CN117554401A - Method for detecting heavy metals in water based on membrane enrichment and X-ray fluorescence combination - Google Patents
Method for detecting heavy metals in water based on membrane enrichment and X-ray fluorescence combination Download PDFInfo
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- CN117554401A CN117554401A CN202410046534.1A CN202410046534A CN117554401A CN 117554401 A CN117554401 A CN 117554401A CN 202410046534 A CN202410046534 A CN 202410046534A CN 117554401 A CN117554401 A CN 117554401A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000012528 membrane Substances 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000004876 x-ray fluorescence Methods 0.000 title claims abstract description 30
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 100
- 238000001514 detection method Methods 0.000 claims abstract description 62
- 150000002500 ions Chemical class 0.000 claims abstract description 62
- 239000008139 complexing agent Substances 0.000 claims abstract description 54
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 20
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 18
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000002189 fluorescence spectrum Methods 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012086 standard solution Substances 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 claims description 6
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 5
- 238000012417 linear regression Methods 0.000 claims description 5
- 229960003330 pentetic acid Drugs 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 claims description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 4
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- TZMVSJNOQJXJMO-UHFFFAOYSA-N 2-[1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound OC(=O)CC1(CC(O)=O)CCCCC1(CC(O)=O)CC(O)=O TZMVSJNOQJXJMO-UHFFFAOYSA-N 0.000 claims description 3
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229940074360 caffeic acid Drugs 0.000 claims description 3
- 235000004883 caffeic acid Nutrition 0.000 claims description 3
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 229940079877 pyrogallol Drugs 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 12
- 230000035945 sensitivity Effects 0.000 abstract description 9
- 241000237536 Mytilus edulis Species 0.000 abstract description 8
- 238000005886 esterification reaction Methods 0.000 abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 abstract description 8
- 235000020638 mussel Nutrition 0.000 abstract description 8
- 239000011664 nicotinic acid Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000010828 elution Methods 0.000 abstract description 4
- 239000002738 chelating agent Substances 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000002479 acid--base titration Methods 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229960001124 trientine Drugs 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- -1 amino-carboxyl Chemical group 0.000 description 3
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000333 X-ray scattering Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000001391 atomic fluorescence spectroscopy Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000673 graphite furnace atomic absorption spectrometry Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to a method for detecting heavy metal ion concentration based on membrane enrichment and X-ray fluorescence combination, which comprises a non-woven fabric polyhydroxy modification procedure, a non-woven fabric ammonia-carboxyl complexing agent functionalization procedure, a standard curve preparation procedure and a heavy metal ion concentration detection procedure. The method for detecting the concentration of heavy metal ions based on the combination of membrane enrichment and X-ray fluorescence is adopted, the hydroxyl content of the surface of the non-woven fabric is improved by utilizing the polyhydroxy polymer grafted chain anchored by the mussel bionic coating, then the chelating agent capable of being combined with various metal ions is introduced into the surface of the non-woven fabric by utilizing the esterification reaction of hydroxyl and an aminocarboxylic complexing agent, and then the heavy metal ions are detected by combining with the X-ray fluorescence, thereby overcoming the defects of weak penetrability, rapid attenuation and low sensitivity of the existing pure X-ray detection in water, avoiding the need of an additional elution flow of an enrichment membrane, realizing the rapid and on-site detection of heavy metal in water quality, and having the advantages of high sensitivity, low detection limit, low cost and the like.
Description
Technical Field
The invention relates to the field of water quality monitoring, in particular to a method for detecting heavy metals in water by utilizing enrichment membrane and X-ray fluorescence.
Background
Heavy metals have the characteristics of nondegradability, high toxicity, enrichment and the like, and heavy metals discharged into natural water bodies can be gradually accumulated to cause serious environmental problems, and can be enriched into human bodies through biological chains to endanger the health of people.
The premise of heavy metal treatment is to detect heavy metal. Currently, the main means for detecting heavy metal ions are atomic absorption spectrometry, atomic fluorescence spectrometry, inductively coupled plasma atomic emission spectrometry, ultraviolet-visible absorption spectrometry and the like. Although the atomic absorption spectrometry, especially the graphite furnace atomic absorption spectrometry, has higher sensitivity, the detection speed is slower, and the method is more suitable for single-element analysis and can not meet the requirement of large sample quantity; the atomic fluorescence spectrum rule has strict requirements on the medium; inductively coupled plasma atomic emission spectrometry, although highly sensitive, is not suitable for high salt samples; the ultraviolet-visible absorption spectrometry has the defects of complex operation, low sensitivity, and the like, and toxic and harmful reagents are often used. In addition, the test technologies often need to take a certain amount of water sample to a laboratory, and a large-scale analysis instrument is used for analyzing the water sample, so that the problems of long analysis process, high cost, complicated steps and the like exist, and the detection result has no timeliness.
