CN115184505B - Method for detecting nitrosamine in gas - Google Patents
Method for detecting nitrosamine in gas Download PDFInfo
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- CN115184505B CN115184505B CN202210876877.1A CN202210876877A CN115184505B CN 115184505 B CN115184505 B CN 115184505B CN 202210876877 A CN202210876877 A CN 202210876877A CN 115184505 B CN115184505 B CN 115184505B
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- nitrosamine
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- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 238000001514 detection method Methods 0.000 claims abstract description 37
- 239000003480 eluent Substances 0.000 claims abstract description 29
- 239000003463 adsorbent Substances 0.000 claims abstract description 28
- ZKXDGKXYMTYWTB-UHFFFAOYSA-N N-nitrosomorpholine Chemical compound O=NN1CCOCC1 ZKXDGKXYMTYWTB-UHFFFAOYSA-N 0.000 claims abstract description 15
- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 claims abstract description 15
- YGJHZCLPZAZIHH-UHFFFAOYSA-N N-Nitrosodi-n-butylamine Chemical compound CCCCN(N=O)CCCC YGJHZCLPZAZIHH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 11
- -1 nitrosamine compound Chemical class 0.000 claims abstract description 11
- 238000012856 packing Methods 0.000 claims abstract description 11
- YLKFDHTUAUWZPQ-UHFFFAOYSA-N N-Nitrosodi-n-propylamine Chemical compound CCCN(N=O)CCC YLKFDHTUAUWZPQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- WNYADZVDBIBLJJ-UHFFFAOYSA-N N-Nitrosopyrrolidine Chemical compound O=NN1CCCC1 WNYADZVDBIBLJJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- WBNQDOYYEUMPFS-UHFFFAOYSA-N N-nitrosodiethylamine Chemical compound CCN(CC)N=O WBNQDOYYEUMPFS-UHFFFAOYSA-N 0.000 claims abstract description 9
- UWSDONTXWQOZFN-UHFFFAOYSA-N N-nitrosopiperidine Chemical compound O=NN1CCCCC1 UWSDONTXWQOZFN-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTDCJKARQCRONF-UHFFFAOYSA-N N-Nitrosomethylethylamine Chemical compound CCN(C)N=O RTDCJKARQCRONF-UHFFFAOYSA-N 0.000 claims abstract description 5
- AUIKJTGFPFLMFP-UHFFFAOYSA-N n,n-di(propan-2-yl)nitrous amide Chemical compound CC(C)N(N=O)C(C)C AUIKJTGFPFLMFP-UHFFFAOYSA-N 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 84
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 78
- 239000007789 gas Substances 0.000 claims description 42
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 38
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 38
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 35
- 150000004005 nitrosamines Chemical class 0.000 claims description 31
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- 229910010272 inorganic material Inorganic materials 0.000 claims description 17
- 239000011147 inorganic material Substances 0.000 claims description 17
- 238000007789 sealing Methods 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 16
- 239000000945 filler Substances 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 238000010828 elution Methods 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 235000006708 antioxidants Nutrition 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical group [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 3
- 238000011084 recovery Methods 0.000 abstract description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000012086 standard solution Substances 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000004364 calculation method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052751 metal Chemical class 0.000 description 6
- 239000002184 metal Chemical class 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 4
- 102100031650 C-X-C chemokine receptor type 4 Human genes 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 101000922348 Homo sapiens C-X-C chemokine receptor type 4 Proteins 0.000 description 3
- 101000603386 Homo sapiens Neuropeptide Y receptor type 1 Proteins 0.000 description 3
- 101000603420 Homo sapiens Nuclear pore complex-interacting protein family member A1 Proteins 0.000 description 3
- 241000208125 Nicotiana Species 0.000 description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 3
- 102100038845 Nuclear pore complex-interacting protein family member A1 Human genes 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 229940116318 copper carbonate Drugs 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 3
- 239000011654 magnesium acetate Substances 0.000 description 3
- 235000011285 magnesium acetate Nutrition 0.000 description 3
- 229940069446 magnesium acetate Drugs 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 210000004907 gland Anatomy 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HVBDBNBRWGIRLT-UHFFFAOYSA-N 4-nitrosoprocainamide Chemical compound CCN(CC)CCNC(=O)C1=CC=C(N=O)C=C1 HVBDBNBRWGIRLT-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- KQVJFBVOFSJAAS-UHFFFAOYSA-N N,N-dimethylnitrous amide Chemical compound CN(C)N=O.CN(C)N=O KQVJFBVOFSJAAS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- PVZKCUMEASBUMM-UHFFFAOYSA-N n,n-diethylnitrous amide Chemical compound CCN(CC)N=O.CCN(CC)N=O PVZKCUMEASBUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The application relates to a detection method of nitrosamine in gas, which comprises the following steps: (1) Providing an adsorption column loaded with an adsorbent packing and a catalyst; (2) Adding a gas to be detected into the adsorption column of the step (1), eluting to obtain an eluent; (3) Detection is carried out by utilizing gas chromatography mass spectrometry to obtain the existence and/or the existence quantity of the nitrosamine. In the present application, the nitrosamine compound includes: n-nitrosodimethylamine, N-nitrosomethylethylamine, N-nitrosodiethylamine, N-nitrosodiisopropylamine, N-nitrosopyrrolidine, N-nitrosodipropylamine, N-nitrosomorpholine, N-nitrosopiperidine, N-nitrosodi-N-butylamine. The method of the application is ideal in the aspects of recovery rate, detection limit, precision and the like, and has the advantages of short detection time, high efficiency and low cost.
