CN109884229A - Impurity composition chromatographic analysis device and its detection method in food-grade carbon-dioxide - Google Patents
Impurity composition chromatographic analysis device and its detection method in food-grade carbon-dioxide Download PDFInfo
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- CN109884229A CN109884229A CN201910281302.3A CN201910281302A CN109884229A CN 109884229 A CN109884229 A CN 109884229A CN 201910281302 A CN201910281302 A CN 201910281302A CN 109884229 A CN109884229 A CN 109884229A
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- quantitative loop
- way valve
- communication port
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 35
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 28
- 239000012535 impurity Substances 0.000 title claims abstract description 23
- 238000004587 chromatography analysis Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 238000001514 detection method Methods 0.000 title claims abstract description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000011064 split stream procedure Methods 0.000 claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 8
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 119
- 238000004891 communication Methods 0.000 claims description 115
- 239000012159 carrier gas Substances 0.000 claims description 112
- 238000010926 purge Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 210000005239 tubule Anatomy 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 2
- 238000005070 sampling Methods 0.000 abstract description 2
- 239000002778 food additive Substances 0.000 description 6
- 235000013373 food additive Nutrition 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- -1 ten-way valve I Chemical compound 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The invention discloses impurity composition chromatographic analysis device and its detection method in food-grade carbon-dioxide, which includes ten-way valve I and ten-way valve II；I both ends of quantitative loop are connected to ten-way valve I, and I both ends of chromatographic column are connected to ten-way valve I；I one end of resisting force column is connected to ten-way valve I, and the other end is connected to methanator entrance；Methanator outlet is connected to fid detector I；II one end of resisting force column is connected to ten-way valve I, other end emptying；Quantitative loop II and III both ends of quantitative loop are connected to ten-way valve II, and II one end of chromatographic column is connected to ten-way valve II, and the other end is connected to fid detector I；Capillary split stream injector, entrance is connected to ten-way valve II, and wherein an outlet is connected to capillary split stream injector, with one end of chromatographic column III, and III other end of chromatographic column is connected to fid detector II.The device can quickly detect eight kinds of benzene, methanol, acetaldehyde, vinyl chloride, ethylene oxide, carbon monoxide, total hydrocarbon and methane components by single injected sampling.
Description
Technical field
The present invention relates to gas chromatographic analysis fields, and in particular to impurity composition chromatography fills in food-grade carbon-dioxide
It sets and its detection method.
Background technique
Carbon dioxide is widely used in soda, beer and food and protects as widest gas food additives
Fresh equal fields.China is second-biggest-in-the-world economy, huge to food-grade carbon-dioxide demand, annual requirement close to 2,000,000 tons,
And sharp rise year by year.
Food-grade carbon-dioxide is necessarily important for the detection of objectionable impurities as a kind of food additives.Carbon dioxide
Source difference, cause the content of the impurity such as the hydrocarbon being harmful to the human body, benzene, sulphur, aldehyde, alcohol to have very big difference, China is current
The main source of food-grade carbon-dioxide is the carbon dioxide air source of chemical products by-product.
In addition, China relatively lags behind in the standard formulation of food-grade carbon-dioxide, GB10621-1989 successively experienced
" food additives liquid CO 2 limekiln method and the synthesis of ammonia ", GB1917-1994 " food additives liquid dioxy
Change carbon fermentation method " and GB10621-2006 " food additives liquid CO 2 ", GB 1886.228-2016 " food
Safe national standard food additives carbon dioxide ", new standard was formally implemented on January 1st, 2017.In new standard for
The requirement of impurity content and detection method have detailed regulation, but some detection methods are relatively complicated in standard, and what is needed sets
The class that makes preparations for sowing is complicated, traceability system is incomplete, detection uncertainty is big.Moreover, the domestic reference substance to food-grade carbon-dioxide
Quality Research is all made of one-component, in actually detected, every kind of component is needed to use an instrument independent analysis.Inspection every in this way
It surveys a kind of component to require into a sample, detection time is long, low efficiency, so being used for quickly detecting food-grade carbon-dioxide is
Technical problem urgently to be resolved.
Summary of the invention
In view of the above shortcomings of the prior art, the object of the invention is that providing a kind of can quickly detect, accurately
Spend impurity composition chromatographic analysis device and its detection method in high food-grade carbon-dioxide.
The technical scheme of the present invention is realized as follows:
Impurity composition chromatographic analysis device in food-grade carbon-dioxide, including ten-way valve I, ten-way valve II, fid detector I, FID
Detector II, methanator, quantitative loop I, quantitative loop II, quantitative loop III, chromatographic column I, resisting force column I, resisting force column II, chromatographic column
II and chromatographic column III.
10 ports of the ten-way valve are sample gas inlet I, I entrance communication port of quantitative loop, I outlet mouth of quantitative loop, color
Compose I entrance communication port of column, I outlet mouth of chromatographic column, I communication port of resisting force column, II communication port of resisting force column, I entrance of carrier gas, carrier gas
II entrance and sample gas outlet I.
