CN103123341A - Method for determining mixed gas content - Google Patents
Method for determining mixed gas content Download PDFInfo
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- CN103123341A CN103123341A CN2011103694241A CN201110369424A CN103123341A CN 103123341 A CN103123341 A CN 103123341A CN 2011103694241 A CN2011103694241 A CN 2011103694241A CN 201110369424 A CN201110369424 A CN 201110369424A CN 103123341 A CN103123341 A CN 103123341A
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Abstract
The invention relates to a method for determining mixed gas content, and mainly solves the problems of high manufacturing cost, narrow component analysis range, incapability of flexibly adjusting target component analysis and the like in the prior art. The method for analyzing mixed gas comprises the following steps that: (a) the mixed gas containing permanent gas and C1-C6 hydrocarbons flows through a quantification tube connected to a gas sampling valve, is switched by the gas sampling valve and carried into a pre-separation column chromatographic column I and a chromatographic column II in sequence by carrier gas, and the gas component separated from the chromatographic column II passes through the switching valve and enters a chromatographic column III connected to an isolation valve; (b) after being switched by the isolation valve, the gas component separated from the chromatographic column II passes through the switching valve and a damping valve connected to the isolation valve in sequence, and the content of the gas component is detected by a thermal conductivity detector; and (c) after being switched by the switching valve and the isolation valve, the gas component separated from the chromatographic column II passes through the switching valve and is emptied, and the gas component in the chromatographic column III is carried into the thermal conductivity detector for detecting by the carrier gas from the switching valve, wherein the gas sampling valve, the switching valve, the isolation valve and the switching operations in the steps (a), (b) and (c) are controlled by time programs. According to the technical scheme, the problems are well solved, and the method can be applied to industrial production of chromatographic analysis devices.
Description
Technical field
The present invention relates to a kind of method of definite mixed gas content.
Background technology
In many chemical process such as petrochemical complex, coal chemical technology, often need to carry out compartment analysis work to the mixed gas that contains permanent gas (hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide) and low-carbon (LC) hydro carbons.In recent years, the cost of being produced ethene, propylene by petroleum resources constantly increases, people begin to greatly develop the substitute energy transformation technology, and as the technique of oxygen-containing compound conversion to produce olefine (OTO), particularly the technique by preparing olefin by conversion of methanol (MTO) is subject to increasing attention.Complicated components in the gas-phase product of preparing olefin by conversion of methanol except comprising low-carbon (LC) hydro carbons and permanent gas, also contains a small amount of oxygenatedchemicals etc.At present, analytical work person has carried out a large amount of analytical works in this respect both at home and abroad.
Further separate on the 5A molecular sieve column after adopting the gases such as PoraPLOT Q post separating hydrogen gas, methane in the CN101650351A patent, complete hydrogen, methane test by pulse helium ionized detecting device, after methane gas flows out PoraPLOT Q post, by two-bit triplet electronics transfer valve, air-flow is cut apart, carbon dioxide and sulfuretted hydrogen after PoraPLOT Q post separates are shunted by the distributing T-pipe device, analyzed by thermal conductivity detector (TCD) and flame photometric detector (FPD).The method can detect gases such as hydrogen, methane, carbon dioxide, sulfuretted hydrogen simultaneously, greatly saved sample size and analysis time, but the compositional range of its analysis is narrower, and needs two detecting devices, exists cost high, expensive shortcoming.
In the CN1885031A patent by adopting a gas transfer valve to realize that different carrier gas switch, make when measuring hydrogen and do carrier gas with nitrogen or argon gas, do carrier gas with hydrogen or helium when measuring remaining gas, the detection of all components is all carried out on single thermal conductivity detector (TCD), has realized that the separate unit analytical equipment completes the analysis of oxygenous, nitrogen and hydrogen gas mixture.But the method is analyzed component and is fixed, the method underaction, and fail to solve the mensuration of oxygenatedchemicals.
