C with 8-15 DEG C/min.For example, setting initial temperature is 50 DEG C, and the constant temperature at 50 DEG C
Then 7min rises to 180 DEG C with 10 DEG C/min.
According to the method for the present invention, in FPD detector, can be passed through hydrogen as combustion gas, be passed through oxygen as combustion-supporting
Gas.Wherein, the purity of combustion gas and combustion-supporting gas can be the purity of this field conventional chromatogram detection, such as purity >=99.999%
(through dehydration and/or deoxidation treatment).
According to the method for the present invention, the column temperature, detector temperature of detection, split ratio have wider range, can carry out
Adjustment, for the purpose of obtaining that there is preferable separating degree, peak shape, detection accuracy.
The present invention will be described in detail by way of examples below.
In following embodiment, gas-chromatography is purchased from agilent company, model 7890B.
Ten-way valve is purchased from Valco company.
First carrier gas is helium, purity >=99.999% (through being dehydrated, deoxidation treatment).
Second carrier gas is nitrogen, purity >=99.999% (through being dehydrated, deoxidation treatment).
Combustion gas is hydrogen, purity >=99.999% (through being dehydrated, deoxidation treatment).
Combustion-supporting gas is oxygen, purity >=99.999% (through dehydration).
Analysis condition is shown in Table 1.
Table 1
Preparation example 1
The sample to be tested of known content is prepared, the substance and content that sample contains are shown in Table 2.
Table 2
| Component | Content (molar ppm) |
| Carbonyl sulfur | 2.2 |
| Methyl mercaptan | 2.5 |
| Ethyl mercaptan | 2.4 |
| Thiophene | 2.0 |
| Methyl sulfide | 2.1 |
| Hydrogen sulfide | 5000 |
| Nitrogen | Balance Air |
Embodiment 1
(A) sample is separated:
(a) sample introduction:
By ten-way valve I switch to first interface 1 is connected to the tenth interface 10, second interface 2 is connected to third interface 3,
Four interfaces 4 are connected to the 5th interface 5, the 6th interface 6 is connected to the 7th interface 7, the 8th interface 8 is connected to the 9th interface 9；
First carrier gas enters ten-way valve I by the 7th interface 7, and the sample containing hydrogen sulfide and organic sulfur passes through the tenth interface
10 are passed through, and full of the quantitative loop being connected with first interface 1 and the 8th interface 8, the determined volume of quantitative loop is 0.25mL, sample
Product are expelled to waste liquid collection vessel from the 9th interface 9；
(b) carbonyl sulfur is detected:
By ten-way valve I switch to first interface 1 is connected to second interface 2, third interface 3 is connected to the 4th interface 4, the 5th
Interface 5 is connected to the 6th interface 6, the 7th interface 7 is connected to the 8th interface 8, the 9th interface 9 is connected to the tenth interface 10；
First carrier gas enters ten-way valve I by the 7th interface 7, and promotion is quantified with what the 8th interface 8 and first interface 1 were connected to
Sample in ring enters the first chromatographic column II from second interface 2, by the first chromatographic column II by hydrogen sulfide in sample and organic
Sulphur is separated, and the carbonyl sulfur in organic sulfur is separated first, flow to the 6th interface 6 by the 5th interface 5, and flow to the second color
Compose column III；
(c) hydrogen sulfide is vented:
By ten-way valve I switch to first interface 1 is connected to the tenth interface 10, second interface 2 is connected to third interface 3,
Four interfaces 4 are connected to the 5th interface 5, the 6th interface 6 is connected to the 7th interface 7, the 8th interface 8 is connected to the 9th interface 9；
Second carrier gas enters ten-way valve I by third interface 3, enters the first chromatographic column II, blowback step from second interface 2
(b) the first chromatographic column II isolated hydrogen sulfide flow to the 4th interface 4 by the 5th interface 5, simultaneously from the outflow of the 4th interface 4
Emptying；
(d) methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide are detected:
By ten-way valve I switch to first interface 1 is connected to second interface 2, third interface 3 is connected to the 4th interface 4, the 5th
Interface 5 is connected to the 6th interface 6, the 7th interface 7 is connected to the 8th interface 8, the 9th interface 9 is connected to the tenth interface 10；
First carrier gas enters ten-way valve I by the 7th interface 7, enters the first chromatographic column II from second interface 2, pushes step
(b) successively isolated methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide by the 5th interface 5 flow to the to the first chromatographic column II
Six interfaces 6, and flow to the second chromatographic column III, wherein second organic sulfur one of is or a variety of.