I entrance of quantitative loop is connected to I entrance communication port of quantitative loop, the outlet of quantitative loop I and I outlet mouth of quantitative loop
Connection；The both ends of the chromatographic column I are connected to I entrance communication port of chromatographic column and I outlet mouth of chromatographic column respectively；Resisting force column I
One end be connected to I communication port of resisting force column, the other end is connected to methanator entrance；It is detected with FID methanator outlet
Device I is connected to；One end of resisting force column II is connected to II communication port of resisting force column, other end connection emptying pipeline.
10 ports of the ten-way valve are sample gas inlet II, II entrance communication port of quantitative loop, II outlet of quantitative loop
Mouth, III entrance communication port of quantitative loop, III outlet mouth of quantitative loop, II entrance communication port of chromatographic column, III communication port of chromatographic column carry
III entrance of gas, IV entrance of carrier gas and sample gas outlet II.
II entrance of quantitative loop is connected to II entrance communication port of quantitative loop, and the outlet of quantitative loop II connects with the outlet of quantitative loop II
Port connection；III entrance of quantitative loop is connected to III entrance communication port of quantitative loop, the outlet of quantitative loop III and III outlet of quantitative loop
Mouth connection；II one end of chromatographic column is connected to II entrance communication port of chromatographic column, and the other end is connected to fid detector I；Chromatographic column III 1
End is connected to III communication port of chromatographic column, and the other end is connected to fid detector II.
Further, the chromatographic column III is capillary chromatographic column, is set between the capillary chromatographic column and ten-way valve II
There is capillary split stream injector, the capillary split stream injector, entrance is connected to III communication port of chromatographic column, and capillary is diverted into
The outlet of sample device is set there are three pipeline, and wherein first pipe is equipped with dottle pin and purges regulating valve；Second pipe, which is equipped with, shunts absorption
Trap shunts adsorption trap one end and is connected to capillary split stream injector, and the pipeline for shunting adsorption trap outlet end is equipped with shunt regulating
Valve；Third pipeline is connected to one end of chromatographic column III.
Further, when the ten-way valve I and ten-way valve II are in original state, the connection status of ten-way valve I are as follows: quantitative
I entrance communication port of ring is connected to sample gas inlet I, and sample gas outlet I is connected to I outlet mouth of quantitative loop, the connection of I entrance of chromatographic column
Mouth is connected to II communication port of resisting force column, and II entrance of carrier gas is connected to I outlet mouth of chromatographic column, I communication port of resisting force column and carrier gas I
Entrance connection；The connected state of ten-way valve II: III entrance of carrier gas is connected to capillary split stream injector, communication port, and quantitative loop II enters
Mouth communication port is connected to sample gas inlet II, and sample gas outlet II is connected to III entrance communication port of quantitative loop, IV entrance of carrier gas and chromatography
The connection of II entrance communication port of column, III outlet mouth of quantitative loop are connected to II outlet mouth of quantitative loop.
When the ten-way valve I and in running order ten-way valve II, the connected state of ten-way valve I are as follows: I entrance of carrier gas and fixed
The connection of I entrance communication port of ring is measured, sample gas inlet I is connected to sample gas outlet I, and I outlet mouth of quantitative loop and I entrance of chromatographic column connect
Port connection, II communication port of resisting force column are connected to II entrance of carrier gas, and I outlet mouth of chromatographic column is connected to I communication port of resisting force column；
The connected state of ten-way valve II: II outlet mouth of quantitative loop is connected to III entrance of carrier gas, capillary split stream injector, communication port
It is connected to II entrance communication port of quantitative loop, sample gas inlet II is connected to sample gas outlet II, III entrance communication port of quantitative loop and carrier gas
The connection of IV entrance；II entrance communication port of chromatographic column is connected to III outlet mouth of quantitative loop.
It further, is H into the carrier gas I and carrier gas II of II entrance of I entrance of carrier gas and carrier gas2；Into III entrance of carrier gas
Carrier gas III and carrier gas IV with IV entrance of carrier gas are H2Or N2One of.
Further, the fid detector II is connected with purging pipeline, and purging pipeline one end connects fid detector import,
One end is purge gas entrance.
Further, the purge gas is N2。
The detection method of impurity composition chromatography in food-grade carbon-dioxide utilizes mentioned-above food-grade titanium dioxide
The method that impurity composition chromatographic analysis device is detected in carbon, specifically includes the following steps:
(1) when ten-way valve I and ten-way valve II are in original state, sample gas passes through sample gas inlet I respectively and sample gas inlet II enters
Ten-way valve I and ten-way valve II, so as to be full of sample gas in quantitative loop I, quantitative loop II and quantitative loop III；
(2) moment rotation ten-way valve I and ten-way valve II, keeps ten-way valve I and ten-way valve II in running order, and carrier gas I is from carrier gas
After entrance I enters ten-way valve I, the sample gas pushed in quantitative loop I sequentially enters chromatographic column I, resisting force column I, methanator, finally
Fid detector I is reached, test sample gas is treated in fid detector I and is detected, out CO and CH4Peak；Meanwhile carrier gas III is from carrier gas
After entrance III enters ten-way valve II, the sample gas pushed in quantitative loop II sequentially enters capillary split stream injector, chromatographic column III, most
Fid detector II is reached afterwards, and fid detector II detects sample to be tested, out benzene, methanol, acetaldehyde, vinyl chloride and epoxy second
The peak of alkane；Meanwhile after carrier gas IV is from carrier gas inlet IV into ten-way valve II, the sample gas pushed in quantitative loop III enters chromatographic column II
Fid detector I is reached after separation, is treated test sample gas in fid detector I and is detected, out the peak of total hydrocarbon, finally obtains gas phase color
Spectrogram.
