CN112730661A - Detection method for simultaneously determining PAEs and AEs plasticizers in waste textile raw materials - Google Patents
Detection method for simultaneously determining PAEs and AEs plasticizers in waste textile raw materials Download PDFInfo
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- CN112730661A CN112730661A CN202011524424.XA CN202011524424A CN112730661A CN 112730661 A CN112730661 A CN 112730661A CN 202011524424 A CN202011524424 A CN 202011524424A CN 112730661 A CN112730661 A CN 112730661A
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- phthalate
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 53
- 238000001514 detection method Methods 0.000 title claims abstract description 43
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- 239000002994 raw material Substances 0.000 title claims abstract description 31
- 150000002500 ions Chemical class 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 38
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- 239000013076 target substance Substances 0.000 claims abstract description 27
- 238000012360 testing method Methods 0.000 claims abstract description 20
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- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 14
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 claims description 12
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 claims description 12
- 238000002137 ultrasound extraction Methods 0.000 claims description 12
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 8
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 8
- RKELNIPLHQEBJO-UHFFFAOYSA-N bis(5-methylhexyl) benzene-1,2-dicarboxylate Chemical compound CC(C)CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC(C)C RKELNIPLHQEBJO-UHFFFAOYSA-N 0.000 claims description 8
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 8
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012634 fragment Substances 0.000 claims description 8
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 claims description 7
- 229940100539 dibutyl adipate Drugs 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 claims description 6
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 claims description 6
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 claims description 6
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 6
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 claims description 6
- 229940031769 diisobutyl adipate Drugs 0.000 claims description 6
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 claims description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- -1 bis- (2-ethoxy) ethyl Chemical group 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 239000008029 phthalate plasticizer Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- PCGGKRXVRHWQGH-UHFFFAOYSA-N C(C=1C(C(=O)O)=CC=CC1)(=O)O.CC(C(C)O)O Chemical compound C(C=1C(C(=O)O)=CC=CC1)(=O)O.CC(C(C)O)O PCGGKRXVRHWQGH-UHFFFAOYSA-N 0.000 claims description 3
- IHTSDBYPAZEUOP-UHFFFAOYSA-N bis(2-butoxyethyl) hexanedioate Chemical compound CCCCOCCOC(=O)CCCCC(=O)OCCOCCCC IHTSDBYPAZEUOP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
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- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000004885 tandem mass spectrometry Methods 0.000 claims description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims 2
- 241000411851 herbal medicine Species 0.000 claims 1
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- 239000000835 fiber Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- 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
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- 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
- G01N30/60—Construction of the column
- G01N30/6052—Construction of the column body
- G01N30/6073—Construction of the column body in open tubular form
- G01N30/6078—Capillaries
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- 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
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
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- 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
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
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Abstract
The invention discloses a detection method for simultaneously determining PAEs and AEs plasticizers in waste textile raw materials. The method comprises the steps of establishing pretreatment conditions and detecting a sample; the method comprises the steps of preparing standard solutions of PAEs and AEs plasticizers, carrying out GC/MS test on the standard solutions, determining the types and characteristic ions of target substances, and further carrying out experimental test on samples. The method for simultaneously measuring the PAEs and AEs plasticizer components in the textile raw material solid waste is established, has the advantages of strong anti-interference capability, high sensitivity and the like, and provides reliable technical support for extraction and detection of the substances in the textile solid waste; meanwhile, the identification and attribution of available textile raw materials are realized, and the method has important significance.
Description
Technical Field
The invention relates to a detection method for simultaneously determining PAEs and AEs plasticizers in waste textile raw materials.
Technical Field
In recent years, with the huge development of the textile industry in China, a large amount of imported textile raw materials become the important strategic demand of the textile industry in China, but the related inspection and judgment standards of waste textile raw material solid wastes do not exist in China at present, so that the illegal import of the waste textile raw material solid wastes which are unavailable and highly polluted is facilitated, and the waste textile raw materials (plant fibers) bring serious threats to the safety of the ecological environment in China due to the practical problems of wide sources, complex processes, complex substances, serious potential risks of toxic substances and the like.