Summary of the invention
Technical matters to be solved by this invention is that the manufacturing cost that exists in prior art is high, analyzes the component narrow range, and the target analysis component such as can not adjust flexibly at the shortcoming, and a kind of method of new definite mixed gas content is provided.The method has low cost of manufacture, analyzes the component wide ranges, and the target analysis component such as can adjust flexibly at the advantage.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of definite mixed gas content, comprise the following steps: the mixed gas that a) comprises permanent gas and C1～C6 hydro carbons is flowed through and is connected to quantity tube on gas sampling valve, after gas sampling valve switches, bring again chromatographic column II into after being brought into pre-separation column chromatography post I by carrier gas, the gas composition of separating from chromatographic column II enters the chromatographic column III that is connected on isolation valve after transfer valve; B) after isolation valve switches, the gas composition of separating from chromatographic column II by transfer valve with after being connected to orifice valve on isolation valve, detects gas composition content through thermal conductivity detector (TCD) successively; C) after transfer valve and isolation valve switch, the gas composition of separating from chromatographic column II is by emptying after transfer valve, and the gas composition in chromatographic column III is brought thermal conductivity detector (TCD) into through the carrier gas that comes from transfer valve and detected gas composition; Wherein, gas sampling valve, transfer valve, isolation valve, a) step, b) step and c) switching of step controlled by time-program(me).
In technique scheme, permanent gas comprises hydrogen, oxygen, nitrogen, carbon monoxide and carbon dioxide.Mixed gas comprises oxygenatedchemicals and sulfocompound.Oxygenatedchemicals comprises methyl alcohol and dimethyl ether, and sulfocompound comprises sulfuretted hydrogen and cos.Carrier gas is helium or argon gas.Gas sampling valve, transfer valve and isolation valve are six-way valve.Chromatographic column I is the bonding ethyl styrene-divinylbenzene chromatographic column of silanization, and chromatographic column II is bonding polystyrene-divinylbenzene chromatographic column, and chromatographic column III is the molecular sieve chromatography post.
adopt method of the present invention, utilize chromatographic column II first to isolate permanent gas and the methane beyond removing carbon dioxide in mixed gas, isolated gas composition is brought into chromatographic column III, after switching by transfer valve and isolation valve, above-mentioned gas is sealed in chromatographic column III, and chromatographic column II continues all the other components in separating mixed gas and reduces phlegm and internal heat and lead detecting device and detect, switching by transfer valve and isolation valve again after the component analysis that needs are analyzed is complete, with the residual gas emptying in chromatographic column II, to be enclosed in simultaneously gas composition in chromatographic column III brings thermal conductivity detector (TCD) into and detects after chromatographic column III separates.Chromatographic column II is separating carbon dioxide, C1～C6 hydro carbons, oxygenatedchemicals and sulfocompound effectively, chromatographic column III is separating hydrogen gas, oxygen, nitrogen, carbon monoxide and methane effectively, this analysis method combines the separation function of chromatographic column II and chromatographic column III just can effectively isolate said components in mixed gas, thereby realizes the purpose of hydrogen in mixed gas, oxygen, nitrogen, carbon monoxide, carbon dioxide, C1～C6 hydro carbons, oxygenatedchemicals and analysis of sulfur compounds.In addition, can also be according to the component analysis requirement of mixed gas, by adjusting the switching time of transfer valve and isolation valve, the heavy constituent of unnecessary analysis in chromatographic column II is switched to emptying, thereby effectively shorten analysis time.Therefore, method of the present invention can be effective to the component analysis of preparing olefin by conversion of methanol gas-phase product, has obtained technique effect preferably.
Description of drawings
Fig. 1 is the chromatographic process figure of the method for the invention.
Fig. 2 is that sample a analyzes chromatogram.
Fig. 3 is that sample b analyzes chromatogram.
In Fig. 1,1 is the carrier gas steel cylinder; 2 are the carrier gas reduction valve; 3 are the carrier gas reduction valve; 4 is gas sampling valve; 5 is quantity tube; 6 is the analytical gas entrance; 7 are the analytical gas outlet; 8 is chromatographic column I; 9 is chromatographic column II; 10 is transfer valve; 11 is drain; 12 is thermal conductivity detector (TCD); 13 is isolation valve; 14 is orifice valve; 15 is chromatographic column III.