Description
Technical Field
The application relates to the technical field of detection of pollutants in gas, in particular to a detection method of nitrosamine compounds in gas.
Background
Nitrosamines are a class of highly carcinogenic organic substances widely existing in food, cosmetics, medicines, tobacco, industrial wastewater, and nitrosamines are also detected in tap water and river water in recent years. In addition, nitrosamines are also present in the air during the production of tobacco smoke, rubber and its products, as well as in the air-polluting particles. Because of the wide range and hazard of the nitrosamine compounds, nitrosamine compounds are brought into the supervision range in various countries, and people are required to continuously search for more advanced, sensitive and low-cost detection methods.
The existing methods for detecting nitrosamine compounds mainly comprise Gas Chromatography (GC), gas chromatography-mass spectrometry (GC-MS), liquid Chromatography (LC), liquid chromatography-mass spectrometry (LC-MS/MS), ultraviolet absorption method, colorimetry, thin layer chromatography and the like.
Although the gas chromatography-thermal energy analysis method (GC-TEA) has high sensitivity and accuracy, the TEA is quite expensive, and can be basically only used for detecting nitrosamine compounds, and has strong specificity and high detection cost.
The liquid chromatograph is simple to operate and low in cost, but nitrosamine can be degraded under the ultraviolet irradiation condition, and detection of nitrosamine by using an ultraviolet detector can cause larger result error, and the liquid chromatograph and the thermal energy analyzer are combined to detect nitrosamine and also can encounter the same problems of GC-TEA.
LC-MS/MS has the advantages of simple operation, high sensitivity and low detection limit, is widely applied to detection of nitrosamine in tobacco at present, is not too much in researches on food, water, cosmetics and the like, and is an important reason for limiting development of the LC-MS/MS due to high price.
At present, the GC-MS method for determining nitrosamines in air has few documents and patent researches.
In the literature Efficient sampling and determination of airborne N-nitrosamines by Needle Trap device coupled with gas chromatography-mass spectrometry (CHEN X, YANG S, HU Q, et al Efficient sampling and determination of airborne N-nitrosamines by Needle Trap device coupled with gas chromatography-mass spectrometry [ J/OL ]. Microchemical Journal,2018, 139:480-486.), a method of dynamic Needle Trap (Needle Trap) sampling in combination with GC-MS for determining 4 volatile nitrosamines is disclosed. Wherein, the needle point of the dynamic needle trapping device is filled with an adsorbent, and the adsorbent uses a carbon molecular sieve Carboxen1000. During analysis, a trapping needle is used to sample from the gas sampling bag, and then a needle is inserted into the sample inlet of the gas chromatograph for analysis. The literature only measures NDMA, NDEA, NOPA, NDBA and cannot be extended to other types of nitrosamines.
CN114073936a discloses an adsorbent for enriching nitrosamines in air, which is formed by mixing an inorganic material and an antioxidant, wherein the inorganic material is an inorganic material modified by a metal oxide or a metal salt. The inorganic material is diatomite, silicon dioxide, zeolite or molecular sieve. The metal salt is magnesium sulfate, magnesium acetate, calcium chloride, calcium carbonate or basic copper carbonate, and the metal oxide is magnesium oxide, calcium oxide or copper oxide. The antioxidant is metabisulfite, sulfamic acid or ascorbic acid. Nine nitrosamines were also tested, but improvements in recovery and stability of the test were needed, as well as further exclusion of false positives.
At present, the detection of the nitrosamine in the air does not have national standard or industry standard, and similar to the detection of the nitrosamine in the air, for example, HJ734-2014 or GB/T29669-2013, can not be applied to the detection of the nitrosamine in the air.
In the national environmental protection standard HJ734-2014, solid phase adsorption-thermal desorption gas chromatography-mass spectrometry for determination of fixed pollution source waste gas-volatile organic matters, an adsorption tube is adopted for sampling, and then detection is carried out by a thermal desorption device-gas chromatography-mass spectrometer. The adsorption tube filler adopts carbon molecular sieve Carboxen1000 as adsorbent.
In the recommended national standard GB/T29669-2013 (determination of 10 volatile nitrosamines such as N-nitrosodimethylamine in cosmetics-mass spectrometry/mass spectrometry), a sample is extracted by a solvent, purified by a solid-phase extraction column, and then determined by a gas chromatograph-mass spectrometer. Pretreatment is complex and cannot be applied to detection of nitrosamines in air.
The prior art is directed to detection of volatile organic compounds, detection of nitrosamines in solids and liquids, or complex pretreatment processes and high cost. Therefore, a low-cost, convenient and effective detection method for the nitrosamine in the air needs to be established, and the detection method is better applied to the detection of the nitrosamine in the air and overcomes the defect that no corresponding standard exists in China.
Disclosure of Invention
The application aims to provide a method for detecting nitrosamine in gas, which is low in cost, convenient and efficient.