Phthalate (PAEs) and Adipate (AEs) are plasticizers existing in waste textile raw materials of plant fibers and have huge potential hazards, and meanwhile, as the waste textile raw materials (plant fibers) are various in types and complex in matrix, a systematic, complete and reliable detection method for the PAEs and the AEs in the textile raw material solid waste is not available in China, so that the textile raw materials which are safe, sanitary and environment-friendly can not be identified and attributed. Therefore, the establishment of the method for detecting the plasticizer in the waste textile has important significance. At present, ultrasonic extraction, solid-phase extraction, liquid-liquid extraction, accelerated solvent extraction, supercritical fluid extraction and the like are mainly adopted as pretreatment methods for detecting PAEs and AEs plasticizers at home and abroad, but the methods have the defects of long treatment and detection process, large consumption of organic solvents and the like, and particularly the matrix effect influences plant fiber textile solid wastes with complex components to further increase the pretreatment difficulty.
Therefore, a detection method which is simple to establish and operate, low in solvent demand, low in cost, environment-friendly and high in enrichment efficiency aiming at complex matrixes is needed to detect harmful substances such as phthalic acid ester and adipate in textile raw material solid wastes.
Disclosure of Invention
Aiming at the problems and the purpose to be achieved, the invention provides a detection method for simultaneously determining PAEs and AEs plasticizers in waste textile raw materials, which adopts an ultrasonic-assisted solid phase extraction (GC/MS) pretreatment method to strengthen the enrichment and purification of a target object and reduce the interference of a matrix effect on the target object; aiming at the complex matrix, the detection method which is simple in operation, small in solvent demand, low in cost, environment-friendly and high in enrichment efficiency is established. The specific technical scheme is as follows:
a detection method for simultaneously determining PAEs and AEs plasticizers in waste textile raw materials is characterized in that ultrasonic-assisted solid-phase extraction gas chromatography-tandem mass spectrometry is used, solid waste of the waste textile raw materials to be detected is subjected to ultrasonic extraction and further enriched and purified by a solid-phase extraction column, and PAEs and AEs plasticizer substances in the solid waste of the waste textile raw materials are determined simultaneously.
The detection method for simultaneously detecting the PAEs and the AEs plasticizer in the waste textile raw materials comprises the steps of establishing a pretreatment condition and detecting a sample; the method comprises the steps of preparing standard solutions of PAEs and AEs plasticizers, carrying out GC/MS test on the standard solutions, determining the types and characteristic ions of target substances, and further carrying out experimental test on samples.
The establishing pretreatment condition specifically comprises the following steps:
s1-1: preparation of standard stock solution: accurately weighing a proper amount of PAEs and AEs plasticizer standard, preparing a mixed standard stock solution of 1000 mu g/mL by using n-hexane, and refrigerating and storing the mixed standard stock solution in a brown reagent bottle at the temperature of 4 ℃;
s1-2: preparation of standard working solution: accurately transferring a proper amount of the mixed standard stock solution prepared in the step S1-1, diluting the concentration with normal hexane, and preparing into mixed standard working solutions with series concentrations;
s1-3: ion detection: performing ion full scanning on the mixed standard working solution prepared in the step S1-2 by adopting a chromatographic column temperature-rising program to obtain a total ion current chromatogram of a target substance;
s1-4: determining the type and characteristic ions: determining the peak-appearing time of each PAEs and AEs plasticizer standard substance in the mixed standard stock solution according to the chromatogram obtained by ion scanning in the step S1-3, and determining the species and characteristic ions of fragment ions in the mass spectrum, thereby establishing the pretreatment condition of the GC/MS-SIM method.
In a preferred embodiment, in step S1-1, the total 23 PAEs and AEs plasticizer standards include: the purity of the 18 phthalate plasticizer standards and the 5 adipate plasticizer standards is more than 98.0 percent. The 18 phthalate plasticizer standards are as follows: DEP, dipropyl phthalate (DPRP), diisobutyl phthalate (DIBP), DBP, dimethylethylene glycol phthalate (DMEP), dipentyl phthalate (DPP), bis-4-methyl-2-pentyl phthalate (BMPP), di- (2-ethoxy) ethyl phthalate (DEEP), dihexyl phthalate (DNHP), BBP, diisoheptyl phthalate (DIHP), dicyclohexyl phthalate (DCHP), diheptyl phthalate (DHP), DEHP, DNOP, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dinonyl phthalate (DNP); the 5 adipate plasticizer standards are as follows: diethyl adipate (DEA), diisobutyl adipate (DIBA), dibutyl adipate (DBA), di (2-butoxyethyl) adipate (BBOEA), di-2-ethylhexyl adipate (DEHA).