It further, further include step (3), as CO and CH out4Peak after moment rotate ten-way valve I, at this time at ten-way valve I
In original state, after carrier gas II enters ten-way valve I by carrier gas inlet II, by chromatographic column I and resisting force column II, by high-content
CO2Emptying.
Compared with prior art, the invention has the following beneficial effects:
1, the present invention is realized by modes such as pre-separation, gas-way inverse blows into one by designing the gas chromatography system of more valve multicolumns
Secondary sample, completion organic gas component (benzene, methanol, acetaldehyde, vinyl chloride, ethylene oxide) and permanent gas component (carbon monoxide,
Total hydrocarbon, methane) detection and analysis, achieve the purpose that quickly to detect.
2, the chromatographic column I in the present invention can be to CO, methane and CO2It is separated, after isolating CO and methane, rotation ten
Port valve I is passed through carrier gas and carries out blowback to chromatographic column I, thus by CO2Discharge, has saved detection time, while also avoiding high-content
CO2Methanator is damaged.
3, use three root chromatogram columns to organic gas component (benzene, methanol, acetaldehyde, chloroethene in GB 1886.228-2016
Alkene, ethylene oxide) it is separated, and the present invention can efficiently separate all of above organic gas using a capillary chromatographic column
Component improves the utilization rate of chromatographic column, improves work efficiency simultaneously.
Detailed description of the invention
Fig. 1-schematic structural diagram of the device of the invention.
Wherein: 1- ten-way valve I；I entrance of A- carrier gas；I entrance communication port of B- quantitative loop；C- sample gas inlet I；The outlet of D- sample gas
Ⅰ；I outlet mouth of E- quantitative loop；I entrance communication port of F- chromatographic column；II communication port of G- resisting force column；II entrance of H- carrier gas；I- color
Compose I outlet mouth of column；I communication port of J- resisting force column；2- chromatographic column I；3- resisting force column I；4- methanator；5-FID detector
Ⅰ；6- resisting force column II；7- quantitative loop I；8- quantitative loop II；9- ten-way valve II；II outlet mouth of K- quantitative loop；L- carrier gas III enters
Mouthful；M- capillary split stream injector, communication port；II entrance communication port of N- quantitative loop；O- sample gas inlet II；P- sample gas outlet II；Q-
III entrance communication port of quantitative loop；IV entrance of R- carrier gas；II entrance communication port of S- chromatographic column；III outlet mouth of T- quantitative loop；10-
Quantitative loop III；11- chromatographic column II；12- dottle pin purges regulating valve；13- shunts adsorption trap；14- shunting valve；15- capillary
Split stream injector,；16-FID detector II；17- chromatographic column III；18- carrier gas I；19- sample gas I；20- carrier gas II；21- carrier gas III；
22- sample gas II；23- carrier gas IV；24- purge gas；25- vent gas；I output end of 26- sample gas；27- dottle pin purges tail gas；
28- shunts tail gas；II output end of 29- sample gas.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Referring to Fig. 1, impurity composition chromatographic analysis device in food-grade carbon-dioxide, including ten-way valve I 1, ten-way valve II 9,
Fid detector I 5, fid detector II 16, methanator 4, quantitative loop I 7, quantitative loop II 8, quantitative loop III 10, chromatographic column I 2,
Resisting force column I 3, resisting force column II 6, chromatographic column II 11 and chromatographic column III 17.
10 ports of the ten-way valve are I C of sample gas inlet, I entrance communication port B of quantitative loop, I outlet mouth of quantitative loop
E, I entrance communication port F of chromatographic column, I outlet mouth I of chromatographic column, I communication port J of resisting force column, II communication port G of resisting force column, carrier gas I
Entrance A, II entrance H of carrier gas and sample gas export I D.
I 7 entrance of quantitative loop is connected to I entrance communication port B of quantitative loop, and the outlet of quantitative loop I 7 connects with the outlet of quantitative loop I
Port E connection；The both ends of the chromatographic column I 2 are connected to I entrance communication port F of chromatographic column and I outlet mouth I of chromatographic column respectively；
One end of resisting force column I 3 is connected to I communication port J of resisting force column, and the other end is connected to 4 entrance of methanator；Methanator 4 goes out
Mouth is connected to fid detector I 5；One end of resisting force column II 6 is connected to II communication port G of resisting force column, other end connection emptying pipeline,
The CO of high-content is discharged2, obtain vent gas 25.