Carrier gas steel cylinder 1 is used for providing reference gas and the carrier gas of the required carrier gas of analytic system and thermal conductivity detector (TCD) 12; Carrier gas reduction valve 2,3 is used for adjusting the top hole pressure of carrier gas; Gas sampling valve 4 and quantity tube 5 are for separating of the chromatogram sample introduction of system; Sample gas enters quantity tube 5 from analytical gas entrance 6, then from analytical gas outlet 7 emptying; Transfer valve 10 is used for the purge vent of chromatographic column II9, and provides carrier gas for chromatographic column III; Isolation valve 13 is used for the components such as isolation hydrogen, oxygen, nitrogen, carbon monoxide, methane component and bypass carbon dioxide, C1～C6 hydro carbons, oxygenatedchemicals, sulfocompound; The fluctuation of system pressure when orifice valve 14 is used for 13 switching of balance isolation valve; Chromatographic column I 8 is used for the initial gross separation blending ingredients; Chromatographic column II is used for the separation of the components such as carbon dioxide, C1～C6 hydro carbons, oxygenatedchemicals, sulfocompound; Chromatographic column III is used for the isolation sealing of the components such as hydrogen, oxygen, nitrogen, carbon monoxide, methane and separates; Component detects and adopts single thermal conductivity detector (TCD) 12 to complete.
Concrete analysis techniqueflow of the present invention is (in Fig. 1, the state of three six-way valves is defaulted as the OFF state, is on the contrary the ON state): after analytical equipment enters and prepares the sample introduction state, start the beginning key, device beginning sample analysis.At first, gas sampling valve 4 and transfer valve 10 switch to the ON state, and the samples in this moment quantity tube 5 are brought chromatographic column I 8 into by carrier gas, carry out pre-separation, and then enter chromatographic column II 9 and separate; Treat that the components such as hydrogen, oxygen, nitrogen, carbon monoxide, methane all leave chromatographic column II 9 and enter chromatographic column III15, and carbon dioxide and all the other components are not when leaving chromatographic column II 9, isolation valve 13 switches to the ON state, the components such as hydrogen, oxygen, nitrogen, carbon monoxide, methane are enclosed in chromatographic column III15 at this moment, and carbon dioxide and all the other components enter thermal conductivity detector (TCD) 12 through orifice valve 14 and detect; After the target components analysis that needs to analyze except hydrogen, oxygen, nitrogen, carbon monoxide, methane is complete, gas sampling valve 4, transfer valve 10 and isolation valve 13 switch to the OFF state, remaining ingredient in chromatographic column II 9 is through transfer valve 10 emptying at this moment, and the components such as the hydrogen in chromatographic column III15, oxygen, nitrogen, carbon monoxide, methane are brought into thermal conductivity detector (TCD) 12 from the carrier gas of transfer valve 10 and detected successively.
In Fig. 2, each chromatographic peak is followed successively by carbon dioxide (3.717), ethene (4.756), ethane (5.714), hydrogen (7.916), oxygen (9.181), nitrogen (10.017), carbon monoxide (12.454), methane (13.105).
In Fig. 3, each chromatographic peak is followed successively by carbon dioxide (3.908), ethene (4.818), ethane (6.104), propylene (14.594), propane (16.310), dimethyl ether (20.452), methyl alcohol (22.028), carbon four (22.800～26.800), hydrogen (28.124), oxygen (30.051), nitrogen (30.467), methane (32.948).
The invention will be further elaborated below by embodiment, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Analytical instrument is 7890 of U.S. Agilent company, configures three six-way valves, and a TCD detecting device connects by chromatographic process figure shown in Figure 1.
Chromatographic column I is Porapak QS packed column, and chromatographic column II is Plot Q post, and chromatographic column III is the 13X molecular sieve column.
Chromatographic condition: temperature programme: 60 ℃ of furnace temperature stopped 15 minutes; The TCD detecting device: 250 ℃ of temperature, reference gas 30 ml/min, make-up gas 2 ml/min are opened negative polarity; Carrier gas is argon gas, and the flow of chromatographic column I, II is 4 ml/min, and chromatographic column III flow is 3 ml/min.
Data processing employing Agilent company chromatographic work station is processed.
Working time, control program saw Table 1.
Table 1 is controlled switching table analysing mixed working time
| Time | Type | State |
| 0.01 | Valve 1 | ON |
| 0.01 | Valve 2 | ON |
| 3.2 | Valve 3 | ON |
| 6.8 | Valve 1 | OFF |
| 6.8 | Valve 2 | OFF |
| 6.8 | Valve 3 | OFF |
Valve 1 finger gas sampling valve-4, valve 2 finger transfer valve-10, valve 3 finger isolation valve-13.
Under above-mentioned chromatographic condition, sample a is analyzed chromatogram see Fig. 2.
[embodiment 2]
Analytical instrument is 7890 of U.S. Agilent company, configures three six-way valves, and a TCD detecting device connects by chromatographic process figure shown in Figure 1.
