CN109884229B - Chromatographic analysis device for impurity components in food-grade carbon dioxide and detection method thereof - Google Patents
Chromatographic analysis device for impurity components in food-grade carbon dioxide and detection method thereof Download PDFInfo
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- CN109884229B CN109884229B CN201910281302.3A CN201910281302A CN109884229B CN 109884229 B CN109884229 B CN 109884229B CN 201910281302 A CN201910281302 A CN 201910281302A CN 109884229 B CN109884229 B CN 109884229B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 27
- 239000012535 impurity Substances 0.000 title claims abstract description 18
- 238000004587 chromatography analysis Methods 0.000 title claims abstract description 15
- 238000001514 detection method Methods 0.000 title abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 54
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004891 communication Methods 0.000 claims description 174
- 239000007789 gas Substances 0.000 claims description 116
- 239000012159 carrier gas Substances 0.000 claims description 114
- 238000010926 purge Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 7
- 125000006850 spacer group Chemical group 0.000 claims description 7
- 235000013305 food Nutrition 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 239000002778 food additive Substances 0.000 description 6
- 235000013373 food additive Nutrition 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 4
- 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
- 238000007664 blowing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FPHNWFFKQCPXPI-UHFFFAOYSA-N 3-chlorooxolane Chemical compound ClC1CCOC1 FPHNWFFKQCPXPI-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 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
- 239000006227 byproduct Substances 0.000 description 1
- NPGILLWFJVZZPP-UHFFFAOYSA-N carbon dioxide;lead Chemical compound [Pb].O=C=O NPGILLWFJVZZPP-UHFFFAOYSA-N 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000009920 food preservation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
Abstract
The invention discloses a chromatographic analysis device and a detection method for impurity components in food-grade carbon dioxide, wherein the device comprises a ten-way valve I and a ten-way valve II; two ends of the quantitative ring I are communicated with the ten-way valve I, and two ends of the chromatographic column I are communicated with the ten-way valve I; one end of the resistance column I is communicated with the ten-way valve I, and the other end of the resistance column I is communicated with the inlet of the methane converter; the outlet of the methane converter is communicated with the FID detector I; one end of the resistance column II is communicated with the ten-way valve I, and the other end of the resistance column II is emptied; both ends of the quantitative ring II and the quantitative ring III are communicated with a ten-way valve II, one end of a chromatographic column II is communicated with the ten-way valve II, and the other end of the chromatographic column II is communicated with an FID detector I; the inlet of the capillary tube split-flow sample injector is communicated with the ten-way valve II, one outlet of the capillary tube split-flow sample injector is communicated with one end of the chromatographic column III, and the other end of the chromatographic column III is communicated with the FID detector II. The device can rapidly detect eight components of benzene, methanol, acetaldehyde, vinyl chloride, ethylene oxide, carbon monoxide, total hydrocarbon and methane through one sample injection.
Description
Technical Field
The invention relates to the field of gas chromatography, in particular to a chromatographic analysis device and a detection method for impurity components in food-grade carbon dioxide.
Background
Carbon dioxide is used as the most widely used gas food additive and is widely applied to the fields of carbonated beverage, beer, food preservation and the like. China is the second major economy of the world, has huge demand for food-grade carbon dioxide, has annual demand of approximately 200 ten thousand tons, and is greatly increased year by year.
Food grade carbon dioxide is necessarily important as a food additive for the detection of harmful impurities. The different sources of carbon dioxide lead to great difference in the contents of hydrocarbon, benzene, sulfur, aldehyde, alcohol and other impurities harmful to human bodies, and the main source of the food-grade carbon dioxide in China is a carbon dioxide gas source of chemical product byproducts.
In addition, china is relatively lagged in the establishment of standards of food-grade carbon dioxide, and is successively subjected to GB10621-1989 food additive liquid carbon dioxide lime kiln method and synthetic ammonia method, GB1917-1994 food additive liquid carbon dioxide fermentation method, GB10621-2006 food additive liquid carbon dioxide, GB 1886.228-2016 food safety national standard food additive carbon dioxide, and new standards are formally implemented in 1 month 1 of 2017. The requirements for impurity content and detection methods in the new standard are specified in detail, but some detection methods in the standard are complicated, the required equipment is complex in type, the traceability system is not perfect enough, and the detection uncertainty is large. Moreover, domestic studies on standard substances of food-grade carbon dioxide all adopt single components, and in practical detection, each component needs to be analyzed independently by using one instrument. Therefore, each component needs to be sampled, the detection time is long, the efficiency is low, and the rapid detection of the food-grade carbon dioxide is a technical problem to be solved urgently.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a chromatographic analysis device and a detection method for impurity components in food-grade carbon dioxide, which can be used for rapidly detecting and have high accuracy.