Here setting resisting force column I is primarily to prevent air-flow during switching ten-way valve I of fid detector I from making to it
At flame-out influence.
10 ports of the ten-way valve are II O of sample gas inlet, II entrance communication port N of quantitative loop, quantitative loop II export and connect
Port K, III entrance communication port Q of quantitative loop, III outlet mouth T of quantitative loop, II entrance communication port S of chromatographic column, chromatographic column III connect
Port, III entrance L of carrier gas, IV entrance R of carrier gas and sample gas export II P.
II 8 entrance of quantitative loop is connected to II entrance communication port N of quantitative loop, and the outlet of quantitative loop II 8 goes out with quantitative loop II
Mouth communication port K connection；III 10 entrance of quantitative loop is connected to III entrance communication port Q of quantitative loop, the outlet of quantitative loop III 10 and quantitative loop
III outlet mouth T connection；II 11 one end of chromatographic column is connected to II entrance communication port S of chromatographic column, the other end and fid detector I 5
Connection；III 17 one end of chromatographic column is connected mouth M with capillary sample inlet device and is connected to, and the other end is connected to fid detector II 16.
Chromatographic column I is for separating CO, methane and CO2, and CO2Separating rate is slow in chromatographic column I, is separated when not yet
When just rotate ten-way valve I carry out blowback, by the CO in chromatographic column I2Emptying.Chromatographic column II is for separating total hydrocarbon.This reality
The chromatographic column I used in example is applied as SC0001 φ 3 × 1m stainless steel chromatographic column, the chromatographic column II used is SCBWQ total hydrocarbon column φ 3
× 1m stainless steel chromatographic column.
The chromatographic column III 17 is capillary chromatographic column, and capillary is equipped between the capillary chromatographic column and ten-way valve II
Split stream injector, 15 entrance of capillary split stream injector, are connected mouth M with the capillary sample inlet device of ten-way valve II and are connected to；Capillary
The outlet of pipe split stream injector, 15 is set there are three pipeline, and wherein first pipe is equipped with dottle pin and purges regulating valve 12, which is used for
Dottle pin purging, setting dottle pin purge the emission flow that regulating valve is used to control dottle pin purging tail gas 27；Second pipe, which is equipped with, to be divided
Adsorption trap 13 is flowed, 13 one end of adsorption trap is shunted and is connected to capillary split stream injector, 15, shunt the pipeline of 13 outlet end of adsorption trap
It is equipped with shunting valve 14, shunting valve is used to adjust the rate of discharge for shunting tail gas 28, thus can be slowly fast
Rate carries out shunting discharge to carrier gas；Third pipeline is connected to one end of chromatographic column III 17, and sample gas is pushed to chromatographic column III and is carried out
Separation, is detected subsequently into fid detector II 16.
Here chromatographic column III 17 be capillary chromatographic column be primarily due to capillary chromatographic column herein will to benzene, methanol,
The components such as acetaldehyde, vinyl chloride, ethylene oxide are separated, and inferior separating effect are carried out using common chromatographic column, after leading to detection
The peak of appearance is unobvious, and is separated using capillary chromatographic column, and capillary chromatographic column is thinner, and separating rate is slow, and different groups
It point can successively be separated, the peak that when detection occurs is also obvious easily to be distinguished.The chromatographic column III used in the present embodiment is KB-
PLOTQ quartz capillary chromatographic column φ 0.32mm (ID) × 30m × 20um.
When the ten-way valve I 1 and ten-way valve II 9 are in original state, the connection status of ten-way valve I are as follows: I entrance of quantitative loop
Communication port B is connected to I C of sample gas inlet, and sample gas exports I D and is connected to I outlet mouth E of quantitative loop, I entrance communication port F of chromatographic column
It is connected to II communication port G of resisting force column, II entrance H of carrier gas is connected to I outlet mouth I of chromatographic column, I communication port J of resisting force column and load
I entrance A of gas connection；The connected state of ten-way valve II: III entrance L of carrier gas is connected to capillary split stream injector, communication port M, quantitative
II entrance communication port N of ring is connected to II O of sample gas inlet, and sample gas exports II P and is connected to III entrance communication port Q of quantitative loop, carrier gas IV
Entrance is connected to II entrance communication port S of R chromatographic column, and III outlet mouth T of quantitative loop is connected to II outlet mouth K of quantitative loop.
When the ten-way valve I 1 and in running order ten-way valve II 9, I entrance communication port B of I entrance A of carrier gas and quantitative loop
Connection, I C of sample gas inlet and sample gas export I D and are connected to, and I outlet mouth E of quantitative loop is connected to I entrance communication port F of chromatographic column, resistance
II communication port G of power column is connected to II entrance H of carrier gas, and I outlet mouth I of chromatographic column is connected to I communication port J of resisting force column；Ten-way valve
II connected state: II outlet mouth K of quantitative loop is connected to III entrance L of carrier gas, capillary split stream injector, communication port M and fixed
II entrance communication port N of ring connection is measured, II O of sample gas inlet exports II P with sample gas and is connected to, III entrance communication port Q of quantitative loop and carrier gas
IV entrance R connection；II entrance communication port S of chromatographic column is connected to III outlet mouth T of quantitative loop.