Currently, technologies suitable for on-site detection of heavy metals mainly include an electrochemical method and a colorimetric method. The colorimetric method can realize on-site detection through complexation of the color reagent and the heavy metal, but the method is easily influenced by factors such as water chromaticity, particulate matters and the like, has low sensitivity and cannot meet the detection of trace heavy metal water samples; the electrochemical method adopts an anodic stripping method, has the advantages of simple operation, realization of on-site water sample detection and the like, but the electrochemical instrument is often required to digest the sample during the test, and is not suitable for on-site rapid and high-sensitivity detection of field water bodies. XRF has been used for detection of solid samples and has standard methods, but XRF still has problems when directly measuring liquid samples, and the enriched heavy metal ions need to be eluted before measurement; when the solution is irradiated by X rays, due to local overheating, each component in the solution can react, and the stability of an analysis signal is seriously affected; in addition, the aqueous solution has stronger absorption capacity to X-rays, the spectral line intensity of the element to be detected can be weakened, a stronger X-ray scattering background is generated, and the signal-to-noise ratio is low.
Therefore, there is a need to develop a detection technique capable of overcoming the above-mentioned defect of rapid detection of heavy metals in aqueous solutions.
Disclosure of Invention
Aiming at the problems, the invention forms a coating on the surface of the non-woven fabric through a mussel bionic technology, then utilizes esterification reaction to functionally modify an ammonia-carboxyl complexing agent on the surface of the non-woven fabric to prepare the heavy metal enrichment membrane, and then is combined with an X-ray fluorescence detection technology to realize rapid and on-site detection of heavy metals in water, thereby overcoming the defects of weak penetrability, rapid attenuation, low sensitivity and the like of X-rays in water and avoiding the elution flow of the enrichment membrane.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
[1] The method for detecting the concentration of heavy metal ions based on the combination of membrane enrichment and X-ray fluorescence comprises the following steps:
a non-woven fabric polyhydroxy modification procedure: in the water added with the non-woven fabric, the molar ratio is 1: 0.1-10: adding catechol derivatives, oxidant and polyamine in a proportion of 0.1-10 into water, reacting for 0.5-3 hours at 20-70 ℃ to form a coating, then adding an etherifying agent of 0.1-10M, a cross-linking agent of 0.01-0.5M and alkali of 0.1-2M, and continuously reacting for 2-5 hours to prepare polyhydroxy modified non-woven fabrics;
functionalization process of non-woven fabric ammonia carboxyl complexing agent: according to the mass ratio of 1: 1-8: 1-4: adding the polyhydroxy modified non-woven fabric, an ammonia carboxyl complexing agent, a catalyst and acid anhydride into an organic solvent according to the proportion of 1-8, reacting for 6-24 hours at the temperature of 50-120 ℃, and sequentially washing and drying by using sodium bicarbonate solution and distilled water to obtain the ammonia carboxyl complexing agent functionalized non-woven fabric;
standard curve making procedure: cutting the ammonia-carboxyl complexing agent functionalized non-woven fabric into a proper shape, loading the proper shape into a filter head of an injector, carrying out dead-end filtration on the standard solution by utilizing the injector to obtain enrichment membranes of each heavy metal ion under different concentrations, drying the enrichment membranes of each heavy metal ion under different concentrations, carrying out X-fluorescence spectrum detection, taking the concentration of the metal ion as an abscissa, taking the signal value of the X-fluorescence spectrum of the heavy metal ion as an ordinate, fitting a linear regression equation, and respectively obtaining standard curves of the concentration of each heavy metal ion and the signal value of the heavy metal;
heavy metal ion concentration detection procedure: cutting the ammonia-carboxyl complexing agent functionalized non-woven fabric into a proper shape, loading the non-woven fabric into a filter head of an injector, carrying out dead-end filtration on a solution containing heavy metal ions to be detected by using the injector to obtain an enrichment membrane, drying the enrichment membrane, carrying out X-fluorescence spectrum detection, and carrying the obtained signal value into a corresponding standard curve to obtain the concentration of the heavy metal ions.
[2] The method for detecting heavy metal ion concentration based on membrane enrichment and X-ray fluorescence combination according to [1], wherein the catechol derivative is at least one selected from dopamine hydrochloride, catechol, pyrogallol and caffeic acid.