The technical scheme of the invention is realized as follows:
the chromatographic analysis device for the impurity components in the food-grade carbon dioxide comprises a ten-way valve I, a ten-way valve II, an FID detector I, an FID detector II, a methane converter, a quantitative ring I, a quantitative ring II and a quantitative ring III, and a chromatographic column I, a resistance column II, a chromatographic column II and a chromatographic column III.
The ten ports of the ten-way valve are a sample gas inlet I, a quantitative ring I inlet communication port, a quantitative ring I outlet communication port, a chromatographic column I inlet communication port, a chromatographic column I outlet communication port, a resistance column I communication port, a resistance column II communication port, a carrier gas I inlet, a carrier gas II inlet and a sample gas outlet I.
The quantitative ring I inlet is communicated with the quantitative ring I inlet communication port, and the quantitative ring I outlet is communicated with the quantitative ring I outlet communication port; the two ends of the chromatographic column I are respectively communicated with an inlet communication port of the chromatographic column I and an outlet communication port of the chromatographic column I; one end of the resistance column I is communicated with the communication port of the resistance column I, and the other end of the resistance column I is communicated with the inlet of the methane converter; the outlet of the methane converter is communicated with the FID detector I; one end of the resistance column II is communicated with the communication port of the resistance column II, and the other end of the resistance column II is connected with an emptying pipeline.
The ten ports of the ten-way valve II are a sample gas inlet II, a quantitative ring II inlet communication port, a quantitative ring II outlet communication port, a quantitative ring III inlet communication port, a quantitative ring III outlet communication port, a chromatographic column II inlet communication port, a chromatographic column III communication port, a carrier gas III inlet, a carrier gas IV inlet and a sample gas outlet II.
The quantitative ring II inlet is communicated with the quantitative ring II inlet communication port, and the quantitative ring II outlet is communicated with the quantitative ring II outlet communication port; the quantitative ring III inlet is communicated with the quantitative ring III inlet communication port, and the quantitative ring III outlet is communicated with the quantitative ring III outlet communication port; one end of the chromatographic column II is communicated with the inlet communication port of the chromatographic column II, and the other end of the chromatographic column II is communicated with the FID detector I; one end of the chromatographic column III is communicated with the communication port of the chromatographic column III, and the other end is communicated with the FID detector II.
Further, the chromatographic column III is a capillary chromatographic column, a capillary shunt sample injector is arranged between the capillary chromatographic column and a ten-way valve II, an inlet of the capillary shunt sample injector is communicated with a communication port of the chromatographic column III, an outlet of the capillary shunt sample injector is provided with three pipelines, and a partition pad purging regulating valve is arranged on a first pipeline; a shunt adsorption trap is arranged on the second pipeline, one end of the shunt adsorption trap is communicated with the capillary shunt sampler, and a shunt regulating valve is arranged on the pipeline at the outlet end of the shunt adsorption trap; the third pipeline is communicated with one end of the chromatographic column III.
Further, when the ten-way valve I and the ten-way valve II are in the initial state, the connection state of the ten-way valve I is as follows: the quantitative ring I inlet communication port is communicated with the sample gas inlet I, the sample gas outlet I is communicated with the quantitative ring I outlet communication port, the chromatographic column I inlet communication port is communicated with the resistance column II communication port, the carrier gas II inlet is communicated with the chromatographic column I outlet communication port, and the resistance column I communication port is communicated with the carrier gas I inlet; communication state of ten-way valve II: the inlet of the carrier gas III is communicated with the communication port of the capillary shunt sampler, the inlet of the quantitative ring II is communicated with the inlet of the sample gas II, the outlet of the sample gas II is communicated with the inlet of the quantitative ring III, the inlet of the carrier gas IV is communicated with the inlet of the chromatographic column II, and the outlet of the quantitative ring III is communicated with the outlet of the quantitative ring II.
