CN103123341B - Method for determining mixed gas content - Google Patents
Method for determining mixed gas content Download PDFInfo
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- CN103123341B CN103123341B CN201110369424.1A CN201110369424A CN103123341B CN 103123341 B CN103123341 B CN 103123341B CN 201110369424 A CN201110369424 A CN 201110369424A CN 103123341 B CN103123341 B CN 103123341B
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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 determining 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 containing permanent gas (hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide) and low-carbon (LC) hydro carbons.In recent years, produce ethene by petroleum resources, the cost of propylene constantly increases, people start to greatly develop substitute energy transformation technology, as the technique of oxygen-containing compound conversion to produce olefine (OTO), be particularly subject to increasing attention by the technique of preparing olefin by conversion of methanol (MTO).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 containing a small amount of oxygenatedchemicals etc.At present, domestic and international analytical work person has carried out a large amount of analytical works in this respect.
Be separated further on 5A molecular sieve column after adopting the gases such as PoraPLOT Q post separating hydrogen gas, methane in CN101650351A patent, hydrogen, methane test is completed by pulse helium ionized detecting device, after methane gas flows out PoraPLOT Q post, by two-bit triplet electronics transfer valve, air-flow is split, carbon dioxide after PoraPLOT Q post is separated and sulfuretted hydrogen are shunted by distributing T-pipe device, is 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 saves sample size and analysis time, but its compositional range analyzed is narrower, and needs two detecting devices, there is cost high, expensive shortcoming.
Realize different carrier gas by employing gas transfer valve in CN1885031A patent to switch, when making to measure hydrogen, nitrogen or argon gas do carrier gas, during mensuration remaining gas, carrier gas done by hydrogen or helium, the detection of all components is all carried out on single thermal conductivity detector (TCD), achieves the analysis that separate unit analytical equipment completes oxygenous, nitrogen and hydrogen gas mixture.But the method is analyzed component and fixed, 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 existed in prior art is high, analyzes component narrow range, and target analysis component such as can not to adjust flexibly at the shortcoming, provides a kind of method of new determination mixed gas content.The method has low cost of manufacture, analyzes component wide ranges, and target analysis component such as can to 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 determining mixed gas content, comprise the following steps: mixed gas a) comprising permanent gas and C1 ~ C6 hydro carbons flows through the quantity tube be connected on gas sampling valve, after gas sampling Vavle switching, chromatographic column II is brought into again after being brought into pre-separation column chromatography post I by carrier gas, the gas composition separated from chromatographic column II, after transfer valve, enters the chromatographic column III be connected on isolation valve; B) after isolation valve switches, the gas composition separated from chromatographic column II by transfer valve with after being connected to isolation valve orifice valve, detects gas composition content through thermal conductivity detector (TCD) successively; C) after transfer valve and isolation valve switch, the gas composition separated from chromatographic column II is by emptying after transfer valve, and the carrier gas of the gas composition in chromatographic column III through coming from transfer valve is brought thermal conductivity detector (TCD) into and detected gas composition; Wherein, the switching of gas sampling valve, transfer valve, isolation valve, a) step, b) step and c) step is 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 molecular sieve chromatography post.
Adopt method of the present invention, chromatographic column II is utilized first to isolate permanent gas in mixed gas beyond removing carbon dioxide and methane, isolated gas composition is brought into chromatographic column III, after the switching of transfer valve and isolation valve, above-mentioned gas is sealed in chromatographic column III, and all the other components that chromatographic column II continues in separating mixed gas go thermal conductivity detector (TCD) to detect, switching again by transfer valve and isolation valve after the component analysis of Water demand, by the residual gas emptying in chromatographic column II, after chromatographic column III is separated, bring the gas composition be enclosed in chromatographic column III into thermal conductivity detector (TCD) to detect simultaneously.Chromatographic column II can effectively separating carbon dioxide, C1 ~ C6 hydro carbons, oxygenatedchemicals and sulfocompound, chromatographic column III can effectively separating hydrogen gas, oxygen, nitrogen, carbon monoxide and methane, the separation function of chromatographic column II and chromatographic column III combines the said components just can effectively isolated in mixed gas by this analysis method, thus realizes the object of hydrogen in mixed gas, oxygen, nitrogen, carbon monoxide, carbon dioxide, C1 ~ C6 hydro carbons, oxygenatedchemicals and analysis of sulfur compounds.In addition, according to the component analysis requirement of mixed gas, by adjusting the switching time of transfer valve and isolation valve, the heavy constituent of analysis unnecessary in chromatographic column II can also be switched to emptying, thus effectively shortens 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, achieves good technique effect.