Carrier gas I 18 and carrier gas II 20 into II entrance H of I entrance A of carrier gas and carrier gas are H2, here in methanator
Require supplementation with H2, directly provided by carrier gas, so that CO and H2Reaction generates methane, detects hence into fid detector I；Into
The carrier gas III 21 and carrier gas IV 23 of IV entrance R of III entrance L of carrier gas and carrier gas is H2Or N2One of.
The fid detector II 16 is connected with purging pipeline, and purging pipeline one end connects fid detector import, and one end is
24 entrance of purge gas.The purge gas 24 is N2。
The detection method of impurity composition chromatography in food-grade carbon-dioxide utilizes mentioned-above food-grade titanium dioxide
The method that impurity composition chromatographic analysis device is detected in carbon, specifically includes the following steps:
(1) when ten-way valve I and ten-way valve II are in original state, sample gas passes through sample gas inlet I respectively and sample gas inlet II enters
Ten-way valve I and ten-way valve II, so as to be full of sample gas in quantitative loop I, quantitative loop II and quantitative loop III；
Under this step, after single injected sampling, sample gas enters gas phase chromatographic device, is then split into sample gas I 19 and sample gas II 22 simultaneously
Ten-way valve I and ten-way valve II are respectively enterd, wherein the airflow process of sample gas I 19 are as follows: sample gas I 19 enters from I C of sample gas inlet
Ten-way valve I, then from I inlet communication mouth B of quantitative loop come out enter quantitative loop I 7, after from I outlet mouth E of quantitative loop enter ten
Port valve I finally exports I D from sample gas and comes out from the discharge of I output end 26 of sample gas.
And the airflow process of sample gas II 22 are as follows: sample gas II 22 enters ten-way valve II from sample gas inlet O, then from quantitative
II inlet communication mouth N of ring enters quantitative loop II 8, then enters ten-way valve II from II outlet mouth K of quantitative loop, then from quantitative loop III
Inlet communication mouth T enters quantitative loop III 10, then exports connection mouth Q from quantitative loop III and enters ten-way valve II, finally goes out from sample gas
II P of mouth, which comes out from II output end 29 of sample gas, to be discharged.
Make sample gas full of quantitative loop I, quantitative loop II and quantitative loop III in this way, enters to carrier gas and it is detected.
(2) moment rotation ten-way valve I and ten-way valve II, keeps ten-way valve I and ten-way valve II in running order, carrier gas I from
After carrier gas inlet I enters ten-way valve I, the sample gas pushed in quantitative loop I sequentially enters chromatographic column I, resisting force column I, methanator,
Fid detector I is finally reached, test sample gas is treated in fid detector I and is detected, out CO and CH4Peak；Meanwhile carrier gas III from
After carrier gas inlet III enters ten-way valve II, the sample gas pushed in quantitative loop II sequentially enters capillary split stream injector, chromatographic column
III, finally reach fid detector II, fid detector II detects sample to be tested, out benzene, methanol, acetaldehyde, vinyl chloride and
The peak of ethylene oxide；Meanwhile after carrier gas IV is from carrier gas inlet IV into ten-way valve II, the sample gas pushed in quantitative loop III enters color
It composes after column II separates and reaches fid detector I, treat test sample gas in fid detector I and detected, the peak of total hydrocarbon, finally obtains out
Gas chromatogram.
Under this step, carrier gas I, carrier gas III and carrier gas IV enter simultaneously pushes sample gas, wherein the gas circuit of carrier gas I 18
The process of circulation are as follows: carrier gas I enters ten-way valve I from I import A of carrier gas, then enters quantitative loop I 7 from I inlet communication mouth B of quantitative loop,
Exported from quantitative loop I and connect mouth E and enter ten-way valve I, then enter chromatographic column I 2 from I inlet communication mouth F of chromatographic column, after from chromatographic column
I outlet mouth I enters ten-way valve I, after from I communication port J intake resistance column I of resisting force column, subsequently into methanator, finally
It is detected into fid detector I, methane and CO are successively separated in chromatographic column I, and in methanator, CO quickly turns
Turn to methane, and methane directly passes through methanator, after detected by fid detector I, the successive peak of CO and methane out.
The gas circuit process of circulation of carrier gas III 21 are as follows: carrier gas III 21 enters ten-way valve II from III entrance L of carrier gas, after from quantitative loop
II outlet mouth K enters quantitative loop II 8, after from II inlet communication mouth N of quantitative loop enter ten-way valve II, after shunted from capillary
Sample injector communication port M enters capillary split stream injector, 15, is split herein, and then the push of part carrier gas III sample gas enters color
Column III is composed, the detection of fid detector II is finally entered, can detecte out benzene, methanol, acetaldehyde, vinyl chloride and ethylene oxide here, i.e.,
They are at the peak that different appearance times occur.