[3] The method for detecting the concentration of heavy metal ions based on membrane enrichment and X-ray fluorescence combination according to [1], wherein the oxidant is at least one selected from sodium persulfate, potassium persulfate and ammonium persulfate.
[4] The method for detecting a concentration of heavy metal ions based on membrane enrichment and X-ray fluorescence according to [1], wherein the polyamine is at least one selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine.
[5] The method for detecting the concentration of heavy metal ions based on membrane enrichment and X-ray fluorescence combination according to [1], wherein the etherifying agent is at least one of glycerol triglycidyl ether, ethylene glycol diglycidyl ether and 1, 4-butanediol diglycidyl ether.
[6] The method for detecting heavy metal ion concentration based on membrane enrichment and X-ray fluorescence combination according to [1], wherein the ammonia-carboxyl complexing agent is at least one selected from ethylenediamine tetraacetic acid, ethylenediamine tetraacetic acid disodium salt, diethylenetriamine pentaacetic acid, cyclohexane tetraacetic acid, ethylene glycol diethylether diamine tetraacetic acid and nitrilotriacetic acid.
[7] The method for detecting heavy metal ion concentration based on membrane enrichment and X-ray fluorescence combination according to [1], wherein the catalyst is at least one selected from concentrated sulfuric acid, pyridine, p-toluenesulfonic acid and 4-dimethylaminopyridine.
[8 ] the method for detecting a concentration of heavy metal ions based on membrane enrichment and X-ray fluorescence according to [1], wherein the acid anhydride is at least one selected from acetic anhydride, trifluoroacetic anhydride, propionic anhydride, BOC-anhydride.
[9] The method for detecting the concentration of heavy metal ions based on membrane enrichment and X-ray fluorescence combination according to the step (1), wherein the thickness of the ammonia-carboxyl complexing agent functionalized non-woven fabric is 0.5-5 mm.
Effects of the invention
The method for detecting the concentration of heavy metal ions based on the combination of membrane enrichment and X-ray fluorescence is adopted, the hydroxyl content of the surface of the non-woven fabric is improved by utilizing the polyhydroxy polymer grafted chain anchored by the mussel bionic coating, then the chelating agent capable of being combined with various metal ions is introduced into the surface of the non-woven fabric by utilizing the esterification reaction of hydroxyl and an aminocarboxylic complexing agent, and then the heavy metal ions are detected by combining with the X-ray fluorescence, thereby overcoming the defects of weak penetrability, rapid attenuation and low sensitivity of the existing pure X-ray detection in water, avoiding the need of an additional elution flow of an enrichment membrane, realizing the rapid and on-site detection of heavy metal in water quality, and having the advantages of high sensitivity, low detection limit, low cost and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 is an infrared spectrum of a nonwoven fabric obtained after the polyhydroxy modification process and a nonwoven fabric obtained after the aminocarboxylic complexing agent functionalization process in example 1.
FIG. 2 shows a Cd obtained from a nonwoven fabric obtained in example 1 by the step of functionalizing the aminocarboxylic complexing agent 2+ A standard curve.
FIG. 3 shows Ni obtained from a nonwoven fabric obtained in the step of functionalizing the aminocarboxylic complexing agent obtained in example 1 2+ A standard curve.
FIG. 4 shows Zn in a nonwoven fabric obtained by the step of functionalizing the aminocarboxylic complexing agent obtained in example 1 2+ A standard curve.
FIG. 5 shows Pb obtained from a nonwoven fabric obtained in the step of functionalizing the aminocarboxylic complexing agent obtained in example 1 2+ A standard curve.
Detailed Description
Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, the same numbers in different drawings refer to the same or similar elements, unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the invention. Rather, they are merely examples of apparatus and methods consistent with aspects of the invention as detailed in the accompanying claims.
The method for detecting the concentration of heavy metal ions based on the combination of membrane enrichment and X-ray fluorescence comprises a non-woven fabric polyhydroxy modification procedure, a non-woven fabric ammonia-carboxyl complexing agent functionalization procedure, a standard curve preparation procedure and a heavy metal ion concentration detection procedure.
In the above-mentioned nonwoven fabric polyhydroxy modification step, in the water to which the nonwoven fabric is added, the molar ratio of each of them is 1: 0.1-10: adding catechol derivative, oxidant and polyamine in a proportion of 0.1-10 into water, reacting for 0.5-3 hours at 20-70 ℃ to form a coating, then adding etherifying agent of 0.1-10M, cross-linking agent of 0.01-0.5M and alkali of 0.1-2M, and continuing to react for 2-5 hours to prepare the polyhydroxy modified non-woven fabric.