In order to achieve the above object, the present application provides a method for detecting a nitrosamine compound in a gas, the method comprising:
(1) Providing an adsorption column loaded with an adsorbent packing and a catalyst; the adsorbent filler is a mixture of inorganic materials and antioxidants; the catalyst is sulfamic acid and sodium bisulfate;
(2) Adding a gas to be detected into the adsorption column of the step (1), eluting to obtain an eluent;
(3) Detection is carried out by utilizing gas chromatography mass spectrometry to obtain the existence and/or the existence quantity of the nitrosamine.
The detection method of the application can realize the detection of at least 9 nitrosamines at one time, and comprises the following steps: n-nitrosodimethylamine, N-nitrosomethylethylamine, N-nitrosodiethylamine, N-nitrosodiisopropylamine, N-nitrosopyrrolidine, N-nitrosodi-N-propylamine, N-nitrosomorpholine, N-nitrosopiperidine and/or N-nitrosodi-N-butylamine.
In the present application, the gas to be measured includes (but is not limited to): air, exhaust gas, industrial waste gas, gas in a vehicle, or the like, or it may be converted from a liquid or solid into a gas by gasification or the like.
As a preferred mode of the present application, in the step (1), the amount of the catalyst is: every 0.4g of adsorbent packing corresponds to: sulfamic acid 30 mg+ -10 mg, sodium bisulfate 10 mg+ -3 mg.
As a preferred mode of the present application, in the step (1), the amount of the catalyst is: every 0.4g of adsorbent packing corresponds to: sulfamic acid 30 mg+ -6 mg, sodium bisulfate 10 mg+ -2 mg.
As a preferred embodiment of the present application, in the adsorbent packing of step (1), the inorganic material is a metal oxide or metal salt modified inorganic material.
As a preferred mode of the present application, the inorganic material is diatomaceous earth, silica, zeolite or molecular sieve.
As a preferred mode of the present application, the metal salt is magnesium sulfate, magnesium acetate, calcium chloride, calcium carbonate, sodium sulfate or basic copper carbonate.
As a preferred embodiment of the present application, the metal oxide is magnesium oxide, calcium oxide, or copper oxide.
As a preferred mode of the present application, the antioxidant is metabisulfite, sulfamic acid or ascorbic acid.
As a preferable mode of the application, the inorganic material and the antioxidant are mixed according to the mass ratio of 1-5:0.01-0.1; preferably, the 1 to 5 includes 2 to 5, 3 to 5, 4 to 5, 2 to 4,3 to 4, 2 to 3, etc.; preferably, the 0.01 to 0.1 includes 0.02 to 0.09, 0.03 to 0.08, 0.04 to 0.07, 0.05 to 0.06, etc.
As a preferred mode of the application, the method comprises the steps of preparing an adsorption column, preprocessing a sample and measuring the sample by using a gas chromatography mass spectrometer.
As a preferred mode of the present application, the preparation of the adsorption column comprises the following steps:
selecting a pure black low-background polypropylene material with a light-shielding effect as a column tube;
selecting a stainless steel screen or a silica gel screen plate as a sealing piece of the air inlet end of the column tube, selecting a silica gel screen plate or a cotton piece as a sealing piece of the air outlet end of the column tube, preferably, the sealing piece needs to meet the detection of no nitrosamine, and preferably, the sieve holes of the sealing piece of the air outlet end are not larger than those of the sealing piece of the air inlet end;
loading a sealing element at the air inlet end to the adsorption column tube, preferably pressing a glass rod into the bottom, wherein the sealing element at the air inlet end is a stainless steel screen or a silica gel screen plate;
loading an adsorbent pack into the column, preferably tapping the table top;
loading a catalyst into the column tube, wherein the catalyst consists of sulfamic acid and sodium bisulfate;
putting a sealing element at the air outlet end, and flattening, wherein the sealing element at the air outlet end is a silica gel sieve plate or a cotton sheet;
the top cap is pressed into the adsorption column, preferably also sealed.
In a preferred embodiment of the present application, the adsorption column is stored in a sealed and light-proof state after being packed.
As a preferred mode of the application, the pressure resistance test is carried out on the adsorption column, so that the pressure can be ensured to meet the use requirement of a conventional sucking pump in a laboratory.
As a preferred mode of the present application, a sample pretreatment step is further included, if necessary; preferably, the sample pretreatment comprises the following steps:
and a single-path control purging carrier gas device is adopted to gasify and purge the liquid nitrosamine mixed standard solution and collect the liquid nitrosamine mixed standard solution by using an adsorption column, and the purging flow rate can ensure that each path can respectively purge at 500 mL/min.
Specifically, a gas phase sample injection needle is used for moving and taking the mixed standard solution, the mixed standard solution is placed at the front end of a column tube of an adsorption column, then the air inlet end of the adsorption column is connected with an aging instrument purged by nitrogen, the air outlet end of the adsorption column is connected with a flowmeter, the purging flow rate is adjusted to 500ml/min, and the mixed standard solution is purged for 8 hours, so that the solution is gasified and then enters the adsorption column for collection.
Eluting the adsorption column by using an eluent, wherein the eluent is prepared by mixing n-hexane, dichloromethane, acetone, isopropanol and methanol according to different proportions, and the preferred combination of the eluent comprises dichloromethane, acetone (1:1), dichloromethane, acetone (1:4), dichloromethane, acetone (4:1), n-hexane, acetone (1:1) and isopropanol, acetone (1:1).
And filtering the eluent by using a PTEE organic phase filter to obtain a sample to be measured for on-machine measurement.