When the ten-way valve I and the ten-way valve II are in the working state, the communication state of the ten-way valve I is as follows: the inlet of the carrier gas I is communicated with the inlet communication port of the quantitative ring I, the sample gas inlet I is communicated with the sample gas outlet I, the outlet communication port of the quantitative ring I is communicated with the inlet communication port of the chromatographic column I, the outlet communication port of the resistance column II is communicated with the inlet communication port of the carrier gas II, and the outlet communication port of the chromatographic column I is communicated with the outlet communication port of the resistance column I; communication state of ten-way valve II: the quantitative ring II outlet communication port is communicated with the carrier gas III inlet, the capillary split-flow sample injector communication port is communicated with the quantitative ring II inlet communication port, the sample gas inlet II is communicated with the sample gas outlet II, and the quantitative ring III inlet communication port is communicated with the carrier gas IV inlet; the inlet communication port of the chromatographic column II is communicated with the outlet communication port of the quantitative ring III.
Further, carrier gas I and carrier gas entering the carrier gas I inlet and carrier gas II inletII is H 2 The method comprises the steps of carrying out a first treatment on the surface of the The carrier gas III and the carrier gas IV entering the carrier gas III inlet and the carrier gas IV inlet are H 2 Or N 2 One of them.
Further, the FID detector II is connected with a purging pipeline, one end of the purging pipeline is connected with an inlet of the FID detector, and the other end of the purging pipeline is a purging gas inlet.
Further, the purge gas is N 2 。
The detection method for the chromatographic analysis of the impurity components in the food-grade carbon dioxide comprises the following steps of:
(1) When the ten-way valve I and the ten-way valve II are in an initial state, sample gas enters the ten-way valve I and the ten-way valve II through the sample gas inlet I and the sample gas inlet II respectively, so that the quantitative ring I, the quantitative ring II and the quantitative ring III are filled with the sample gas;
(2) The ten-way valve I and the ten-way valve II are instantaneously rotated to enable the ten-way valve I and the ten-way valve II to be in a working state, after the carrier gas I enters the ten-way valve I from the carrier gas inlet I, the sample gas in the push quantitative ring I sequentially enters the chromatographic column I, the resistance column I and the methane converter, finally reaches the FID detector I, detects the sample gas to be detected at the FID detector I, and outputs CO and CH 4 Is a peak of (2); meanwhile, after the carrier gas III enters the ten-way valve II from the carrier gas inlet III, pushing sample gas in the quantitative ring II to sequentially enter the capillary split-flow sample injector and the chromatographic column III, and finally reaching the FID detector II, and detecting a sample to be detected by the FID detector II to obtain peaks of benzene, methanol, acetaldehyde, vinyl chloride and ethylene oxide; meanwhile, after the carrier gas IV enters the ten-way valve II from the carrier gas inlet IV, the sample gas in the pushing quantitative ring III enters the chromatographic column II for separation and then reaches the FID detector I, the sample gas to be detected is detected by the FID detector I, the peak of total hydrocarbon is obtained, and finally the gas chromatogram is obtained.
Further, the method also comprises a step (3) when CO and CH are generated 4 The ten-way valve I is instantaneously rotated after the peak of the pressure sensor, and is in an initial state at the moment, and the carrier gas II enters the ten-way valve I through the carrier gas inlet II and passes through the chromatographic column I and the resistance column II so as to obtain high contentCO of (c) 2 And (5) evacuating.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention realizes the primary sample by designing a multi-valve multi-column gas chromatography system and adopting the modes of pre-separation, gas circuit back blowing and the like, and completes the detection and analysis of organic gas components (benzene, methanol, acetaldehyde, vinyl chloride and ethylene oxide) and permanent gas components (carbon monoxide, total hydrocarbon and methane) so as to achieve the aim of rapid detection.
2. The chromatographic column I in the invention can be used for CO, methane and CO 2 Separating, rotating a ten-way valve I after separating CO and methane, and introducing carrier gas to blow back the chromatographic column I so as to treat CO 2 Discharging, saving detection time and avoiding high content CO 2 Causing damage to the methanator.
3. In GB 1886.228-2016, three chromatographic columns are adopted to separate organic gas components (benzene, methanol, acetaldehyde, chloroethylene and ethylene oxide), and the invention adopts one capillary chromatographic column to effectively separate all the organic gas components, thereby improving the utilization rate of the chromatographic column and improving the working efficiency.
Drawings
FIG. 1-schematic diagram of the device structure of the present invention.