Chromatographic column I is Porapak QS packed column, and chromatographic column II is 30 meters 0.53 millimeter Plot Q post, and chromatographic column III is the 13X molecular sieve column.
Chromatographic condition: temperature programme: 60 ℃ of furnace temperature, stopped 8 minutes, then rise to 80 ℃ with 10 ℃ of/minute clock rate and stopped 6 minutes, then rise to 160 ℃ with 20 ℃ of/minute clock rate and stopped 5 minutes, then be down to 60 ℃ with 100 ℃ of/minute clock rate and stopped 9 minutes; The TCD detecting device: 250 ℃ of temperature, reference gas 30 ml/min, make-up gas 2 ml/min are opened negative polarity; Carrier gas is argon gas, and the flow of chromatographic column I, II is 4 ml/min, and chromatographic column III flow is 3 ml/min.
Data processing employing Agilent company chromatographic work station is processed.
Working time, control program saw Table 2.
Table 2 is controlled switching table analysing mixed working time
| Time | Type | State |
| 0.01 | Valve 1 | ON |
| 0.01 | Valve 2 | ON |
| 3.2 | Valve 3 | ON |
| 27 | Valve 1 | OFF |
| 27 | Valve 2 | OFF |
| 27 | Valve 3 | OFF |
Valve 1 finger gas sampling valve-4, valve 2 finger transfer valve-10, valve 3 finger isolation valve-13.
Under above-mentioned chromatographic condition, sample b is analyzed chromatogram see Fig. 3.
Obviously, adopt method of the present invention, each component good separation and peak shape are symmetrical, can effectively analyze permanent gas, C1～C6 hydro carbons and oxygenatedchemicals in mixed gas, the target analysis component can be adjusted flexibly, and easy to operate, can be used in the commercial production of chromatographic analysis device.
Claims (7)
1. the method for a definite mixed gas content comprises the following steps:
A) mixed gas that comprises permanent gas and C1～C6 hydro carbons is flowed through and is connected to quantity tube on gas sampling valve, after gas sampling valve switches, bring again chromatographic column II into after being brought into pre-separation column chromatography post I by carrier gas, the gas composition of separating from chromatographic column II enters the chromatographic column III that is connected on isolation valve after transfer valve;
B) after isolation valve switches, the gas composition of separating from chromatographic column II by transfer valve with after being connected to orifice valve on isolation valve, detects gas composition content through thermal conductivity detector (TCD) successively;
C) after transfer valve and isolation valve switch, the gas composition of separating from chromatographic column II is by emptying after transfer valve, and the gas composition in chromatographic column III is brought thermal conductivity detector (TCD) into through the carrier gas that comes from transfer valve and detected gas composition;
Wherein, gas sampling valve, transfer valve, isolation valve, a) step, b) step and c) switching of step controlled by time-program(me).
2. determine according to claim 1 the method for mixed gas content, it is characterized in that permanent gas comprises hydrogen, oxygen, nitrogen, carbon monoxide and carbon dioxide.
3. determine according to claim 1 the method for mixed gas content, it is characterized in that mixed gas comprises oxygenatedchemicals and sulfocompound.
4. determine according to claim 3 the method for mixed gas content, it is characterized in that oxygenatedchemicals comprises methyl alcohol and dimethyl ether, sulfocompound comprises sulfuretted hydrogen and cos.
5. determine according to claim 1 the method for mixed gas content, it is characterized in that carrier gas is helium or argon gas.
6. determine according to claim 1 the method for mixed gas content, it is characterized in that gas sampling valve, transfer valve and isolation valve are six-way valve.
7. determine according to claim 1 the method for mixed gas content, it is characterized in that chromatographic column I is the bonding ethyl styrene-divinylbenzene chromatographic column of silanization, chromatographic column II is bonding polystyrene-divinylbenzene chromatographic column, and chromatographic column III is the molecular sieve chromatography post.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109975449A (en) * | 2017-12-28 | 2019-07-05 | 内蒙古伊泰煤基新材料研究院有限公司 | The Gas Chromatographic Method of hydrogen sulfide and carbonyl sulfur in a kind of crude synthesis gas |
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Cited By (1)
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| CN109975449A (en) * | 2017-12-28 | 2019-07-05 | 内蒙古伊泰煤基新材料研究院有限公司 | The Gas Chromatographic Method of hydrogen sulfide and carbonyl sulfur in a kind of crude synthesis gas |
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| CN103123341B (en) | 2015-07-08 |
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