As a preferred mode of the application, the method further comprises a sample pretreatment step during actual air sample detection; preferably, the sample pretreatment comprises the following steps:
the air outlet end of the adsorption column is connected to the air sampling pump, the flow rate is set, the sampling time is recorded, and the air sample collection work can be completed.
Eluting the adsorption column by using an eluent, wherein the eluent is prepared by mixing n-hexane, dichloromethane, acetone, isopropanol and methanol according to different proportions, and the preferred combination of the eluent comprises dichloromethane, acetone (1:1), dichloromethane, acetone (1:4), dichloromethane, acetone (4:1), n-hexane, acetone (1:1) and isopropanol, acetone (1:1).
And filtering the eluent by using a PTEE organic phase filter to obtain a sample to be measured for on-machine measurement.
As a preferred mode of the present application, the gas chromatography mass spectrometer analysis method comprises:
(1) Gas chromatography mass spectrometer: TRACE1300-ISQ7000;
(2) Chromatographic column: CD-624,30mx0.25mmx1.4 μm;
(3) Sample inlet temperature: 220 ℃;
(4) Sample injection mode: split sample injection, split ratio 10:1, a step of;
(5) Carrier gas: helium gas; the control mode is as follows: constant current; flow rate: 1.0mL/min;
(6) Heating program: the initial temperature is 50 ℃, kept for 3min, and is raised to 120 ℃ at 20 ℃/min, kept for 2min, raised to 140 ℃ at 3 ℃/min, kept for 1min, raised to 160 ℃ at 20 ℃/min, and kept for 5min;
(7) Sample injection amount: 1 μl;
(8) Transmission line temperature: 250 ℃;
(9) Ion source temperature: 250 ℃;
(10) Ionization mode: electron bombardment ionization (EI);
(11) Solvent delay time: 6min;
(12) Scanning mode: full scan (30-450);
although there are various methods for detecting a target compound in the art (for example, GC-TEA is currently mostly used for gaseous nitrosamines), a gas chromatograph-mass spectrometer (GC-MS) is preferably used in the present application. The inventor discovers that for the target compound, namely the nitrosamine compound, the method is an effective and efficient method, and the target compound and the interfering substance are separated through gas chromatography and qualitatively and quantitatively analyzed through mass spectrum, so that the nitrosamine can be detected rapidly, accurately and simply, and the accuracy and the sensitivity are improved. The method of the present application is less costly than GC-TEA and LC-MS/MS based detection techniques and does not require the use of expensive reagents or other consumables.
In one embodiment, the use of a catalyst increases recovery.
In one embodiment, the amount of the catalyst is verified and analyzed to obtain the optimal proportioning range of the catalyst: every 0.4g of the filler, the dosage of sulfamic acid is 30 mg+/-6 mg, and the dosage of sodium bisulfate is 10 mg+/-2 mg.
In one embodiment, the elution effect of different combinations of eluents is verified, the combination comprises n-hexane, dichloromethane, acetone, isopropanol and methanol, the eluents are obtained by mixing according to different proportions, and the preferred combination of the eluents comprises dichloromethane: acetone (1:1), dichloromethane: acetone (1:4), dichloromethane: acetone (4:1), n-hexane: acetone (1:1) and isopropanol: acetone (1:1).
Compared with the prior art, the detection method provided by the application simplifies the pretreatment process, and the whole detection process can be carried out by only adopting a nitrosamine adsorption column to adsorb and collect a gas sample and then eluting the gas sample. The operation process is simple, and the detection time and cost are greatly saved. Meanwhile, through the use of the catalyst, the interference of impurities is shielded, so that nitrosamine is mainly adsorbed when an adsorption column adsorbs, adsorption sites cannot be occupied by other substances, the adsorption selectivity of nitrosamine compounds is improved, and the recovery rate is remarkably improved. The impurity doping is reduced, so that the interference on the target object is reduced, the experimental error is reduced, and the sensitivity and the accuracy of detection are improved.
Drawings
The application may be better understood by describing embodiments thereof in conjunction with the accompanying drawings, in which:
FIG. 1 is a SIM profile of a 500ppb nitrosamine standard;
FIG. 2 is a comparison of recovery for various sodium bisulfate dosages at a fixed sulfamic acid dosage;
FIG. 3 is a comparison of recovery for different amounts of sulfamic acid at fixed sodium bisulfate usage;
FIG. 4 is the effect of different eluents on recovery.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be clearly described below with reference to specific embodiments of the present application and corresponding drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1Method for detecting 9 nitrosamines in air
In this example, the detection of 9 nitrosamines in air was performed, comprising the steps of:
1. instrument and reagent
(1) Instrument for measuring and controlling the intensity of light
Siemens femtocells Trace1300-ISQ7000 gas chromatograph-mass spectrometer (GCMS);
six-bit single-flow control aging instrument;
and a column pipe gland device.
(2) Reagent and consumable
Dichloromethane, acetone, methanol, 10ul sample injection needle, pipette, gun head, PTFE needle filter, sample injection vial, bottle cap, and syringe.
2. Nitrosamine standard solution
Information of the 9 types of nitrosamine compound standard substances is shown in table 1.