In a preferred embodiment, in step S1-2, the concentrations of the series of mixed standard working solutions include: 1. mu.g/mL, 2. mu.g/mL, 5. mu.g/mL, 10. mu.g/mL and 20. mu.g/mL.
Preferably, in step S1-3, the chromatographic column is HP-5MS capillary chromatographic column with specification of 30.0m × 0.25mm × 0.25 μm; the temperature raising procedure is as follows: maintaining at 60 deg.C for 1min, increasing to 200 deg.C at 5 deg.C/min, maintaining for 1min, increasing to 280 deg.C at 15 deg.C/min, and maintaining for 5 min; injecting sample without shunting, wherein the temperature of a sample injection port is 280 ℃, the flow rate is 1.0mL/min, and the sample injection amount is 1.2 mu L; the ionization source is an EI source, and the ionization energy is 70 eV.
In the foregoing detection method for simultaneously determining PAEs and AEs plasticizers in waste textile materials, the experimental test performed on the sample specifically includes the following steps:
s2-1: ultrasonic extraction: cutting a textile solid waste sample to be detected into fragments, and ultrasonically extracting the fragments in a conical flask with a plug by using an extracting solution; extracting the supernatant in a heart-shaped flask for 1 time; mixing the extractive solutions, and performing rotary evaporation for further enrichment and purification;
s2-2: solid phase extraction: eluting the extract obtained by ultrasonic extraction in the step S2-1 by using an eluent by using a solid phase extraction column to well enrich and purify target substances in the extract, and carrying out nitrogen blowing on the obtained eluent to be subjected to ion detection;
s2-3: ion detection: scanning the eluent extracted from the solid phase in the step S2-2 by adopting an HP-5MS capillary chromatographic column heating program to obtain an ion current chromatogram of a target substance contained in the eluent;
s2-4: determining the target substance: and analyzing the ion current chromatogram in the step S2-3, determining the types and characteristic ions according to the total ion current chromatogram of the mixed standard working solution, and simultaneously determining PAEs and AEs plasticizer substances contained in the textile solid waste sample to be detected.
In a preferred technical scheme, in the step S2-1, the sample is cut to a size of 3X 3 mm; the extracting solution is a mixed solvent of n-hexane and dichloromethane; the ultrasonic extraction conditions are as follows: the temperature is 30 deg.C, frequency is 40KHz, and extraction time is 30 min.
In a preferred embodiment, in step S2-2, the solid-phase extraction column used for the solid-phase extraction is an Alumina-N solid-phase extraction column, and the eluent is a mixed solvent of N-hexane and dichloromethane.
In a further preferred embodiment, the mixed solvent of n-hexane and dichloromethane used in the extraction liquid in step S2-1 and the eluent in step S2-2 has a mixed volume ratio of 4: 1; wherein the amount of the eluent used in the solid-phase extraction in step S2-2 was 10 mL.
The invention has the beneficial effects that:
the method utilizes an ultrasonic-assisted solid-phase extraction pretreatment mode, uses N-hexane-dichloromethane as an extracting agent and an extracting solution, purifies and enriches the extracting solution through an Alumina-N solid-phase extraction column, and detects the extracting solution by adopting GC/MS (gas chromatography/mass spectrometry).
The method adopts the HP-5MS capillary chromatographic column, adopts a temperature raising program of the chromatographic column and carries out testing in a selective ion scanning mode, and because the SIM carries out selective detection according to certain characteristic ions of the target substance, the method can greatly increase the chromatographic peak intensity of the target substance, effectively reduce the generation of miscellaneous peaks, reduce the interference of other components in the matrix on the target substance and improve the accuracy and the selectivity of the analysis method. In addition, the invention treats the sample extracting solution by a solid phase extraction method, so that target substances can be well enriched and purified, and the accuracy of subsequent ion scanning tests is ensured. The method has the advantages that the accuracy and the precision meet the requirements of relevant standards and regulations at home and abroad, and the detection result is accurate and reliable; the method is simple to operate, low in solvent demand, low in cost, environment-friendly and high in enrichment efficiency, can effectively detect the complex matrix in the waste plant fiber textile raw materials, realizes identification and attribution of the usable textile raw materials which are safe, sanitary and environment-friendly, and has important significance.