Wherein: 1-ten-way valve I; a-a carrier gas I inlet; b-the inlet communication port of the quantitative ring I; c-sample gas inlet I; d-a sample gas outlet I; e-the outlet communication port of the quantitative ring I; f-chromatographic column I inlet communication port; g-resistance column II communication port; h-carrier gas II inlet; i-chromatographic column I outlet communication port; j-resistance column I communication port; 2-chromatographic column I; 3-a resistance column I; a 4-methanator; a 5-FID detector I; 6-a resistance column II; 7-quantifying ring I; 8-quantifying ring II; 9-ten-way valve II; the outlet of the K-quantitative ring II is communicated with the opening; an L-carrier gas III inlet; the M-capillary shunt sampler is communicated with the port; an inlet communication port of the N-quantitative ring II; an O-sample gas inlet II; p-sample gas outlet II; q-quantitative ring III inlet communication port; an R-carrier IV inlet; s-chromatographic column II inlet communication port; an outlet communication port of the T-quantitative ring III; 10-quantifying ring III; 11-chromatographic column II; 12-a spacer purge control valve; 13-split adsorption trap; 14-a split-flow regulating valve; 15-a capillary split sample 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-evacuating the gas; 26-sample gas I output end; 27-sweeping tail gas through a spacer; 28-splitting tail gas; 29-sample gas II output end.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
Referring to fig. 1, the chromatographic analysis device for impurity components in food-grade carbon dioxide comprises a ten-way valve I1, a ten-way valve II 9, an FID detector I5, an FID detector II 16, a methane converter 4, a quantitative ring I7, a quantitative ring II 8, a quantitative ring III 10, a chromatographic column I2, a resistance column I3, a resistance column II 6, a chromatographic column II 11 and a chromatographic column III 17.
The ten ports of the ten-way valve I are a sample gas inlet IC, a quantitative ring I inlet communication port B, a quantitative ring I outlet communication port E, a chromatographic column I inlet communication port F, a chromatographic column I outlet communication port I, a resistance column I communication port J, a resistance column II communication port G, a carrier gas I inlet A, a carrier gas II inlet H and a sample gas outlet ID.
The inlet of the quantitative ring I7 is communicated with the inlet communication port B of the quantitative ring I, and the outlet of the quantitative ring I7 is communicated with the outlet communication port E of the quantitative ring I; the two ends of the chromatographic column I2 are respectively communicated with an inlet communication port F of the chromatographic column I and an outlet communication port I of the chromatographic column I; one end of the resistance column I3 is communicated with the communication port J of the resistance column I, and the other end of the resistance column I is communicated with the inlet of the methane converter 4; the outlet of the methane converter 4 is communicated with the FID detector I5; one end of the resistance column II 6 is communicated with the resistance column II communication port G, and the other end is connected with an emptying pipeline to discharge high-content CO 2 An evacuated gas 25 is obtained.
The resistance column I is provided here mainly to prevent the FID detector I from causing flameout during switching of the ten-way valve I.
The ten ports of the ten-way valve II are a sample gas inlet II O, a quantitative ring II inlet communication port N, a quantitative ring II outlet communication port K, a quantitative ring III inlet communication port Q, a quantitative ring III outlet communication port T, a chromatographic column II inlet communication port S, a chromatographic column III communication port, a carrier gas III inlet L, a carrier gas IV inlet R and a sample gas outlet II P.
The inlet of the quantitative ring II 8 is communicated with the inlet communication port N of the quantitative ring II, and the outlet of the quantitative ring II 8 is communicated with the outlet communication port K of the quantitative ring II; the inlet of the quantitative ring III 10 is communicated with the inlet communication port Q of the quantitative ring III, and the outlet of the quantitative ring III is communicated with the outlet communication port T of the quantitative ring III; one end of the chromatographic column II 11 is communicated with the inlet communication port S of the chromatographic column II, and the other end of the chromatographic column II is communicated with the FID detector I5; one end of the chromatographic column III 17 is communicated with the capillary sample injector through hole M, and the other end is communicated with the FID detector II 16.
Chromatographic column I for separating CO, methane and CO 2 And CO 2 The separation speed in the chromatographic column I is low, and when the chromatographic column I is not separated, the ten-way valve I is rotated to carry out back blowing, so that CO in the chromatographic column I is separated 2 And (5) evacuating. The chromatographic column II is used for separating the total hydrocarbon. The chromatographic column I used in this example is an SC0001 phi 3 x 1m stainless steel chromatographic column, and the chromatographic column II used is an SCBWQ total hydrocarbon column phi 3 x 1m stainless steel chromatographic column.