Accompanying drawing explanation
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 carrier gas steel cylinder; 2 is carrier gas reduction valve; 3 is carrier gas reduction valve; 4 is gas sampling valve; 5 is quantity tube; 6 is analytical gas entrance; 7 is 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 for providing reference gas and the carrier gas of carrier gas needed for analytic system and thermal conductivity detector (TCD) 12; Carrier gas reduction valve 2,3 is for adjusting the top hole pressure of carrier gas; Gas sampling valve 4 and quantity tube 5 are for separating of the chromatography column feed materials of system; Sample gas enters quantity tube 5 from analytical gas entrance 6, then exports 7 emptying from analytical gas; Transfer valve 10 for the purge vent of chromatographic column II9, and provides carrier gas for chromatographic column III; Isolation valve 13 is for isolating hydrogen, oxygen, nitrogen, carbon monoxide, methane component the components such as bypass carbon dioxide, C1 ~ C6 hydro carbons, oxygenatedchemicals, sulfocompound; Orifice valve 14 is for balancing the fluctuation of system pressure when isolation valve 13 switches; Chromatographic column I 8 is for 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; The isolation that chromatographic column III is used for the components such as hydrogen, oxygen, nitrogen, carbon monoxide, methane is closed and is separated; 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 OFF state, is ON state on the contrary): after analytical equipment enters and prepares sample introduction state, start and start key, device starts sample analysis.First, gas sampling valve 4 and transfer valve 10 switch to ON state, and the sample now in quantity tube 5 brings chromatographic column I 8 into by carrier gas, carries out pre-separation, and then enter chromatographic column II 9 and be separated; Treat that the components such as hydrogen, oxygen, nitrogen, carbon monoxide, methane are all left chromatographic column II 9 and entered chromatographic column III15, and carbon dioxide and all the other components are not when leaving chromatographic column II 9, isolation valve 13 switches to ON state, now the component such as hydrogen, oxygen, nitrogen, carbon monoxide, methane is enclosed in chromatographic column III15, and carbon dioxide and all the other components enter thermal conductivity detector (TCD) 12 through orifice valve 14 and detect; After except hydrogen, oxygen, nitrogen, carbon monoxide, methane, the target components of Water demand is analyzed, gas sampling valve 4, transfer valve 10 and isolation valve 13 switch to OFF state, remaining ingredient now in chromatographic column II 9 is through transfer valve 10 emptying, and the components such as the hydrogen in chromatographic column III15, oxygen, nitrogen, carbon monoxide, methane are brought into thermal conductivity detector (TCD) 12 by the carrier gas from 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).
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Analytical instrument is 7890 of Agilent company of the U.S., configures three six-way valves, a TCD detecting device, connects by the chromatographic process figure shown in Fig. 1.
Chromatographic column I is Porapak QS packed column, and chromatographic column II is Plot Q post, and chromatographic column III is 13X molecular sieve column.
Chromatographic condition: temperature programme: furnace temperature 60 DEG C, stops 15 minutes; TCD detecting device: temperature 250 DEG C, reference gas 30 ml/min, make-up gas 2 ml/min, opens 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 adopts Agilent company chromatographic work station to process.
Working time, control program was in table 1.
Table 1 controls 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 refers to gas sampling valve-4, and valve 2 refers to transfer valve-10, and valve 3 refers to isolation valve-13.
Under above-mentioned chromatographic condition, analysis analysis chromatogram is carried out to sample a and sees Fig. 2.
[embodiment 2]
Analytical instrument is 7890 of Agilent company of the U.S., configures three six-way valves, a TCD detecting device, connects by the chromatographic process figure shown in Fig. 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 13X molecular sieve column.
Chromatographic condition: temperature programme: furnace temperature 60 DEG C, stops 8 minutes, then rises to 80 DEG C with 10 DEG C/min of speed and stops 6 minutes, then rises to 160 DEG C with 20 DEG C/min of speed and stops 5 minutes, is then down to 60 DEG C with 100 DEG C/min of speed and stops 9 minutes; TCD detecting device: temperature 250 DEG C, reference gas 30 ml/min, make-up gas 2 ml/min, opens 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 adopts Agilent company chromatographic work station to process.
Working time, control program was in table 2.
Table 2 controls 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 refers to gas sampling valve-4, and valve 2 refers to transfer valve-10, and valve 3 refers to isolation valve-13.
Under above-mentioned chromatographic condition, analysis analysis chromatogram is carried out to sample b and sees Fig. 3.
Obviously, adopt method of the present invention, each Component seperation is respond well and peak shape symmetrical, effectively can analyze the permanent gas in mixed gas, C1 ~ C6 hydro carbons and oxygenatedchemicals, target analysis component can adjust flexibly, and easy to operate, can be used in the commercial production of chromatographic analysis device.
Claims (1)
1. determine a method for mixed gas content, comprise the following steps:
A) mixed gas comprising permanent gas and C1 ~ C6 hydro carbons flows through the quantity tube be connected on gas sampling valve, after gas sampling Vavle switching, chromatographic column II is brought again into after being brought into pre-separation column chromatography post I by carrier gas, the gas composition I separated from chromatographic column II, after transfer valve, enters the chromatographic column III be connected on isolation valve;
B) after isolation valve switches, the gas composition II separated from chromatographic column II by transfer valve with after being connected to isolation valve orifice valve, detects gas composition content through thermal conductivity detector (TCD) successively;
C) after transfer valve and isolation valve switch, the gas composition III separated from chromatographic column II is by emptying after transfer valve, and the carrier gas of the gas composition in chromatographic column III through coming from transfer valve is brought thermal conductivity detector (TCD) into and detected gas composition;
Wherein, the switching of gas sampling valve, transfer valve, isolation valve, a) step, b) step and c) step is controlled by time-program(me); Mixed gas comprises oxygenatedchemicals and sulfocompound; Carrier gas is helium or argon gas; Gas sampling valve, transfer valve and isolation valve are six-way valve;
Wherein, described permanent gas comprises hydrogen, oxygen, nitrogen and carbon monoxide;
Wherein, described oxygenatedchemicals comprises methyl alcohol and dimethyl ether, and sulfocompound comprises sulfuretted hydrogen and cos;
Wherein, described 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 molecular sieve chromatography post.
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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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| US20070193336A1 (en) * | 2006-02-21 | 2007-08-23 | Mccurry James D | Single stage flow modulator for performing comprehensive chromatography |
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| JP2007010442A (en) * | 2005-06-30 | 2007-01-18 | Shimadzu Corp | Gas chromatograph |
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