Drawings
FIG. 1 is a total ion flow chromatogram of a mixed standard working solution of the detection method for simultaneously determining PAEs and AEs plasticizers in waste textile raw materials according to the invention;
FIG. 2 is a chromatogram before solid phase extraction of an ultrasonic extracting solution of a textile solid waste sample according to the present invention;
FIG. 3 is a chromatogram after solid-phase extraction of an ultrasonic extracting solution of a textile solid waste sample according to the present invention.
In the figure: DEA, 2.DEP, 3.DIBA, 4.DBA, 5.DPrP, 6.DIBP, 7.DBP, 8.DMEP, 9.DPP, 10.BMPP, 11.BBOEA, 12.DEEP, 13.DNHP, 14.BBP, 15.DEHA, 16.DIHP, 17.DCHP, 18.DHP, 19.DEHP, 20.DNOP, 21.DINP, 22.DIDP, 23. DNP.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments and the accompanying drawings.
Example 1
The method comprises the steps of carrying out ultrasonic extraction on waste solid waste of the waste textile raw material to be detected and further enriching and purifying the waste solid waste by using a solid-phase extraction column through ultrasonic-assisted solid-phase extraction gas chromatography-tandem mass spectrometry, and simultaneously measuring substances of the PAEs and the AEs plasticizer in the waste solid waste of the waste textile raw material.
The detection method for simultaneously detecting PAEs and AEs plasticizers in waste textile raw materials comprises the steps of establishing pretreatment conditions and detecting samples; the method comprises the steps of preparing standard solutions of PAEs and AEs plasticizers, carrying out GC/MS test on the standard solutions, determining the types and characteristic ions of target substances, and further carrying out experimental test on samples.
The establishing pretreatment condition specifically comprises the following steps:
s1-1: preparation of standard stock solution: accurately weighing a proper amount of PAEs and AEs plasticizer standard, preparing a mixed standard stock solution of 1000 mu g/mL by using n-hexane, and refrigerating and storing the mixed standard stock solution in a brown reagent bottle at the temperature of 4 ℃; the PAEs and AEs plasticizer standards included: the 18 phthalate plasticizer standards are as follows: DEP, dipropyl phthalate (DPRP), diisobutyl phthalate (DIBP), DBP, dimethylethylene glycol phthalate (DMEP), dipentyl phthalate (DPP), bis-4-methyl-2-pentyl phthalate (BMPP), di- (2-ethoxy) ethyl phthalate (DEEP), dihexyl phthalate (DNHP), BBP, diisoheptyl phthalate (DIHP), dicyclohexyl phthalate (DCHP), diheptyl phthalate (DHP), DEHP, DNOP, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dinonyl phthalate (DNP); and 5 adipate plasticizer standards were: diethyl adipate (DEA), diisobutyl adipate (DIBA), dibutyl adipate (DBA), di (2-butoxyethyl) adipate (BBOEA), di-2-ethylhexyl adipate (DEHA). A total of 23, all purchased from dr. ehrenstorfer gmbh, germany, were greater than 98.0% pure.
S1-2: preparation of standard working solution: and (3) accurately transferring a proper amount of the mixed standard stock solution prepared in the step S1-1, and diluting the mixed standard stock solution into a standard working solution with the concentration of 20 mu g/mL by using normal hexane, or respectively preparing series of mixed standard working solutions with the concentrations of 1, 2, 5, 10 and 20 mu g/mL according to requirements for GC/MS test.
S1-3: ion detection: performing ion full scanning on the mixed standard working solution prepared in the step S1-2 by adopting a chromatographic column temperature-rising program to obtain a total ion current chromatogram of the target substance, which is shown in FIG. 1; the chromatographic column used was an HP-5MS capillary chromatographic column with a specification of 30.0 m.times.0.25 mm.times.0.25. mu.m. The temperature programming is as follows: keeping the temperature at 60 ℃ for 1min, increasing the temperature to 200 ℃ at 5 ℃/min, keeping the temperature for 1min, increasing the temperature to 280 ℃ at 15 ℃/min, keeping the temperature for 5min, injecting samples without shunting, wherein the temperature of an injection port is 280 ℃, and the flow rate is 1.0 mL/min; the sample volume was 1.2. mu.L, the ionization source was an EI source, the ionization energy was 70eV, and the selected ion detection (SIM), CAS number, retention time, and SIM parameters of 23 plasticizers are shown in Table 1.