Tables 1 and 9 types of nitrosamine Compound Standard substances
| Chinese name of compound | English name of the Compound | Abbreviations (abbreviations) | CAS No. |
| N-nitrosodimethylamine | N-nitrosodimethylamine | NDMA | 62-75-9 |
| N-nitrosomethylethylamine | N-nitrosomethylethylamine | NMEA | 10595-95-6 |
| N-nitrosodiethylamine | N-nitrosodiethylamine | NDEA | 55-18-5 |
| N-nitrosodiisopropylamine | N-nitrosodiisopropylamine | NDiPA | 601-77-4 |
| N-nitrosopyrrolidines | N-nitrosopyrollidine | NPYR | 930-55-2 |
| N-nitrosodi-N-propylamine | N-nitrosodipropylamine | NDPA | 621-64-7 |
| N-nitrosomorpholines | N-nitrosoMorpholine | NMOR | 59-89-2 |
| N-nitrosopiperidine | N-nitrosopiperidine | NPIP | 100-75-4 |
| N-nitrosodi-N-butylamine | N-nitrosodibutylamine | NDBA | 924-16-3 |
The SIM spectrum of the 500ppb nitrosamine standard is shown in FIG. 1.
3. Adsorbent and adsorption column preparation
The adsorbent filler is formed by mixing an inorganic material and an antioxidant, wherein the inorganic material is a metal oxide or metal salt modified inorganic material. The inorganic material and the antioxidant are mixed according to the mass ratio of 1-5:0.01-0.1. The inorganic material is diatomite, silicon dioxide, zeolite or molecular sieve. The metal salt is magnesium sulfate, magnesium acetate, calcium chloride, calcium carbonate, sodium sulfate or basic copper carbonate. The metal oxide is magnesium oxide, calcium oxide or copper oxide. The antioxidant is metabisulfite, sulfamic acid or ascorbic acid. Specifically, when the column packing is carried out subsequently, the applied adsorbent filler takes a molecular sieve as an inorganic material and pyrosulfite as an antioxidant, and the mass ratio of the molecular sieve to the pyrosulfite is 50:1, mixing to obtain the adsorbent filler.
Through experimental analysis for a wide variety of catalysts, the inventors determined that a combination of sulfamic acid and sodium bisulfate was utilized as the catalyst for the present application. The adsorption column was prepared as follows:
(1) Selecting a pure black low-background polypropylene material with a light-shielding effect as a column tube;
(2) Filling a silica gel sieve plate into the adsorption column tube, and pressing the silica gel sieve plate into the bottom of the adsorption column tube by using a glass rod, wherein the volume of the column tube is 1mL;
(3) Weighing 0.8g of the adsorbent filling material by a balance, filling the adsorbent filling material into the column tube, and tapping a tabletop;
(4) Filling a catalyst into the column tube, wherein the catalyst consists of sulfamic acid and sodium bisulfate, and the dosage of the sulfamic acid is 30mg and the dosage of the sodium bisulfate is 10mg for each 0.4g of the adsorbent filling;
(5) Placing another silica gel sieve plate;
(6) Pressing the top cover into the adsorption column by using a gland device, and tightly screwing and sealing the two ends of the adsorption column by using luer sealing caps; when in storage, the assembled column is sealed by an aluminum foil bag.
4. Sample pretreatment
(1) Mixing the standard solution: 500ppm of 9 kinds of nitrosamine mixed standard solution (each nitrosamine concentration is 500 ppm);
(2) Gasifying 4uL of the mixed standard solution and adsorbing and collecting the mixed standard solution by using an adsorption column;
specifically, a gas phase sample injection needle is used for moving and taking 4uL of mixed standard solution, the mixed standard solution is placed at the gas inlet end of the adsorption column, the gas inlet end of the adsorption column is connected with a nitrogen purging aging instrument, the gas outlet end of the adsorption column is connected with a flowmeter, the nitrogen purging flow rate is adjusted to 500ml/min, and the mixed standard solution is purged for 8 hours, so that the solution is gasified and then enters the adsorption column for adsorption collection.
(3) Eluting the adsorption column with 4mL of eluent, wherein the eluent is dichloromethane and acetone (1:1), and the flow rate is controlled to be 1-2 drops/second;
(4) And filtering the eluted solution through a PTFE organic phase filter to obtain a sample to be detected.
5. Analysis method of gas chromatography mass spectrometer
(1) Chromatographic column: CD-624,30mx0.25mmx1.4 μm;
(2) Sample inlet temperature: 220 ℃;
(3) Sample injection mode: split sample injection, split ratio 10:1, a step of;
(4) Carrier gas: helium gas; the control mode is as follows: constant current; flow rate: 1.0mL/min;
(5) Heating program: the initial temperature is 50 ℃, kept for 3min, and is raised to 120 ℃ at 20 ℃/min, kept for 2min, raised to 140 ℃ at 3 ℃/min, kept for 1min, raised to 160 ℃ at 20 ℃/min, and kept for 5min;
(6) Sample injection amount: 1 μl;
(7) Transmission line temperature: 250 ℃;
(8) Ion source temperature: 250 ℃;
(9) Ionization mode: electron bombardment ionization (EI);
(10) Solvent delay time: 6min;
(11) Scanning mode: full scan (30-450).
6. Analysis results
(1) Every 0.4g of the adsorbent filler, the dosage of sulfamic acid is 30mg, and the dosage of sodium bisulfate is 10mg; and the eluent adopts methylene dichloride and acetone (1:1). The retention times and detection limits for each of the 9 nitrosamines on GCMS are shown in table 2. As shown in Table 2, 9 gas nitrosamines were successfully detected using the present method. Compared with the prior art, the method not only can detect the gas nitrosamine, but also has the advantages of simple pretreatment steps, better quantitative lower limit and higher sensitivity. Other detection methods of nitrosamines at present can only achieve ng level.