The chromatographic column III 17 is a capillary chromatographic column, a capillary shunt sample injector is arranged between the capillary chromatographic column and the ten-way valve II, and the inlet of the capillary shunt sample injector 15 is communicated with a capillary sample injector inlet M of the ten-way valve II; the outlet of the capillary shunt sampler 15 is provided with three pipelines, wherein a spacer purge regulating valve 12 is arranged on a first pipeline and is used for spacer purge, and the spacer purge regulating valve is arranged for controlling the discharge flow of the spacer purge tail gas 27; the second pipeline is provided with a split-flow adsorption trap 13, one end of the split-flow adsorption trap 13 is communicated with a capillary split-flow sample injector 15, the pipeline at the outlet end of the split-flow adsorption trap 13 is provided with a split-flow regulating valve 14, and the split-flow regulating valve is used for regulating the discharge rate of split-flow tail gas 28, so that the carrier gas can be split-flow discharged at a slow rate; the third pipeline is communicated with one end of the chromatographic column III 17, pushes sample gas to the chromatographic column III for separation, and then enters the FID detector II 16 for detection.
The chromatographic column III 17 is mainly because the capillary chromatographic column is used for separating components such as benzene, methanol, acetaldehyde, chloroethylene, ethylene oxide and the like, the common chromatographic column is used for separating poorly, so that the peak appearing after detection is not obvious, the capillary chromatographic column is used for separating, the capillary chromatographic column is thin, the separation speed is low, different components can be separated successively, and the peak appearing during detection is also obvious and easy to distinguish. The column III used in this example was KB-PLOTQ quartz capillary column phi 0.32mm (ID). Times.30 m.times.20 um.
When the ten-way valve I1 and the ten-way valve II 9 are in an initial state, the connection state of the ten-way valve I is as follows: the quantitative ring I inlet communication port B is communicated with the sample gas inlet IC, the sample gas outlet ID is communicated with the quantitative ring I outlet communication port E, the chromatographic column I inlet communication port F is communicated with the resistance column II communication port G, the carrier gas II inlet H is communicated with the chromatographic column I outlet communication port I, and the resistance column I communication port J is communicated with the carrier gas I inlet A; communication state of ten-way valve II: the inlet L of the carrier gas III is communicated with the communication port M of the capillary shunt sampler, the inlet communication port N of the quantitative ring II is communicated with the inlet II O of the sample gas, the outlet II P of the sample gas is communicated with the inlet communication port Q of the quantitative ring III, the inlet of the carrier gas IV is communicated with the inlet communication port S of the R chromatographic column II, and the outlet communication port T of the quantitative ring III is communicated with the outlet communication port K of the quantitative ring II.
When the ten-way valve I1 and the ten-way valve II 9 are in a working state, a carrier gas I inlet A is communicated with a quantitative ring I inlet communication port B, a sample gas inlet IC is communicated with a sample gas outlet ID, a quantitative ring I outlet communication port E is communicated with a chromatographic column I inlet communication port F, a resistance column II communication port G is communicated with a carrier gas II inlet H, and a chromatographic column I outlet communication port I is communicated with a resistance column I communication port J; communication state of ten-way valve II: the quantitative ring II outlet communication port K is communicated with the carrier gas III inlet L, the capillary shunt sampler communication port M is communicated with the quantitative ring II inlet communication port N, the sample gas inlet II O is communicated with the sample gas outlet II P, and the quantitative ring III inlet communication port Q is communicated with the carrier gas IV inlet R; the inlet communication port S of the chromatographic column II is communicated with the outlet communication port T of the quantitative ring III.
The carrier gas I18 and the carrier gas II 20 entering the carrier gas I inlet A and the carrier gas II inlet H are H 2 Where H supplementation is required in the methanator 2 Is directly supplied by carrier gas, so that CO and H 2 Methane is generated by the reaction, and then enters the FID detector I for detection; the carrier gas III 21 and the carrier gas IV 23 entering the carrier gas III inlet L and the carrier gas IV inlet R are H 2 Or N 2 One of them.
The FID detector II 16 is connected with a purging pipeline, one end of the purging pipeline is connected with an inlet of the FID detector, and the other end of the purging pipeline is provided with an inlet of purging gas 24. The purge gas 24 is N 2 。
The detection method for the chromatographic analysis of the impurity components in the food-grade carbon dioxide comprises the following steps of:
(1) When the ten-way valve I and the ten-way valve II are in an initial state, sample gas enters the ten-way valve I and the ten-way valve II through the sample gas inlet I and the sample gas inlet II respectively, so that the quantitative ring I, the quantitative ring II and the quantitative ring III are filled with the sample gas;
under this step, once advance the sample back, the sample gas gets into gas chromatography device, then is divided into sample gas I19 and sample gas II 22 and gets into ten-way valve I and ten-way valve II respectively simultaneously, and wherein the air current circulation process of sample gas I19 is: sample gas I19 enters the ten-way valve I from the sample gas inlet IC, then enters the quantitative ring I7 from the quantitative ring I inlet communication port B, then enters the ten-way valve I from the quantitative ring I outlet communication port E, and finally is discharged from the sample gas I output end 26 from the sample gas outlet ID.