By adopting the non-woven fabric polyhydroxy modification procedure and adopting the mussel bionic anchored surface grafting technology, polyhydroxy polymer grafted chains are introduced on the surface of the non-woven fabric, so that the density of hydroxyl functional groups is improved. Specifically, a hydroxyl functional non-woven fabric is prepared by adopting a mussel bionic anchored grafting technology, and then the non-woven fabric functionalized by an amino-carboxyl complexing agent is prepared through esterification reaction. Mussel bionic technology is a surface functionalization technology, and can form a coating on the surface of almost all materials. According to the invention, by utilizing the bionic characteristic of mussels, catechol is oxidized by an oxidant to form o-benzoquinone, then the o-benzoquinone reacts with polyamine rapidly to form a coating on the surface of the non-woven fabric, then an etherifying agent is added, and a ring-opening coupling reaction is carried out on the polyamine and glycidyl ether to form a polymer chain with hydroxyl, so that the hydroxyl functional non-woven fabric is formed. The dual-function etherifying agent and the cross-linking agent act together in the reaction process, so that the stability of the hydroxyl functional non-woven fabric is improved. Finally, obtaining the non-woven fabric functionalized by the aminocarboxylic complexing agent through esterification reaction. The following shows the reaction process of one embodiment. As can be seen from this process, in the following step (1) of the reaction process for forming a coating layer on the nonwoven fabric surface, chemical bonding with the nonwoven fabric does not occur. Therefore, the functional group or the like on the nonwoven fabric surface is not particularly limited, that is, any commercially available nonwoven fabric may be used, for example, model N95 nonwoven fabric manufactured by the company nitafida clean materials, ltd, used in the examples of the present application.
(1) Reaction process for forming coating on non-woven fabric surface
(2) Reaction process for forming hydroxyl functional non-woven fabric by ring opening of etherifying agent and amino
(3) Preparation of ammonia carboxyl complexing agent functional non-woven fabric by esterification reaction
In some embodiments, the catechol derivative is preferably at least one selected from the group consisting of dopamine hydrochloride, catechol, pyrogallol, and caffeic acid.
In some embodiments, the foregoing oxidizing agent is preferably at least one selected from sodium persulfate, potassium persulfate, and ammonium persulfate, for example.
In some embodiments, the aforementioned polyamine is preferably at least one selected from, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and polyethyleneimine.
In some embodiments, the aforementioned etherifying agent is preferably at least one of glycerol triglycidyl ether, ethylene glycol diglycidyl ether, and 1, 4-butanediol diglycidyl ether, for example.
In the functionalization process of the non-woven fabric aminocarboxylic complexing agent, the mass ratio of the non-woven fabric to the aminocarboxylic complexing agent is 1: 1-8: 1-4: and (3) adding the polyhydroxy modified non-woven fabric, the aminocarboxylic complexing agent, the catalyst and the anhydride into an organic solvent according to the proportion of 1-8, reacting for 6-24 hours at the temperature of 50-120 ℃, and sequentially washing and drying by using sodium bicarbonate solution and distilled water to obtain the aminocarboxylic complexing agent functionalized non-woven fabric.
In some embodiments, the aforementioned aminocarboxylic complexing agent is preferably at least one selected from, for example, ethylenediamine tetraacetic acid disodium salt, diethylenetriamine pentaacetic acid, cyclohexane tetraacetic acid, ethylene glycol diethylether diamine tetraacetic acid, nitrilotriacetic acid.
In some embodiments, the foregoing catalyst is preferably at least one selected from, for example, concentrated sulfuric acid, pyridine, p-toluenesulfonic acid, 4-dimethylaminopyridine.
In some embodiments, the thickness of the above-mentioned aminocarboxylic complexing agent functionalized nonwoven is preferably, for example, 0.5 to 5 mm.
Through the above-mentioned non-woven fabric ammonia carboxyl complexing agent functionalization procedure, the ammonia carboxyl complexing agent is combined to the non-woven fabric surface by utilizing esterification reaction, thereby improving the density of the ammonia carboxyl complexing agent functional groups on the non-woven fabric surface, and remarkably improving the adsorption capacity.
In the standard curve manufacturing process, the ammonia-carboxyl complexing agent functionalized non-woven fabric is cut into a proper shape, the proper shape is put into a filter head of an injector, dead-end filtration is carried out on standard solutions containing heavy metal ions with different concentrations by the injector to obtain enrichment membranes of the heavy metal ions with different concentrations, then the enrichment membranes of the heavy metal ions with different concentrations are dried and then subjected to X-fluorescence spectrum detection, the concentration of the heavy metal ions is taken as an abscissa, the signal value of the X-fluorescence spectrum of the heavy metal ions is taken as an ordinate, and a linear regression equation is fitted to obtain standard curves of the concentration of the heavy metal ions and the signal value of the heavy metal respectively.