S1-4: determining the type and characteristic ions: determining the peak-appearing time of each PAEs and AEs plasticizer standard substance in the mixed standard stock solution according to the chromatogram obtained by ion scanning in the step S1-3, and determining the species and characteristic ions of fragment ions in the mass spectrum, thereby establishing the pretreatment condition of the GC/MS-SIM method.
TABLE 1.23 CAS number, residence time and SIM parameters for plasticizers
The experimental test of the sample specifically comprises the following steps:
s2-1: ultrasonic extraction: cutting a textile solid waste sample to be detected, which is randomly sampled and inspected in a solid waste recovery market, into 3 multiplied by 3mm fragments, uniformly mixing, accurately weighing 5g (accurate value is 0.01g) in a conical flask with a plug of 150mL, adding 20mL of n-hexane-dichloromethane (4:1, V/V) as an extracting solution, shaking uniformly, carrying out ultrasonic extraction for 30min at 30 ℃ and 40KHz, taking supernatant in a heart bottle, repeating the operation for 1 time, combining the extracting solutions, carrying out rotary evaporation to 1mL, and waiting for further enrichment and purification of a solid phase extraction column.
S2-2: solid phase extraction: eluting the extract liquid ultrasonically extracted in the step S2-1 by using an eluent by adopting a solid phase extraction column, which specifically comprises the following steps: activating an Alumina-N solid phase extraction column with 4mL of N-hexane-dichloromethane (4:1, V/V), balancing with 5mL of N-hexane, eluting the extract with 10mL of N-hexane-dichloromethane (4:1, V/V) eluent, blowing nitrogen to 1mL, and analyzing by GC/MS test. The solid-phase extraction can well enrich and purify target substances in the extracting solution of the sample to be detected, so that the subsequent GC/MS test analysis is more accurate, and the chromatogram before and after the ultrasonic extracting solution solid-phase extraction of the textile solid waste sample is compared, as shown in fig. 2 and fig. 3.
S2-3: ion detection: and scanning the eluent of the solid phase extraction in the step S2-2 by adopting the HP-5MS capillary chromatographic column heating program in the step S1-3 to obtain an ion current chromatogram of the target substance contained in the eluent.
S2-4: determining the target substance: and analyzing the ion current chromatogram in the step S2-3, and determining PAEs and AEs plasticizer substances contained in the textile solid waste sample to be detected according to the total ion current chromatogram of the mixed standard working solution in the step S1-3 and the types and characteristic ions determined in the step S1-4.
Example 2
In this example, the detection method described in example 1 was verified for correlation and detection limit, and the accuracy and precision of the method were also verified.
The correlation and detection limit verification in this embodiment is: and (3) performing quantitative analysis by adopting an external standard method, drawing a standard working curve of 23 plasticizers by taking the mass concentration of the standard working solution as a horizontal coordinate and the peak area of the quantitative ion mass chromatogram as a vertical coordinate to obtain a linear equation and a correlation coefficient, wherein the result is shown in a table 2.
TABLE 2.23 Linear correlation coefficients, Linear Range and detection limits of the plasticizers
As can be seen from the above table, the linear correlation coefficient R of the detection method of the invention is not less than 0.9907, the detection limit (S/N is 3) is 0.084-1.748 mu g/g, wherein the detection limits of the three substances, namely DIHP, DINP and DIDP are respectively 1.464 mu g/g, 1.423 mu g/g and 1.423 mu g/g, which are obviously higher than the detection limits of the other 17 substances, because the three substances have higher measurement lower limits and 748 multiple peaks, and the linear range is 5 times that of the other substances, therefore, the detection limit is higher than that of the other substances.
The accuracy and precision in this example were verified as follows: taking a textile solid waste sample without target substances as an object, adding 3 standard adding levels of 5, 10 and 20 mu g/mL (DIHP, DINP and DIDP are 25, 50 and 100 mu g/mL), processing the sample according to the pretreatment method, performing machine test according to the instrument conditions, performing standard adding recovery test for 6 parallel control groups of each standard adding level, and obtaining the results of standard adding recovery and relative standard deviation (n is 6) of 23 plasticizers shown in Table 3.