The air flow process of the sample gas II 22 is as follows: sample gas II 22 enters the ten-way valve II from the sample gas inlet O, then enters the quantitative ring II 8 from the quantitative ring II inlet communication port N, then enters the ten-way valve II from the quantitative ring II outlet communication port K, then enters the quantitative ring III 10 from the quantitative ring III inlet communication port T, then enters the ten-way valve II from the quantitative ring III outlet communication port Q, and finally comes out from the sample gas outlet II P to be discharged from the sample gas II output end 29.
So that the sample gas fills the quantitative ring I, the quantitative ring II and the quantitative ring III, and the carrier gas enters the quantitative ring I, the quantitative ring II and the quantitative ring III for detection.
(2) Instantaneously rotating the ten-way valve I and the ten-way valve II to enable the ten-way valve I and the ten-way valve II to be positionedIn the working state, after the carrier gas I enters the ten-way valve I from the carrier gas inlet I, the sample gas in the pushing quantitative ring I sequentially enters the chromatographic column I, the resistance column I and the methane converter, finally reaches the FID detector I, and detects the sample gas to be detected at the FID detector I to obtain CO and CH 4 Is a peak of (2); meanwhile, after the carrier gas III enters the ten-way valve II from the carrier gas inlet III, pushing sample gas in the quantitative ring II to sequentially enter the capillary split-flow sample injector and the chromatographic column III, and finally reaching the FID detector II, and detecting a sample to be detected by the FID detector II to obtain peaks of benzene, methanol, acetaldehyde, vinyl chloride and ethylene oxide; meanwhile, after the carrier gas IV enters the ten-way valve II from the carrier gas inlet IV, the sample gas in the pushing quantitative ring III enters the chromatographic column II for separation and then reaches the FID detector I, the sample gas to be detected is detected by the FID detector I, the peak of total hydrocarbon is obtained, and finally the gas chromatogram is obtained.
Under this step, carrier gas I, carrier gas III and carrier gas IV get into simultaneously and carry out the propelling movement to the sample gas, and wherein the gas circuit circulation process of carrier gas I18 is: the carrier gas I enters the ten-way valve I from the carrier gas I inlet A, then enters the quantitative ring I7 from the quantitative ring I inlet communication port B, enters the ten-way valve I from the quantitative ring I outlet port E, then enters the chromatographic column I2 from the chromatographic column I inlet communication port F, then enters the ten-way valve I from the chromatographic column I outlet communication port I, then enters the resistance column I from the resistance column I communication port J, then enters the methane converter, finally enters the FID detector I for detection, methane and CO are separated in the chromatographic column I in sequence, the CO is quickly converted into methane in the methane converter, the methane directly passes through the methane converter and then is detected by the FID detector I, and the peak of the CO and the methane is sequentially output.
The gas path circulation process of the carrier gas III 21 is as follows: the carrier gas III 21 enters the ten-way valve II from the carrier gas III inlet L, then enters the quantitative ring II 8 from the quantitative ring II outlet communication port K, then enters the ten-way valve II from the quantitative ring II inlet communication port N, then enters the capillary shunt sampler 15 from the capillary shunt sampler communication port M, is split, then part of carrier gas III pushes sample gas to enter the chromatographic column III, finally enters the FID detector II for detection, and benzene, methanol, acetaldehyde, vinyl chloride and ethylene oxide can be detected, namely peaks of the benzene, the methanol, the acetaldehyde, the vinyl chloride and the ethylene oxide appear at different peak-out times.
The gas path circulation process of the carrier gas IV 23 comprises the following steps: the carrier gas IV enters the ten-way valve II from the carrier gas IV inlet R, then enters the quantitative ring III from the quantitative ring III outlet communication port Q, then enters the ten-way valve II from the quantitative ring III inlet communication port T, then enters the chromatographic column II from the chromatographic column II inlet communication port S, and finally enters the FID detector I for detection, and the peak of total hydrocarbon is obtained.
At this time, the carrier gas II 20 directly comes out from the connecting port of the resistance column II 6 after entering the carrier gas II inlet H, and then is emptied through the resistance column II, so as to obtain the emptying gas 25.