The heavy metal ions mentioned above are, for example, co 2+ 、Cd 2+ 、Ni 2+ 、Zn 2+ 、Pb 2+ Etc.
In the standard curve forming step, the standard solution may be, for example, co 2+ 、Cd 2+ 、Ni 2+ 、Zn 2+ 、Pb 2 + And the like, and the concentration of the standard solution may be, for example, 10. Mu.g/L, 50. Mu.g/L, 100. Mu.g/L, 200. Mu.g/L, 300. Mu.g/L, 400. Mu.g/L, 500. Mu.g/L, 600. Mu.g/L, and the like.
The syringe may have a capacity of, for example, 5mL, 10mL, 20mL, or the like, and is not particularly limited. Those skilled in the art can adjust appropriately as needed.
The above-mentioned cutting of the nonwoven fabric into an appropriate shape means cutting the nonwoven fabric into a shape appropriate for the filter head of the syringe, and is preferably circular.
The fitting linear regression equation may be performed by using software such as origin8.5 to obtain a regression equation, and the software used for fitting is not particularly limited, and can be appropriately selected as required by those skilled in the art.
In the heavy metal ion concentration detection procedure, the ammonia-carboxyl complexing agent functionalized non-woven fabric is cut into a proper shape, the non-woven fabric is put into a filter head of an injector, the injector is used for dead-end filtering of a solution containing heavy metal ions to be detected, an enrichment membrane is obtained, the enrichment membrane is dried and then subjected to X-fluorescence spectrum detection, and the obtained signal value is brought into a corresponding standard curve, so that the concentration of the heavy metal ions is obtained.
By adopting the method for detecting the concentration of the heavy metal ions based on the combination of membrane enrichment and X-ray fluorescence, the hydroxyl content of the surface of the non-woven fabric is improved by utilizing the polyhydroxy polymer grafted chain anchored by the mussel bionic coating, then the chelating agent capable of being combined with various metal ions is introduced into the surface of the non-woven fabric by utilizing the esterification reaction of the hydroxyl and the aminocarboxylic complexing agent, and then the heavy metal ions are detected by combining with the X-ray fluorescence, thereby overcoming the defects of weak penetrability, rapid attenuation and low sensitivity of the existing pure X-ray detection in water, and realizing the rapid and on-site detection of the heavy metal in water without setting an additional enrichment membrane elution flow, and the detection limit can be as low as 1 mug/L, and is greatly improved compared with the detection limit of 20 mug/L in the prior art.
The following examples are intended to illustrate the invention in further detail, but the scope of the invention is not limited to the following specific examples.
Example 1[ preparation of Ammonia Carboxylic complexing agent functionalized nonwoven Fabric ]
Dissolving 0.88 g catechol, 1.82 g ammonium persulfate and 2 mL tetraethylenepentamine in 200 mL distilled water, adding a washed nonwoven fabric with the thickness of 0.5mm (nonwoven fabric model N95, manufactured by Tianjin Tadada clean materials Co., ltd.), reacting at 70 ℃ for 0.5 h, adding 2 mL glycol diglycidyl ether, 0.8 g sodium hydroxide and 2 mL glutaraldehyde, continuously stirring for 1.5 h, taking out and washing, drying to obtain a polyhydroxy modified nonwoven fabric, weighing 0.5 g ethylenediamine tetraacetic acid, 1 mL pyridine and 2 mL acetic anhydride, dissolving in 30 mL of N, N-dimethylformamide, adding the polyhydroxy modified fabric, reacting at 50 ℃ for 20 h, washing with 10% sodium bicarbonate solution and distilled water in sequence, drying to obtain an aminocarboxylic complexing agent functionalized nonwoven fabric, and measuring the carboxyl content of the surface to be 0.78 mmol/g by an acid-base titration method.