The gas circuit process of circulation of carrier gas IV 23 are as follows: carrier gas IV enters ten-way valve II from IV entrance R of carrier gas, after from quantitative loop III
Outlet mouth Q enters quantitative loop III, then enters ten-way valve II from III inlet communication mouth T of quantitative loop, then enter from chromatographic column II
Mouth communication port S enters chromatographic column II, finally enters the detection of fid detector I, out the peak of total hydrocarbon.
Carrier gas at this time II 20 after II entrance H of carrier gas directly from II 6 communication port of resisting force column come out after through II heel row of resisting force column
Sky obtains vent gas 25.
(3) when there is CO and CH4Peak after moment rotate ten-way valve I, ten-way valve I is in original state, carrier gas II at this time
After entering ten-way valve I by carrier gas inlet II, by chromatographic column I and resisting force column II, by the CO of high-content2Emptying.
Under this step, the gas circuit process of circulation of carrier gas II are as follows: carrier gas II enters ten-way valve I from II entrance H of carrier gas, after from color
Spectrum I outlet mouth I of column enters chromatographic column I, then enters ten-way valve I from I entrance communication port F of chromatographic column, then connect from resisting force column
Port G intake resistance column II is emptied finally by resisting force column II, the CO of high-content in such chromatographic column I2Emptying, to avoid CO2
Damage methanator.
Analytical conditions for gas chromatography of the present invention are as follows: 200 DEG C of injector temperature, post case temperature are 60 DEG C, I and of fid detector
The temperature of fid detector II is 230 DEG C, flow rate of carrier gas is 30 mL/min.
Finally, it should be noted that the above embodiment of the present invention is only example to illustrate the invention, and it is not
It is the restriction to embodiment of the present invention.For those of ordinary skill in the art, on the basis of the above description also
Other various forms of variations and variation can be made.Here all embodiments can not be exhaustive.It is all to belong to this
The technical solution changes and variations that derived from of invention are still in the scope of protection of the present invention.
Claims (8)
1. impurity composition chromatographic analysis device in food-grade carbon-dioxide, which is characterized in that including ten-way valve I, ten-way valve II,
Fid detector I, fid detector II, methanator, quantitative loop I, quantitative loop II, quantitative loop III, chromatographic column I, resisting force column I,
Resisting force column II, chromatographic column II and chromatographic column III；
10 ports of the ten-way valve are sample gas inlet I, I entrance communication port of quantitative loop, I outlet mouth of quantitative loop, chromatographic column
I entrance communication port, I outlet mouth of chromatographic column, I communication port of resisting force column, II communication port of resisting force column, I entrance of carrier gas, carrier gas II enter
Mouth and sample gas outlet I；
I entrance of quantitative loop is connected to I entrance communication port of quantitative loop, and the outlet of quantitative loop I connects with I outlet mouth of quantitative loop
It is logical；The both ends of the chromatographic column I are connected to I entrance communication port of chromatographic column and I outlet mouth of chromatographic column respectively；Resisting force column I
One end is connected to I communication port of resisting force column, and the other end is connected to methanator entrance；Methanator outlet and fid detector I
Connection；One end of resisting force column II is connected to II communication port of resisting force column, other end connection emptying pipeline；
10 ports of the ten-way valve are sample gas inlet II, II entrance communication port of quantitative loop, II outlet mouth of quantitative loop, determine
Measure III entrance communication port of ring, III outlet mouth of quantitative loop, II entrance communication port of chromatographic column, III communication port of chromatographic column, carrier gas III
Entrance, IV entrance of carrier gas and sample gas outlet II；
II entrance of quantitative loop is connected to II entrance communication port of quantitative loop, the outlet of quantitative loop II and II outlet mouth of quantitative loop
Connection；III entrance of quantitative loop is connected to III entrance communication port of quantitative loop, and the outlet of quantitative loop III connects with III outlet mouth of quantitative loop
It is logical；II one end of chromatographic column is connected to II entrance communication port of chromatographic column, and the other end is connected to fid detector I；III one end of chromatographic column with
The connection of III communication port of chromatographic column, the other end are connected to fid detector II.
2. impurity composition chromatographic analysis device in food-grade carbon-dioxide according to claim 1, which is characterized in that described
Chromatographic column III is capillary chromatographic column, and capillary split stream injector, institute are equipped between the capillary chromatographic column and ten-way valve II
Capillary split stream injector, entrance to be stated to be connected to III communication port of chromatographic column, the outlet of capillary split stream injector, is set there are three pipeline,
Wherein first pipe is equipped with dottle pin and purges regulating valve；Second pipe, which is equipped with, shunts adsorption trap, shunts adsorption trap one end and hair
The connection of tubule split stream injector, the pipeline for shunting adsorption trap outlet end are equipped with shunting valve；Third pipeline and chromatographic column III
One end connection.