Table 2, 9 nitrosamine retention times and LOD
(2) The column was used to compare a commercial brand of inlet column.
A certain commercial brand adsorption column is defined as a standard tube, and the adsorption column is a tube to be tested. Sample collection and elution were performed according to the same sample pretreatment step (step 4), and analytical tests were performed on the standard tube and the tube to be tested, and the recovery rates of the samples were compared and the precision was calculated. The calculation formula is as follows:
recovery calculation
X＝B/A*100％
Wherein X is recovery rate, A is sample peak area of standard tube treatment, and B is sample peak area of tube treatment to be detected.
Precision calculation
Y＝STDEV(B 1 /A+B 2 /A+…+Bn/A)/AVERAGE(B 1 /A+B 2 /A+…+Bn/A)*100％
Wherein Y is precision, A is the peak area of the sample processed by the standard tube, and B1 … Bn is the peak area of the sample processed by the tube to be detected.
Using the above method, tests of a plurality of batches of tubes to be tested were performed, and recovery rates and precision of 9 gas nitrosamine detection samples in the test results are shown in Table 3. As shown in the results of Table 3, the overall recovery rate of the 9 gas nitrosamines by the adsorption column is obviously better than that of the similar products.
Table 3 recovery and precision of samples obtained from 6 experiments
| Recovery rate | 1 | 2 | 3 | 4 | 5 | 6 | RSD |
| NDMA | 117.0％ | 118.1％ | 107.5％ | 105.7％ | 111.3％ | 98.0％ | 6.9％ |
| NEMA | 112.4％ | 128.3％ | 112.0％ | 117.7％ | 120.8％ | 100.4％ | 8.2％ |
| NDEA | 92.5％ | 146.7％ | 134.8％ | 130.6％ | 133.4％ | 113.2％ | 15.4％ |
| NDiPA | 82.6％ | 130.1％ | 114.4％ | 125.9％ | 121.5％ | 126.6％ | 15.1％ |
| NDPA | 88.9％ | 135.4％ | 116.9％ | 121.1％ | 116.3％ | 111.6％ | 13.2％ |
| NMOR | 94.8％ | 194.0％ | 166.2％ | 190.8％ | 147.2％ | 107.0％ | 27.9％ |
| NPYR | 99.2％ | 197.3％ | 174.3％ | 174.3％ | 158.0％ | 126.1％ | 23.3％ |
| NPIP | 90.3％ | 162.1％ | 138.2％ | 160.0％ | 119.9％ | 113.6％ | 21.5％ |
| NDBA | 83.4％ | 106.6％ | 92.8％ | 86.0％ | 91.0％ | 105.3％ | 10.3％ |
Example 2Comparison of catalyst technical effects
The difference in adsorption effect of the adsorption column without catalyst and with catalyst added was compared. In this example, the other conditions are as given in example 1, with the catalyst amounts: the amount of sulfamic acid used was 30mg and the amount of sodium bisulfate used was 10mg per 0.4g of the adsorbent filler. The eluent is methylene dichloride and acetone (1:1).
A certain commercial brand adsorption column is defined as a standard tube, and the adsorption column is a tube to be tested. Randomly extracting two batches of tubes to be tested, wherein one batch is free from catalyst, the other batch is free from catalyst, and sample collection and elution are carried out on the standard tube and the tubes to be tested according to the same sample pretreatment step (step 4), and analysis and test are carried out. The recovery of the samples was compared and the precision calculated. The calculation formula is as follows:
recovery calculation
No catalyst is added: x1=b1/a 100%;
adding a catalyst: x2=b2/a X100%
Wherein X1 and X2 are recovery rates, A is the sample peak area of the standard tube treatment, B1 is the sample peak area of the to-be-detected tube treatment without catalyst, and B2 is the sample peak area of the to-be-detected tube treatment with catalyst.
The adsorption effect obtained is shown in Table 4.
TABLE 4 influence of catalyst addition or absence on recovery
| Recovery rate | Without adding | Adding in |
| NDMA | 99.8％ | 117.0％ |
| NEMA | 99.4％ | 112.4％ |
| NDEA | 80.6％ | 92.5％ |
| NDiPA | 72.7％ | 82.6％ |
| NDPA | 74.8％ | 88.9％ |
| NMOR | 76.9％ | 94.8％ |
| NPYR | 81.4％ | 99.2％ |
| NPIP | 75.8％ | 90.3％ |
| NDBA | 71.6％ | 83.4％ |
As shown in the results of table 4, the adsorption column to which the catalyst was added had higher recovery rates of various nitrosamines and better overall adsorption performance than the adsorption column using only the filler. For gas adsorption experiments, higher recovery values indicate better adsorption and desorption, and therefore, the addition of the catalyst improves the adsorption of nitrosamines by the adsorption column. The catalyst can shield the interference of other nitrogen oxides, and ensure that the adsorption column mainly adsorbs nitrosamine during adsorption and cannot occupy adsorption sites by other substances.
Example 3Comparison of catalyst usage
The present inventors also analyzed and compared the catalyst amount ratio while optimizing sulfamic acid and sodium bisulfate as catalysts. In this example, the other conditions were the same as those given in example 1, but the catalyst usage ratio was varied.