Cd 2+ And (3) standard curve preparation:
preparation of Cd of 10. Mu.g/L, 50. Mu.g/L, 100. Mu.g/L, 200. Mu.g/L, 300. Mu.g/L, 400. Mu.g/L, 500. Mu.g/L, 600. Mu.g/L 2+ Filling the ammonia-carboxyl complexing agent functionalized non-woven fabric prepared by the method into a filter head of an injector, injecting 10mL of standard solution with different concentrations into the injector, controlling the filtering flow rate to be 0.5 mL/min, carrying out dead-end filtering so as to enrich, taking out the filtered ammonia-carboxyl complexing agent functionalized non-woven fabric, placing the non-woven fabric in a blast drying box for drying, then regulating the detection voltage of a portable X-fluorescence spectrometer to be 20 KV, the current to be 30 mA and the irradiation time to be 90 s, and randomly taking four points on the ammonia-carboxyl complexing agent functionalized non-woven fabric for detection to obtain the average signal value of metal ions. The concentration of the metal ions is taken as an abscissa, the signal value of the metal ions detected by the portable X-fluorescence spectrometer is taken as an ordinate, and a linear regression equation is fitted to obtain the metal ions Cd 2+ A standard curve of concentration versus signal value is shown in fig. 2.
Ni 2+ Standard curve making
In addition to Cd as described above 2+ Substitution of solution to Ni 2+ In addition to the aforementioned Cd 2+ Standard curve preparation was performed in the same manner to prepare Ni 2+ The standard curve is shown in fig. 3.
Zn 2+ Standard curve making
In addition to Cd as described above 2+ Replacement of solution with Zn 2+ In addition to the aforementioned Cd 2+ The standard curve was prepared in the same manner as Zn 2+ The standard curve is shown in fig. 4.
Pb 2+ Standard curve making
In addition to Cd as described above 2+ Replacement of solution with Pb 2+ In addition to the aforementioned Cd 2+ The standard curve was prepared in the same manner as Pb 2+ The standard curve is shown in fig. 5.
And (3) taking samples to be detected of different ions, enriching through a non-woven fabric membrane, and detecting by adopting a portable X-fluorescence spectrometer. As a result, the detection limit of Ni was 1.5. Mu.g/L, the detection limit of Cd was 1.78g/L, the detection limit of Zn was 2.36g/L, the detection limit of Pb was 1.65g/L, and the relative error range of the detection values was within 20%.
Example 2[ preparation of Ammonia-carboxyl complexing agent functionalized nonwoven Fabric ]
Dissolving 0.88 g catechol, 0.91 g ammonium persulfate and 2 mL tetraethylenepentamine in 200 mL distilled water, adding the washed non-woven fabric, reacting at 70 ℃ for 0.5 h, adding 2 mL ethylene glycol diglycidyl ether, 0.8 g potassium hydroxide and 2 mL glutaraldehyde, continuously stirring for 1.5 h, taking out, washing, drying to obtain polyhydroxy modified non-woven fabric, weighing 0.5 g ethylenediamine tetraacetic acid, 1 mL pyridine and 2 mL acetic anhydride, dissolving in 30 mL of N, N-dimethylformamide, adding polyhydroxy modified cloth, reacting at 50 ℃ for 20 h, washing sequentially with 10% sodium bicarbonate solution and distilled water, drying to obtain the ammonia-carboxylic complexing agent functionalized non-woven fabric enrichment membrane, and measuring the surface carboxyl content of the ammonia-carboxylic agent functionalized non-woven fabric enrichment membrane by an acid-base titration method to be 0.7 mmol/g.
As a result of preparing a standard curve of each ion and further detecting a sample to be measured in the same manner as in example 1, the detection limit of Ni was 1.23. Mu.g/L, the detection limit of Cd was 1.75g/L, the detection limit of Zn was 2.36g/L, the detection limit of Pb was 1.36g/L, and the relative error range of the detection values was within 20%.
Example 3[ preparation of Ammonia Carboxylic complexing agent functionalized nonwoven Fabric ]
Dissolving 0.88 g catechol, 0.91 g ammonium persulfate and 2 mL ethylenediamine in 200 mL distilled water, adding a washed non-woven fabric with the thickness of 0.5mm, reacting at 70 ℃ for 0.5 h, adding 2 mL ethylene glycol diglycidyl ether, 0.8 g sodium hydroxide and 2 mL glutaraldehyde, continuously stirring for 1.5 h, taking out, washing, drying to obtain a polyhydroxy modified non-woven fabric, weighing 1 g ethylenediamine tetraacetic acid, 1.5 mL of 4-dimethylaminopyridine and 2 mL acetic anhydride, dissolving in 30 mL of N, N-dimethylformamide, adding polyhydroxy modified fabric, reacting at 100 ℃ for 20 h, washing with 10% sodium bicarbonate solution and distilled water in sequence, drying to obtain an aminocarboxylic complexing agent functionalized non-woven fabric enrichment membrane, and measuring the surface carboxyl content of the membrane to be 0.8 mmol/g by an acid-base titration method. The standard curve of each ion was prepared in the same manner as in example 1, and further the sample to be measured was detected, and as a result, the detection limit was 1.23. Mu.g/L, and the relative error range of the detection value was within 20%.