(B) it sample introduction and detects:
Carbonyl sulfur that second chromatographic column III successively separates step (b) and step (d), methyl mercaptan, ethyl mercaptan, thiophene and
Methyl sulfide imports FPD detector IV and detects its content by FPD detector IV；
Ten-way valve I sample introduction is controlled by work station, collects the voltage signal data of FPD detector IV, and calculates organic sulfur
Content.Measurement the results are shown in Table 3.
After repeating detection 50 times, operation is accurate and steady.
Embodiment 2
According to the method for embodiment 1, repetitive operation 12 times, the result that 12 times are tested carry out relative standard according to formula I
Deviation calculates, and the S in Formulas I is calculated according to formula II, the results are shown in Table 3.
Relative standard deviation
Standard deviation
In formula:
S --- standard deviation；
xi--- unitary determination value；
--- the average value of n times measurement result；
N --- measurement number.
Comparative example 1
According to the method for embodiment 1, unlike, hydrogen sulfide is not vented, but enter the second chromatographic column III and
FPD detector is detected, and FPD detector failures can not continue to use.
Table 3
Can be seen that by the result of table 3 can detecte the higher organic sulfur sample of hydrogen sulfide content using the method for the present invention
Product, detection accuracy is high, and accuracy is high, and relative standard deviation is small to illustrate repeated height.And chromatogram arrangement is not easy to be lost, Neng Gouyan
The service life of long chromatogram arrangement.And the method for comparative example 1 leads to FPD detector failures since concentration of hydrogen sulfide is higher, Wu Faji
It is continuous to use.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of chromatographic detection apparatus, which is characterized in that the device includes: ten-way valve (I), the first chromatographic column (II), the second color
Compose column (III), FPD detector (IV) and work station, wherein
First chromatographic column (II) by sample hydrogen sulfide and organic sulfur separate；
Second chromatographic column (III) is used to organic sulfur importing FPD detector (IV)；
Ten-way valve (I) communication with carrier gas source, sample source, first chromatographic column (II) and second chromatographic column (III)；
The ten-way valve (I) is controlled by the work station, for by the sample delivery to the first chromatographic column (II), by the sulphur
Change hydrogen and carry out blowback and emptying, and the organic sulfur is passed through the second chromatographic column (III)；
The FPD detector (IV) is used to detect the content of organic sulfur.
2. chromatographic detection apparatus according to claim 1, wherein the first interface (1) and the 8th of the ten-way valve (I) connects
Mouth (8) is connected to the both ends of quantitative loop respectively；Second interface (2) and the 5th interface (5) respectively with the first chromatographic column (II) two
End connection；Third interface (2) is connected to the second carrier gas source of supply；4th interface (4) is connected to blow-down pipe；6th interface (6)
It is connected to the second chromatographic column (III)；7th interface (7) is connected to the first carrier gas source of supply；Tenth interface (10) and sample are supplied
Source connection；9th interface (9) is connected to waste liquid collection vessel.
3. chromatographic detection apparatus according to claim 1 or 2, wherein first chromatographic column is GAS-pro chromatographic column,
PreferablyGAS-pro chromatographic column；
Preferably, second chromatographic column is empty tube column, it is highly preferred that the internal diameter of second chromatographic column is less than 5 μm, further
Preferably 0.1-0.18 μm.
4. a kind of method for detecting organic sulfur, comprising:
(A) sample is separated:
Carrier gas and sample containing hydrogen sulfide and organic sulfur are passed through ten-way valve (I), and are delivered to the first chromatographic column (II), pass through
First chromatographic column (II) by sample hydrogen sulfide and organic sulfur separate, will be described then by the switching of ten-way valve (I)
Hydrogen sulfide carries out blowback and emptying, and the organic sulfur is passed through the second chromatographic column (III)；
(B) it sample introduction and detects:
The organic sulfur is imported FPD detector (IV) and detects organic sulfur by FPD detector (IV) by the second chromatographic column (III)
Content；
Ten-way valve (I) sample introduction is controlled by work station, collects the voltage signal data of FPD detector (IV), and calculates organic sulfur
Content.