Catalyst proportions corresponding to each 0.4g of the adsorbent filler:
the dosage of the fixed sulfamic acid is 10mg, and the dosage of the sodium bisulfate is changed to 0mg, 10mg, 20mg, 30mg, 40mg and 50mg.
The dosage of the fixed sodium bisulfate is 10mg, and the dosage of the sulfamic acid is changed to 0mg, 10mg, 20mg, 30mg, 40mg and 50mg;
the catalyst was added as designed above.
(1) Influence of sodium bisulfate consumption on recovery rate when sulfamic acid remains unchanged
The standard sample is defined when the sodium bisulfate dosage is 0mg, and the sample to be detected is defined when the sodium bisulfate dosage is 10mg, 20mg, 30mg, 40mg and 50mg.
The recovery rate calculation formula is as follows
X＝B/A*100％；
Wherein X is recovery rate, A is peak area of the standard sample, and B is peak area of the sample to be detected.
The test results are shown in Table 5.
TABLE 5 influence of the amount of sulfamic acid to the recovery rate with unchanged sodium bisulfate
As shown in Table 5 or FIG. 2, the amount of sulfamic acid was kept constant, and the adsorption recovery rate of the adsorption column was highest for 9 nitrosamines when the amount of sodium bisulfate was 10mg. When the sodium bisulfate is used for 20mg, the recovery rate is higher than that of the sodium bisulfate without using the sodium bisulfate; when the amount of sodium bisulfate is more than 20mg, the recovery rate of partial nitrosamine adsorption is reduced; when the amount of sodium bisulfate used is 30mg, 40mg, 50mg, the recovery rate of partial nitrosamine adsorption is already lower than that of sodium bisulfate not used.
(2) Influence of sulfamic acid usage on recovery rate when sodium bisulfate remains unchanged
The standard sample is defined when the sulfamic acid dosage is 0mg, and the sample to be detected is defined when the sulfamic acid dosage is 10mg, 20mg, 30mg, 40mg and 50mg.
The recovery rate calculation formula is as follows
X＝B/A*100％；
Wherein X is recovery rate, A is peak area of the standard sample, and B is peak area of the sample to be detected.
The test results are shown in Table 6.
TABLE 6 influence of the amount of sulfamic acid used on recovery while sodium bisulfate remains unchanged
As shown in Table 6 or FIG. 3, the amount of sodium bisulfate was kept constant, and the adsorption recovery rate of the adsorption column was highest for 9 kinds of nitrosamines when the amount of sulfamic acid was 30 mg. When the amount of sulfamic acid used is less than 30mg, the recovery rate increases as the amount added becomes larger, and when the amount of sulfamic acid added is further increased, the value of the recovery rate by adsorption decreases.
In conclusion, the sulfamic acid and the sodium bisulfate in the catalyst can adsorb trace nitrosamine and other nitrogen oxides, and meanwhile, the adsorption capacity of the sulfamic acid and the sodium bisulfate on the nitrosamine is obviously weaker than that of the filler, and the characteristic can be used for shielding the interference of other nitrogen oxides and protecting the filler, so that the overall adsorption effect is obviously improved. Meanwhile, after the addition amount of sulfamic acid and sodium bisulfate is increased to an extreme value, the shielding effect is maximized, and the residual sulfamic acid and sodium bisulfate can slightly adsorb nitrosamine, so that the adsorption effect is reduced. The dosage of the catalyst can achieve optimal adsorption effect when sulfamic acid is 30mg and sodium bisulfate is 10mg.
Example 4Analysis of adsorption column eluent
In this example, the other conditions are as given in example 1, with the catalyst amounts: the amount of sulfamic acid was 30mg and the amount of sodium bisulfate was 10mg per 0.4g of the adsorbent packing, but the composition and the ratio of the eluents were changed.
In the research work of the present application, the analysis of the eluate was also performed. After experiments and analysis with respect to a wide variety of organic solvents, the inventors believe that proper compounding of n-hexane, dichloromethane, acetone, isopropanol facilitates elution.
Mixing an agent selected from the group consisting of: n-hexane, dichloromethane, acetone, isopropanol, methanol. The elution effect is shown in Table 7 at various ratios.
The eluent combination dichloromethane and acetone (1:4) are defined as standard samples, and the combination of other reagents is defined as a sample to be detected.
The recovery rate calculation formula is as follows
X＝B/A*100％；
Wherein X is recovery rate, A is peak area of the standard sample, and B is peak area of the sample to be detected.
The test results are shown in Table 7.
TABLE 7 recovery after elution with different eluents
As shown in the results of table 7 or fig. 4, the elution effects of the different elution systems are quite different, and it is apparent that the higher the recovery rate in the results, the better the elution effect. It is therefore evident from the figure that the combination with good elution effect comprises: dichloromethane to acetone (1:1), dichloromethane to acetone (1:4), dichloromethane to acetone (4:1), n-hexane to acetone (1:1), acetone to isopropanol (1:1). Wherein, the optimal elution condition is methylene dichloride and acetone (1:1).
Various changes and modifications may be made therein by those skilled in the art in light of the teachings of this application, but such changes and modifications are intended to be included within the scope of the appended claims.