Example 4[ preparation of Ammonia Carboxylic complexing agent functionalized nonwoven Fabric ]
Dissolving 0.88 g catechol, 0.91 g ammonium persulfate and 2 mL triethylene tetramine in 200 mL distilled water, adding washed non-woven fabric with the thickness of 0.5mm, reacting at 70 ℃ for 0.5 h, adding 2 mL ethylene glycol diglycidyl ether, 0.8 g calcium hydroxide and 2 mL glutaraldehyde, continuously stirring for 1.5 h, taking out, washing, drying to obtain polyhydroxy modified non-woven fabric, weighing 1 g diethylenetriamine pentaacetic acid, 1.5 mL 4-dimethylaminopyridine and 2 mL acetic anhydride, dissolving in 30 mL N, N-dimethylformamide, adding polyhydroxy modified cloth, reacting at 100 ℃ for 20 h, washing with 10% sodium bicarbonate solution and distilled water in sequence, drying to obtain the amino-carboxyl complexing agent functionalized non-woven fabric enrichment membrane, and measuring the surface carboxyl content of the amino-carboxyl enriched membrane to be 0.85 mmol/g by an acid-base titration method. As a result of preparing a standard curve of each ion and further detecting a sample to be measured in the same manner as in example 1, the detection limit of Ni was 1.12. Mu.g/L, the detection limit of Cd was 1.68g/L, the detection limit of Zn was 2.24g/L, the detection limit of Pb was 1.23g/L, and the relative error range of the detection values was within 20%.
Example 5[ preparation of Ammonia Carboxylic complexing agent functionalized nonwoven Fabric ]
Dissolving 0.88 g catechol, 1.82 g ammonium persulfate and 2 mL triethylene tetramine in 200 mL distilled water, adding a washed non-woven fabric, reacting at 70 ℃ for 0.5 h, adding 2 mL glycol diglycidyl ether, 0.8 g potassium hydroxide and 2 mL glutaraldehyde, continuously stirring for 1.5 h, taking out, washing, drying to obtain a polyhydroxy modified non-woven fabric, weighing 1 g diethylenetriamine pentaacetic acid, 0.5 mL 4-dimethylaminopyridine and 2 mL acetic anhydride, dissolving in 30 mL N, N-dimethylformamide, adding polyhydroxy modified fabric, reacting at 90 ℃ for 20 h, washing with 10% sodium bicarbonate solution and distilled water in sequence, drying to obtain an aminocarboxylic complexing agent functionalized non-woven fabric enrichment membrane, and measuring the surface carboxyl content of the membrane to be 0.85 mmol/g by an acid-base titration method. As a result of preparing a standard curve of each ion and further detecting a sample to be measured in the same manner as in example 1, the detection limit of Ni was 1.08. Mu.g/L, the detection limit of Cd was 1.43g/L, the detection limit of Zn was 1.96g/L, the detection limit of Pb was 1.15g/L, and the relative error range of the detection values was within 20%.
Example 6[ preparation of Ammonia Carboxylic complexing agent functionalized nonwoven Fabric ]
Dissolving 0.88 g catechol, 1.82 g ammonium persulfate and 2 mL triethylene tetramine in 200 mL distilled water, adding a washed non-woven fabric with the thickness of 0.5mm, reacting at 70 ℃ for 0.5 h, adding 2 mL ethylene glycol diglycidyl ether, 0.8 g sodium hydroxide and 2 mL glutaraldehyde, continuously stirring for 1.5 h, taking out, washing, drying to obtain a polyhydroxy modified non-woven fabric, weighing 1 g nitrilotriacetic acid, 0.5 mL 4-dimethylaminopyridine and 2 mL acetic anhydride, dissolving in 30 mL N, N-dimethylformamide, adding polyhydroxy modified fabric, reacting at 90 ℃ for 20 h, washing with 10% sodium bicarbonate solution and distilled water sequentially, drying to obtain an aminocarboxylic complexing agent functionalized non-woven fabric enrichment membrane, and measuring the surface carboxyl content of 0.82 mmol/g by an acid-base titration method. As a result of preparing a standard curve of each ion and further detecting a sample to be measured in the same manner as in example 1, the detection limit of Ni was 2.56. Mu.g/L, the detection limit of Cd was 2.87g/L, the detection limit of Zn was 3.12g/L, the detection limit of Pb was 2.47g/L, and the relative error range of the detection values was within 20%.