(3) When CO and CH are present 4 The ten-way valve I is instantaneously rotated after the peak of the pressure sensor, and is in an initial state at the moment, and the carrier gas II enters the ten-way valve I through the carrier gas inlet II and passes through the chromatographic column I and the resistance column II so as to treat high-content CO 2 And (5) evacuating.
Under this step, the gas path circulation process of the carrier gas II is as follows: the carrier gas II enters the ten-way valve I from the carrier gas II inlet H, then enters the chromatographic column I from the chromatographic column I outlet communication port I, then enters the ten-way valve I from the chromatographic column I inlet communication port F, then enters the resistance column II from the resistance column communication port G, finally is emptied through the resistance column II, and thus the high-content CO in the chromatographic column I is discharged 2 Evacuation to avoid CO 2 Damaging the methanator.
The gas chromatography analysis conditions of the invention are as follows: the sample inlet temperature was 200deg.C, the column box temperature was 60deg.C, the FID detector I and the FID detector II temperatures were 230deg.C, and the carrier gas flow rate was 30 mL/min.
Finally, it should be noted that the above-mentioned examples of the present invention are only illustrative of the present invention and are not limiting of the embodiments of the present invention. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. Not all embodiments are exhaustive. Obvious changes and modifications which are extended by the technical proposal of the invention are still within the protection scope of the invention.
Claims (6)
1. The chromatographic analysis device for the impurity components in the food-grade carbon dioxide is characterized by comprising a ten-way valve I, a ten-way valve II, an FID detector I, an FID detector II, a methane converter, a quantitative ring I, a quantitative ring II and a quantitative ring III, and a chromatographic column I, a resistance column II, a chromatographic column II and a chromatographic column III;
the ten ports of the ten-way valve I are a sample gas inlet I, a quantitative ring I inlet communication port, a quantitative ring I outlet communication port, a chromatographic column I inlet communication port, a chromatographic column I outlet communication port, a resistance column I communication port, a resistance column II communication port, a carrier gas I inlet, a carrier gas II inlet and a sample gas outlet I;
the quantitative ring I inlet is communicated with the quantitative ring I inlet communication port, and the quantitative ring I outlet is communicated with the quantitative ring I outlet communication port; the two ends of the chromatographic column I are respectively communicated with an inlet communication port of the chromatographic column I and an outlet communication port of the chromatographic column I; one end of the resistance column I is communicated with the communication port of the resistance column I, and the other end of the resistance column I is communicated with the inlet of the methane converter; the outlet of the methane converter is communicated with the FID detector I; one end of the resistance column II is communicated with the communication port of the resistance column II, and the other end of the resistance column II is connected with an emptying pipeline;
the ten ports of the ten-way valve II are a sample gas inlet II, a quantitative ring II inlet communication port, a quantitative ring II outlet communication port, a quantitative ring III inlet communication port, a quantitative ring III outlet communication port, a chromatographic column II inlet communication port, a chromatographic column III communication port, a carrier gas III inlet, a carrier gas IV inlet and a sample gas outlet II;
the quantitative ring II inlet is communicated with the quantitative ring II inlet communication port, and the quantitative ring II outlet is communicated with the quantitative ring II outlet communication port; the quantitative ring III inlet is communicated with the quantitative ring III inlet communication port, and the quantitative ring III outlet is communicated with the quantitative ring III outlet communication port; one end of the chromatographic column II is communicated with the inlet communication port of the chromatographic column II, and the other end of the chromatographic column II is communicated with the FID detector I; one end of the chromatographic column III is communicated with the chromatographic column III communication port, and the other end of the chromatographic column III is communicated with the FID detector II;
the carrier gas I and the carrier gas II entering the carrier gas I inlet and the carrier gas II inlet are H 2 The method comprises the steps of carrying out a first treatment on the surface of the The carrier gas III and the carrier gas IV entering the carrier gas III inlet and the carrier gas IV inlet are H 2 Or N 2 One of the following;
the FID detector II is connected with a purging pipeline, one end of the purging pipeline is connected with an inlet of the FID detector, and the other end of the purging pipeline is a purging gas inlet.