Table 3.23 additive recovery and relative standard deviation of plasticizers (n ═ 6)
It can be seen from the above table that the normalized recovery rate of the 23 targets is 83.3% -104.3%, the relative standard deviation (RSD, n is 6) is 1.9% -8.1%, and the method is accurate and reliable, and meets the requirements of relevant standards and regulations at home and abroad.
Example 3
In this example, the measurement of 23 target components was performed on 50 batches of waste textile solid waste samples of market entrustment and import inspection according to the detection method described in example 1. Through detection, 5 target substances are detected in different degrees, and the target substances are detected for waste cotton yarns with paint: DBA, DIBP and DBP with the content of 0.42-0.81 mu g/g, 0.26-0.57 mu g/g and 0.68-1.32 mu g/g respectively, DEHP with the content of 0.37-0.65 mu g/g is detected in the sample of the blowing noil and the cotton linter, DEP with the content of 0.25-0.84 mu g/g is detected in other waste cotton samples.
The detection method adopts the HP-5MS capillary chromatographic column, adopts a chromatographic column temperature-rising program and a selective ion scanning mode for testing, and because the SIM carries out selective detection according to certain characteristic ions of the target substance, the chromatographic peak intensity of the target substance can be greatly increased, the generation of miscellaneous peaks can be effectively reduced, the interference of other components in the matrix on the target substance can be reduced, and the accuracy and the selectivity of the analysis method can be improved. Through the solid phase extraction method, the sample extracting solution is treated, so that target substances can be well enriched and purified, and the accuracy of subsequent ion scanning tests is ensured. And the method has the advantages that the accuracy and the precision meet the requirements of relevant standards and regulations at home and abroad, and the detection result is accurate and reliable. In addition, the detection method disclosed by the invention is simple to operate, low in solvent demand, low in cost, environment-friendly, high in enrichment efficiency, strong in anti-interference capability, high in sensitivity and the like, provides reliable technical support for extraction and detection of the substances in the textile solid waste, realizes identification and attribution of the textile raw materials which are safe, sanitary and environment-friendly and can be used, and has important significance.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. Furthermore, it should be understood that although the present specification describes embodiments, these embodiments are not intended to be included solely, and such description is for clarity only, and those skilled in the art will be able to make the present specification as a whole, and the embodiments of the present invention may be appropriately combined to form other embodiments understood by those skilled in the art.
Claims (10)
1. A detection method for simultaneously determining PAEs and AEs plasticizers in waste textile raw materials is characterized in that: the method comprises the steps of performing ultrasonic extraction on waste textile raw material solid waste to be detected through ultrasonic-assisted-solid phase extraction gas chromatography-tandem mass spectrometry, further enriching and purifying the waste textile raw material solid waste by using a solid phase extraction column, and simultaneously determining PAEs and AEs plasticizer substances in the waste textile raw material solid waste.
2. The method for simultaneously detecting PAEs and AEs plasticizers in waste textile materials as claimed in claim 1, wherein: the method comprises the steps of establishing a pretreatment condition and detecting a sample; the method comprises the steps of preparing standard solutions of PAEs and AEs plasticizers, carrying out GC/MS test on the standard solutions, determining the types and characteristic ions of target substances, and further carrying out experimental test on samples.
3. The method for simultaneously detecting PAEs and AEs plasticizers in waste textile materials as claimed in claim 2, wherein: the establishing of the pretreatment condition specifically comprises the following steps:
s1-1: preparation of standard stock solution: accurately weighing a proper amount of PAEs and AEs plasticizer standard, preparing mixed standard stock solution of 1000 mug/mL by using n-hexane, and refrigerating and storing the mixed standard stock solution in a brown reagent bottle at 4 ℃;
s1-2: preparation of standard working solution: accurately transferring a proper amount of the mixed standard stock solution prepared in the step S1-1, diluting the concentration with normal hexane, and preparing into mixed standard working solutions with series concentrations;
s1-3: ion detection: performing ion full scanning on the mixed standard working solution prepared in the step S1-2 by adopting a chromatographic column temperature-rising program to obtain a total ion current chromatogram of a target substance;
s1-4: determining the type and characteristic ions: determining the peak-appearing time of each PAEs and AEs plasticizer standard substance in the mixed standard stock solution according to the chromatogram obtained by ion scanning in the step S1-3, and determining the species and characteristic ions of fragment ions in the mass spectrum, thereby establishing the pretreatment condition of the GC/MS-SIM method.