It is apparent that the above examples are given by way of illustration and not limitation of the embodiments. Other variations or modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that the invention is not limited to the precise arrangements and instrumentalities shown in the drawings, which have been described above, and that various modifications and changes may be effected without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (9)
1. The method for detecting the concentration of heavy metal ions based on membrane enrichment and X-ray fluorescence comprises the following steps:
a non-woven fabric polyhydroxy modification procedure: in the water added with the non-woven fabric, the molar ratio is 1: 0.1-10: adding catechol derivatives, oxidant and polyamine in a proportion of 0.1-10 into water, reacting for 0.5-3 hours at 20-70 ℃ to form a coating, then adding an etherifying agent of 0.1-10M, a cross-linking agent of 0.01-0.5M and alkali of 0.1-2M, and continuously reacting for 2-5 hours to prepare polyhydroxy modified non-woven fabrics;
functionalization process of non-woven fabric ammonia carboxyl complexing agent: according to the mass ratio of 1: 1-8: 1-4: adding the polyhydroxy modified non-woven fabric, an ammonia carboxyl complexing agent, a catalyst and acid anhydride into an organic solvent according to the proportion of 1-8, reacting for 6-24 hours at the temperature of 50-120 ℃, and sequentially washing and drying by using sodium bicarbonate solution and distilled water to obtain the ammonia carboxyl complexing agent functionalized non-woven fabric;
standard curve making procedure: cutting the ammonia carboxyl complexing agent functionalized non-woven fabric into a proper shape, loading the proper shape into a filter head of an injector, carrying out dead-end filtration on standard solutions containing heavy metal ions with different concentrations by utilizing the injector to obtain enrichment membranes of the heavy metal ions with different concentrations, drying the enrichment membranes of the heavy metal ions with different concentrations, carrying out X-fluorescence spectrum detection, taking the concentration of the heavy metal ions as an abscissa, taking the signal value of the X-fluorescence spectrum of the heavy metal ions as an ordinate, fitting a linear regression equation, and respectively obtaining standard curves of the concentration of the heavy metal ions and the signal value of the heavy metal;
heavy metal ion concentration detection procedure: cutting the ammonia-carboxyl complexing agent functionalized non-woven fabric into a proper shape, loading the non-woven fabric into a filter head of an injector, carrying out dead-end filtration on a solution containing heavy metal ions to be detected by using the injector to obtain an enrichment membrane, drying the enrichment membrane, carrying out X-fluorescence spectrum detection, and carrying the obtained signal value into a corresponding standard curve to obtain the concentration of the heavy metal ions.
2. The method for detecting heavy metal ion concentration based on membrane enrichment and X-ray fluorescence combination according to claim 1, wherein the catechol derivative is at least one selected from dopamine hydrochloride, catechol, pyrogallol, caffeic acid.
3. The method for detecting heavy metal ion concentration based on membrane enrichment and X-ray fluorescence combination according to claim 1, wherein the oxidant is at least one selected from sodium persulfate, potassium persulfate and ammonium persulfate.
4. The method for detecting heavy metal ion concentration based on membrane enrichment and X-ray fluorescence combination according to claim 1, wherein the polyamine is at least one selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine.
5. The method for detecting the concentration of heavy metal ions based on membrane enrichment and X-ray fluorescence combination according to claim 1, wherein the etherifying agent is at least one selected from glycerol triglycidyl ether, ethylene glycol diglycidyl ether and 1, 4-butanediol diglycidyl ether.
6. The method for detecting heavy metal ion concentration based on membrane enrichment and X-ray fluorescence combination according to claim 1, wherein the ammonia-carboxyl complexing agent is at least one selected from ethylenediamine tetraacetic acid, ethylenediamine tetraacetic acid disodium salt, diethylenetriamine pentaacetic acid, cyclohexane tetraacetic acid, ethylene glycol diethylether diamine tetraacetic acid and nitrilotriacetic acid.
7. The method for detecting the concentration of heavy metal ions based on membrane enrichment and X-ray fluorescence combination according to claim 1, wherein the catalyst is at least one selected from concentrated sulfuric acid, pyridine, p-toluenesulfonic acid and 4-dimethylaminopyridine.
8. The method for detecting heavy metal ion concentration based on membrane enrichment and X-ray fluorescence combination according to claim 1, wherein the acid anhydride is at least one selected from acetic anhydride, trifluoroacetic anhydride, propionic anhydride and BOC-anhydride.
9. The method for detecting the concentration of heavy metal ions based on the combination of membrane enrichment and X-ray fluorescence according to claim 1, wherein the thickness of the ammonia carboxyl complexing agent functionalized non-woven fabric is 0.5-5 mm.
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