2. The chromatographic analysis device for impurity components in food-grade carbon dioxide according to claim 1, wherein the chromatographic column III is a capillary chromatographic column, a capillary shunt sample injector is arranged between the capillary chromatographic column and the ten-way valve II, an inlet of the capillary shunt sample injector is communicated with a communication port of the chromatographic column III, an outlet of the capillary shunt sample injector is provided with three pipelines, and a spacer purge regulating valve is arranged on a first pipeline; a shunt adsorption trap is arranged on the second pipeline, one end of the shunt adsorption trap is communicated with the capillary shunt sampler, and a shunt regulating valve is arranged on the pipeline at the outlet end of the shunt adsorption trap; the third pipeline is communicated with one end of the chromatographic column III.
3. The chromatographic analysis device for impurity components in food grade carbon dioxide according to claim 2, wherein when the ten-way valve i and the ten-way valve ii are in the initial state, the connection state of the ten-way valve i is: the quantitative ring I inlet communication port is communicated with the sample gas inlet I, the sample gas outlet I is communicated with the quantitative ring I outlet communication port, the chromatographic column I inlet communication port is communicated with the resistance column II communication port, the carrier gas II inlet is communicated with the chromatographic column I outlet communication port, and the resistance column I communication port is communicated with the carrier gas I inlet; communication state of ten-way valve II: the inlet of the carrier gas III is communicated with the communication port of the capillary split-flow sample injector, the inlet of the quantitative ring II is communicated with the inlet of the sample gas II, the outlet of the sample gas II is communicated with the inlet of the quantitative ring III, the inlet of the carrier gas IV is communicated with the inlet of the chromatographic column II, and the outlet of the quantitative ring III is communicated with the outlet of the quantitative ring II;
when the ten-way valve I and the ten-way valve II are in the working state, the communication state of the ten-way valve I is as follows: the inlet of the carrier gas I is communicated with the inlet communication port of the quantitative ring I, the sample gas inlet I is communicated with the sample gas outlet I, the outlet communication port of the quantitative ring I is communicated with the inlet communication port of the chromatographic column I, the outlet communication port of the resistance column II is communicated with the inlet communication port of the carrier gas II, and the outlet communication port of the chromatographic column I is communicated with the outlet communication port of the resistance column I; communication state of ten-way valve II: the quantitative ring II outlet communication port is communicated with the carrier gas III inlet, the capillary split-flow sample injector communication port is communicated with the quantitative ring II inlet communication port, the sample gas inlet II is communicated with the sample gas outlet II, and the quantitative ring III inlet communication port is communicated with the carrier gas IV inlet; the inlet communication port of the chromatographic column II is communicated with the outlet communication port of the quantitative ring III.
4. The apparatus for chromatographic analysis of impurity components in food grade carbon dioxide according to claim 1, wherein said purge gas is N 2 。
5. A method for detecting a chromatographic analysis of an impurity component in food-grade carbon dioxide, characterized by comprising the steps of:
(1) When the ten-way valve I and the ten-way valve II are in an initial state, sample gas enters the ten-way valve I and the ten-way valve II through the sample gas inlet I and the sample gas inlet II respectively, so that the quantitative ring I, the quantitative ring II and the quantitative ring III are filled with the sample gas;
(2) The ten-way valve I and the ten-way valve II are instantaneously rotated to enable the ten-way valve I and the ten-way valve II to be in a working state, after the carrier gas I enters the ten-way valve I from the carrier gas inlet I, the sample gas in the push quantitative ring I sequentially enters the chromatographic column I, the resistance column I and the methane converter, finally reaches the FID detector I, detects the sample gas to be detected at the FID detector I, and outputs CO and CH 4 Is a peak of (2); meanwhile, after the carrier gas III enters the ten-way valve II from the carrier gas inlet III, pushing sample gas in the quantitative ring II to sequentially enter the capillary split-flow sample injector and the chromatographic column III, and finally reaching the FID detector II, and detecting a sample to be detected by the FID detector II to obtain peaks of benzene, methanol, acetaldehyde, vinyl chloride and ethylene oxide; meanwhile, after the carrier gas IV enters the ten-way valve II from the carrier gas inlet IV, the sample gas in the pushing quantitative ring III enters the chromatographic column II for separation and then reaches the FID detector I, the sample gas to be detected is detected by the FID detector I, the peak of total hydrocarbon is obtained, and finally the gas chromatogram is obtained.
6. The method for detecting the chromatographic analysis of an impurity component in food grade carbon dioxide as claimed in claim 5, further comprising the step of (3) extracting CO and CH 4 The ten-way valve I is instantaneously rotated after the peak of the pressure sensor, and is in an initial state at the moment, and the carrier gas II enters the ten-way valve I through the carrier gas inlet II and passes through the chromatographic column I and the resistance column II so as to treat high-content CO 2 And (5) evacuating.
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