Claims (9)
1. A method for detecting nitrosamine in a gas, said method comprising:
(1) Providing an adsorption column loaded with an adsorbent packing and a catalyst; the adsorbent filler is a mixture of inorganic materials and antioxidants according to the mass ratio of 1-5:0.01-0.1; the catalyst is sulfamic acid and sodium bisulfate, and each 0.4g of adsorbent filler corresponds to 30 mg+/-10 mg of sulfamic acid and 10 mg+/-3 mg of sodium bisulfate; the inorganic material is diatomite, silicon dioxide, zeolite or molecular sieve; the antioxidant is metabisulfite or ascorbic acid;
(2) Adding a gas to be detected into the adsorption column of the step (1), eluting to obtain an eluted solution; the eluent used for the elution is selected from: dichloromethane and acetone mixed solution, normal hexane and acetone mixed solution, acetone and isopropanol mixed solution;
(3) Detecting by utilizing a gas chromatography-mass spectrometry, and obtaining the existence and/or the existence quantity of nitrosamine by utilizing a gas chromatography-mass spectrometer;
wherein the nitrosamine comprises: n-nitrosodimethylamine, N-nitrosomethylethylamine, N-nitrosodiethylamine, N-nitrosodiisopropylamine, N-nitrosopyrrolidine, N-nitrosodi-N-propylamine, N-nitrosomorpholine, N-nitrosopiperidine and/or N-nitrosodi-N-butylamine.
2. The method according to claim 1, wherein in the step (1), the amount of the catalyst is: every 0.4g of adsorbent packing corresponds to: sulfamic acid 30 mg+ -6 mg, sodium bisulfate 10 mg+ -2 mg.
3. The method of claim 1, wherein the adsorption column of step (1) is prepared by:
taking pure black low background polypropylene material with a light shielding effect as a column tube;
filling a sealing element of an air inlet end into the bottom of the column tube, wherein the sealing element of the air inlet end is a stainless steel screen or a silica gel screen plate;
uniformly packing the adsorbent packing into the column tube;
loading the catalyst into the column;
placing a sealing element of an air outlet end above the adsorbent filler, and flattening, wherein the sealing element of the air outlet end is a silica gel sieve plate or a cotton sheet, and the sieve holes of the sealing element of the air outlet end are not larger than those of the sealing element of the air inlet end;
and pressing the top cover into the adsorption column.
4. The method according to claim 1, wherein in step (2), the gas to be measured includes: air, tail gas, industrial waste gas and gas in a vehicle.
5. The method according to claim 1, wherein in the step (2), the eluted solution is filtered and used in the step (3).
6. The method of claim 5, wherein the eluent comprises:
eluent with the volume ratio of dichloromethane to acetone being 1:1;
eluent with the volume ratio of dichloromethane to acetone being 1:4;
eluent with the volume ratio of dichloromethane to acetone being 4:1;
eluent with the volume ratio of n-hexane to acetone being 1:1; or (b)
Eluent with the volume ratio of acetone to isopropanol being 1:1.
7. The method of claim 1, wherein in step (3), the detecting comprises: sample pretreatment and detection using gas chromatography mass spectrometry.
8. The method according to claim 7, wherein the gas chromatograph-mass spectrometer parameters are set as follows:
chromatographic column: CD-624,30 m0.25mm.times.1.4. Mu.m;
sample inlet temperature: 220 DEG C
Sample injection mode: split sample injection, split ratio 10:1, a step of;
carrier gas: helium gas; the control mode is as follows: constant current; flow rate: 1.0mL/min;
heating program: the initial temperature is 50 ℃, kept for 3min, and is raised to 120 ℃ at 20 ℃/min, kept for 2min, raised to 140 ℃ at 3 ℃/min, kept for 1min, raised to 160 ℃ at 20 ℃/min, and kept for 5min;
sample injection amount: 1 μl;
transmission line temperature: 250 ℃;
ion source temperature: 250 ℃;
ionization mode: electron bombardment ionization;
solvent delay time: 6min;
scanning mode: and (5) full scanning.
9. Use of the detection method according to any one of claims 1 to 8 for detecting nitrosamines in a gas, wherein the nitrosamines comprise: n-nitrosodimethylamine, N-nitrosomethylethylamine, N-nitrosodiethylamine, N-nitrosodiisopropylamine, N-nitrosopyrrolidine, N-nitrosodi-N-propylamine, N-nitrosomorpholine, N-nitrosopiperidine and/or N-nitrosodi-N-butylamine.
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| CN114073936A (en) * | 2021-08-13 | 2022-02-22 | 上海安谱实验科技股份有限公司 | Adsorbent for enriching nitrosamine in air and preparation method thereof |
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| CN114073936A (en) * | 2021-08-13 | 2022-02-22 | 上海安谱实验科技股份有限公司 | Adsorbent for enriching nitrosamine in air and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Gas Chromatographic/Mass Spectrometric Analysis of Extracts of Workplace Air Samples for Nitrosamines;CHARLES V. COOPER;《American Industrial Hygiene Association Journal》;第48卷(第3期);265-270 * |
| Simple quantification method for N-nitrosamines in atmospheric particulates based on facile pretreatment and GC-MS/MS;Youngmin Hong 等;《Environmental Pollution》;1-11 * |
| 气相色谱-质谱法同时测定肉制品中9种N-亚硝胺的含量;杨金川 等;《贵州农业科学》;第44卷(第11期);155-158 * |
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