5. the organic sulfur is carbonyl sulfur according to the method described in claim 4, wherein, and selected from methyl mercaptan, ethyl mercaptan,
One of thiophene and methyl sulfide are a variety of；
Preferably, the content of the hydrogen sulfide in the sample is greater than 0.1 mole of %, more preferably 0.2-5 moles of %, further excellent
It is selected as 0.5-1 moles of %.
6. according to the method described in claim 5, wherein, the process of step (A) the separation sample includes:
(a) sample introduction:
By ten-way valve (I) switch to first interface (1) be connected to the tenth interface (10), second interface (2) and third interface (3) even
It is logical, the 4th interface (4) is connected to the 5th interface (5), the 6th interface (6) is connected to the 7th interface (7), the 8th interface (8) and the
Nine interfaces (9) connection；
First carrier gas enters ten-way valve (I) by the 7th interface (7), and the sample containing hydrogen sulfide and organic sulfur passes through the tenth interface
(10) it is passed through, and full of the quantitative loop being connected with first interface (1) and the 8th interface (8), sample is discharged from the 9th interface (9)
To waste liquid collection vessel；
(b) carbonyl sulfur is detected:
By ten-way valve (I) switch to first interface (1) be connected to second interface (2), third interface (3) and the 4th interface (4) even
It is logical, the 5th interface (5) is connected to the 6th interface (6), the 7th interface (7) is connected to the 8th interface (8), the 9th interface (9) and the
Ten interfaces (10) connection；
First carrier gas enters ten-way valve (I) by the 7th interface (7), what promotion was connected to the 8th interface (8) and first interface (1)
Sample in quantitative loop enters the first chromatographic column (II) from second interface (2), by the first chromatographic column (II) by the sulphur in sample
Change hydrogen and organic sulfur is separated, the carbonyl sulfur in organic sulfur is separated first, flow to the 6th interface by the 5th interface (5)
(6), and it flow to the second chromatographic column (III)；
(c) hydrogen sulfide is vented:
By ten-way valve (I) switch to first interface (1) be connected to the tenth interface (10), second interface (2) and third interface (3) even
It is logical, the 4th interface (4) is connected to the 5th interface (5), the 6th interface (6) is connected to the 7th interface (7), the 8th interface (8) and the
Nine interfaces (9) connection；
Second carrier gas enters ten-way valve (I) by third interface (3), enters the first chromatographic column (II) from second interface (2), blowback
The isolated hydrogen sulfide of the first chromatographic column (II) of step (b) flow to the 4th interface (4) by the 5th interface (5), from the 4th
Interface (4) is flowed out and is vented；
(d) one of methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide or a variety of are detected:
By ten-way valve (I) switch to first interface (1) be connected to second interface (2), third interface (3) and the 4th interface (4) even
It is logical, the 5th interface (5) is connected to the 6th interface (6), the 7th interface (7) is connected to the 8th interface (8), the 9th interface (9) and the
Ten interfaces (10) connection；
First carrier gas enters ten-way valve (I) by the 7th interface (7), enters the first chromatographic column (II) from second interface (2), pushes
Successively isolated the second organic sulfur by the 5th interface (5) flow to the 6th interface to the first chromatographic column (II) of step (b)
(6), and it flow to the second chromatographic column (III), wherein second organic sulfur is in methyl mercaptan, ethyl mercaptan, thiophene and methyl sulfide
It is one or more.
7. according to the method described in claim 6, wherein, the determined volume of the quantitative loop is 0.1-1mL, preferably 0.2-
0.3mL。
8. method according to claim 6 or 7, wherein first carrier gas and the second carrier gas be each independently helium,
Nitrogen or argon gas.
9. the method according to any one of claim 4-8, wherein first chromatographic column is GAS-pro chromatographic column,
PreferablyGAS-pro chromatographic column；
Preferably, second chromatographic column is empty tube column, it is highly preferred that the internal diameter of second chromatographic column is less than 5 μm, further
Preferably 0.1-0.18 μm.
10. the method according to any one of claim 4-9, wherein the temperature-programmed mode of the column temperature are as follows: setting
Initial temperature is 40-60 DEG C, and constant temperature 5-10min, then rises to 160-200 DEG C with 8-15 DEG C/min.
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