3. impurity composition chromatographic analysis device in food-grade carbon-dioxide according to claim 2, which is characterized in that described
When ten-way valve I and ten-way valve II are in original state, the connection status of ten-way valve I are as follows: I entrance communication port of quantitative loop and sample gas enter
Mouth I is connected to, and sample gas outlet I is connected to I outlet mouth of quantitative loop, and I entrance communication port of chromatographic column and II communication port of resisting force column connect
Logical, II entrance of carrier gas is connected to I outlet mouth of chromatographic column, and I communication port of resisting force column is connected to I entrance of carrier gas；Ten-way valve II
Connected state: III entrance of carrier gas is connected to capillary split stream injector, communication port, II entrance communication port of quantitative loop and sample gas inlet
II connection, sample gas outlet II are connected to III entrance communication port of quantitative loop, and IV entrance of carrier gas is connected to II entrance communication port of chromatographic column,
III outlet mouth of quantitative loop is connected to II outlet mouth of quantitative loop；
When the ten-way valve I and in running order ten-way valve II, the connected state of ten-way valve I are as follows: I entrance of carrier gas and quantitative loop
The connection of I entrance communication port, sample gas inlet I are connected to sample gas outlet I, I entrance communication port of I outlet mouth of quantitative loop and chromatographic column
Connection, II communication port of resisting force column are connected to II entrance of carrier gas, and I outlet mouth of chromatographic column is connected to I communication port of resisting force column；Ten is logical
The connected state of valve II: II outlet mouth of quantitative loop is connected to III entrance of carrier gas, capillary split stream injector, communication port and fixed
The connection of II entrance communication port of ring is measured, sample gas inlet II is connected to sample gas outlet II, and III entrance communication port of quantitative loop and carrier gas IV enter
Mouth connection；II entrance communication port of chromatographic column is connected to III outlet mouth of quantitative loop.
4. impurity composition chromatographic analysis device in food-grade carbon-dioxide according to claim 1, which is characterized in that enter
The carrier gas I and carrier gas II of II entrance of I entrance of carrier gas and carrier gas are H2；Into III He of carrier gas of IV entrance of III entrance of carrier gas and carrier gas
Carrier gas IV is H2Or N2One of.
5. impurity composition chromatographic analysis device in food-grade carbon-dioxide according to claim 1, which is characterized in that described
Fid detector II is connected with purging pipeline, and purging pipeline one end connects fid detector import, and one end is purge gas entrance.
6. impurity composition chromatographic analysis device in food-grade carbon-dioxide according to claim 5, which is characterized in that described
Purge gas is N2。
7. the detection method of impurity composition chromatography in food-grade carbon-dioxide, which is characterized in that using described in claim 3
Food-grade carbon-dioxide in the method that is detected of impurity composition chromatographic analysis device, specifically includes the following steps:
(1) when ten-way valve I and ten-way valve II are in original state, sample gas passes through sample gas inlet I respectively and sample gas inlet II enters
Ten-way valve I and ten-way valve II, so as to be full of sample gas in quantitative loop I, quantitative loop II and quantitative loop III；
(2) moment rotation ten-way valve I and ten-way valve II, keeps ten-way valve I and ten-way valve II in running order, and carrier gas I is from carrier gas
After entrance I enters ten-way valve I, the sample gas pushed in quantitative loop I sequentially enters chromatographic column I, resisting force column I, methanator, finally
Fid detector I is reached, test sample gas is treated in fid detector I and is detected, out CO and CH4Peak；Meanwhile carrier gas III is from carrier gas
After entrance III enters ten-way valve II, the sample gas pushed in quantitative loop II sequentially enters capillary split stream injector, chromatographic column III, most
Fid detector II is reached afterwards, and fid detector II detects sample to be tested, out benzene, methanol, acetaldehyde, vinyl chloride and epoxy second
The peak of alkane；Meanwhile after carrier gas IV is from carrier gas inlet IV into ten-way valve II, the sample gas pushed in quantitative loop III enters chromatographic column II
Fid detector I is reached after separation, is treated test sample gas in fid detector I and is detected, out the peak of total hydrocarbon, finally obtains gas phase color
Spectrogram.