4. The method for simultaneously detecting PAEs and AEs plasticizers in waste textile materials as claimed in claim 3, wherein: in step S1-1, the PAEs and AEs plasticizer standards comprise:
18 phthalate plasticizer standards: DEP, dipropyl phthalate, diisobutyl phthalate, DBP, dimethylethylene glycol phthalate, dipentyl phthalate, bis-4-methyl-2-pentyl phthalate, bis- (2-ethoxy) ethyl phthalate, dihexyl phthalate, BBP, diisoheptyl phthalate, dicyclohexyl phthalate, diheptyl phthalate, DEHP, DNOP, diisononyl phthalate, diisodecyl phthalate, dinonyl phthalate;
5 adipate plasticizer standards: diethyl adipate, diisobutyl adipate, dibutyl adipate, di (2-butoxyethyl) adipate, di-2-ethylhexyl adipate;
the purity of 23 kinds of the Chinese herbal medicines is more than 98.0%.
5. The method for simultaneously detecting PAEs and AEs plasticizers in waste textile materials as claimed in claim 3, wherein: in step S1-2, the concentrations of the series of mixed standard working solutions include: 1 mug/mL, 2 mug/mL, 5 mug/mL, 10 mug/mL and 20 mug/mL.
6. The method for simultaneously detecting PAEs and AEs plasticizers in waste textile materials as claimed in claim 3, wherein: in step S1-3, the chromatographic column is HP-5MS capillary chromatographic column with specification of 30.0m × 0.25mm × 0.25 μm; the temperature raising procedure is as follows: maintaining at 60 deg.C for 1min, increasing to 200 deg.C at 5 deg.C/min, maintaining for 1min, increasing to 280 deg.C at 15 deg.C/min, and maintaining for 5 min; injecting sample without shunting, wherein the temperature of a sample injection port is 280 ℃, the flow rate is 1.0mL/min, and the sample injection amount is 1.2 mu L; the ionization source is an EI source, and the ionization energy is 70 eV.
7. The method for simultaneously detecting PAEs and AEs plasticizers in waste textile materials as claimed in claim 2, wherein: the experimental test of the sample specifically comprises the following steps:
s2-1: ultrasonic extraction: cutting a textile solid waste sample to be detected into fragments, and ultrasonically extracting the fragments in a conical flask with a plug by using an extracting solution; extracting the supernatant in a heart-shaped flask for 1 time; mixing the extractive solutions, and performing rotary evaporation for further enrichment and purification;
s2-2: solid phase extraction: eluting the extract obtained by ultrasonic extraction in the step S2-1 by using an eluent by using a solid phase extraction column to well enrich and purify target substances in the extract, and carrying out nitrogen blowing on the obtained eluent to be subjected to ion detection;
s2-3: ion detection: scanning the eluent extracted from the solid phase in the step S2-2 by adopting an HP-5MS capillary chromatographic column heating program to obtain an ion current chromatogram of a target substance contained in the eluent;
s2-4: determining the target substance: and analyzing the ion current chromatogram in the step S2-3, determining the types and characteristic ions according to the total ion current chromatogram of the mixed standard working solution, and simultaneously determining PAEs and AEs plasticizer substances contained in the textile solid waste sample to be detected.
8. The method of claim 7 for simultaneously detecting PAEs and AEs plasticizers in waste textile materials, wherein: in step S2-1, the sample is cut to a size of 3 x 3 mm; the extracting solution is a mixed solvent of n-hexane and dichloromethane; the ultrasonic extraction conditions are as follows: the temperature is 30 deg.C, frequency is 40KHz, and extraction time is 30 min.
9. The method of claim 7 for simultaneously detecting PAEs and AEs plasticizers in waste textile materials, wherein: in step S2-2, the solid-phase extraction column used for the solid-phase extraction is an Alumina-N solid-phase extraction column, and the eluent is a mixed solvent of N-hexane and dichloromethane.
10. The method for simultaneously detecting PAEs and AEs plasticizers in waste textile materials according to claim 8 or 9, wherein: the mixed solvent of n-hexane and dichloromethane used by the extracting solution in the step S2-1 and the eluent in the step S2-2 has the mixed volume ratio of the n-hexane and the dichloromethane of 4: 1; wherein the amount of the eluent used in the solid-phase extraction in step S2-2 was 10 mL.
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