8. the detection method of impurity composition chromatography, feature exist in food-grade carbon-dioxide according to claim 7
In further including step (3), as CO and CH out4Peak after moment rotate ten-way valve I, ten-way valve I be in original state at this time, load
After gas II enters ten-way valve I by carrier gas inlet II, by chromatographic column I and resisting force column II, by the CO of high-content2Emptying.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02120661A (en) * | 1988-10-28 | 1990-05-08 | Shimadzu Corp | Gas chromatograph |
| CN2886567Y (en) * | 2005-09-07 | 2007-04-04 | 上海华爱色谱分析技术有限公司 | Gas chromatograph for complete gas analysis |
| CN101923098A (en) * | 2010-08-20 | 2010-12-22 | 南京特种气体厂有限公司 | Continuous on-line analysis device of benzene, total hydrocarbons, methane and CO in carbon dioxide |
| CN102095827A (en) * | 2009-12-09 | 2011-06-15 | 中国科学院大气物理研究所 | System and method for measuring carbon dioxide, methane and nitrous oxide in air simultaneously |
| CN202421140U (en) * | 2011-11-25 | 2012-09-05 | 北京北分瑞利分析仪器(集团)有限责任公司 | Gas chromatograph for detecting mine gas |
| CN202770815U (en) * | 2012-06-27 | 2013-03-06 | 上海科创色谱仪器有限公司 | Special gas chromatograph for analysis of high-purity carbon dioxide |
| CN203745437U (en) * | 2014-03-27 | 2014-07-30 | 山西易高煤层气有限公司 | Separation and analysis device for light components in coal-bed methane |
| CN104614474A (en) * | 2014-12-31 | 2015-05-13 | 中国农业科学院农业环境与可持续发展研究所 | Gas circuit configuration method for measuring three major greenhouse gases by using double-valve system |
| CN204359757U (en) * | 2015-01-19 | 2015-05-27 | 大连中汇达科学仪器有限公司 | A kind of New type coal methanol project special-purpose gas chromatograph |
| CN105510503A (en) * | 2015-12-31 | 2016-04-20 | 上海正帆科技股份有限公司 | Analysis device and method of electronic-grade chlorine gas |
| CN105510492A (en) * | 2015-12-31 | 2016-04-20 | 上海正帆科技股份有限公司 | Analysis device and method of electronic-grade hydrogen chloride |
| WO2017061804A1 (en) * | 2015-10-06 | 2017-04-13 | 주식회사 엘지화학 | High-speed gas sample analysis device using gas chromatography, and method thereof |
| WO2017184748A1 (en) * | 2016-04-20 | 2017-10-26 | Waters Technologies Corporation | Method and apparatus for flame ionization detection for chromatography |
| CN206974972U (en) * | 2017-05-22 | 2018-02-06 | 北京竹青世纪科技有限公司 | A kind of NMHC gas analyzer |
| CN209656641U (en) * | 2019-04-09 | 2019-11-19 | 重庆市计量质量检测研究院 | Impurity composition chromatographic analysis device in food-grade carbon-dioxide |
-
2019
- 2019-04-09 CN CN201910281302.3A patent/CN109884229B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02120661A (en) * | 1988-10-28 | 1990-05-08 | Shimadzu Corp | Gas chromatograph |
| CN2886567Y (en) * | 2005-09-07 | 2007-04-04 | 上海华爱色谱分析技术有限公司 | Gas chromatograph for complete gas analysis |
| CN102095827A (en) * | 2009-12-09 | 2011-06-15 | 中国科学院大气物理研究所 | System and method for measuring carbon dioxide, methane and nitrous oxide in air simultaneously |
| CN101923098A (en) * | 2010-08-20 | 2010-12-22 | 南京特种气体厂有限公司 | Continuous on-line analysis device of benzene, total hydrocarbons, methane and CO in carbon dioxide |
| CN202421140U (en) * | 2011-11-25 | 2012-09-05 | 北京北分瑞利分析仪器(集团)有限责任公司 | Gas chromatograph for detecting mine gas |
| CN202770815U (en) * | 2012-06-27 | 2013-03-06 | 上海科创色谱仪器有限公司 | Special gas chromatograph for analysis of high-purity carbon dioxide |
| CN203745437U (en) * | 2014-03-27 | 2014-07-30 | 山西易高煤层气有限公司 | Separation and analysis device for light components in coal-bed methane |
| CN104614474A (en) * | 2014-12-31 | 2015-05-13 | 中国农业科学院农业环境与可持续发展研究所 | Gas circuit configuration method for measuring three major greenhouse gases by using double-valve system |
| CN204359757U (en) * | 2015-01-19 | 2015-05-27 | 大连中汇达科学仪器有限公司 | A kind of New type coal methanol project special-purpose gas chromatograph |
| WO2017061804A1 (en) * | 2015-10-06 | 2017-04-13 | 주식회사 엘지화학 | High-speed gas sample analysis device using gas chromatography, and method thereof |
| CN105510503A (en) * | 2015-12-31 | 2016-04-20 | 上海正帆科技股份有限公司 | Analysis device and method of electronic-grade chlorine gas |
| CN105510492A (en) * | 2015-12-31 | 2016-04-20 | 上海正帆科技股份有限公司 | Analysis device and method of electronic-grade hydrogen chloride |
| WO2017184748A1 (en) * | 2016-04-20 | 2017-10-26 | Waters Technologies Corporation | Method and apparatus for flame ionization detection for chromatography |
| CN206974972U (en) * | 2017-05-22 | 2018-02-06 | 北京竹青世纪科技有限公司 | A kind of NMHC gas analyzer |
| CN209656641U (en) * | 2019-04-09 | 2019-11-19 | 重庆市计量质量检测研究院 | Impurity composition chromatographic analysis device in food-grade carbon-dioxide |
Non-Patent Citations (1)
| Title |
|---|
| 赵亚军 等: "煤制烯烃微量一氧化碳、二氧化碳气相色谱法测定方法", 石化技术, no. 01, pages 102 - 104 * |
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