CN109115712A - Detect the device and method of dissolved organic matter different molecular weight component ETC - Google Patents
Detect the device and method of dissolved organic matter different molecular weight component ETC Download PDFInfo
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- CN109115712A CN109115712A CN201811088004.4A CN201811088004A CN109115712A CN 109115712 A CN109115712 A CN 109115712A CN 201811088004 A CN201811088004 A CN 201811088004A CN 109115712 A CN109115712 A CN 109115712A
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000005446 dissolved organic matter Substances 0.000 title claims abstract description 26
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 147
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 21
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 19
- 238000000825 ultraviolet detection Methods 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 238000006479 redox reaction Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000001514 detection method Methods 0.000 claims description 31
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 16
- 229960005070 ascorbic acid Drugs 0.000 claims description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 238000001802 infusion Methods 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000012491 analyte Substances 0.000 claims description 4
- 238000005374 membrane filtration Methods 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 239000008055 phosphate buffer solution Substances 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- SIZUFDOZCJLMAV-UHFFFAOYSA-N N1=CC=CC2=CC(=CC=C12)S(=O)(=O)O.C(C)N1CSC2=C1C=CC=C2 Chemical compound N1=CC=CC2=CC(=CC=C12)S(=O)(=O)O.C(C)N1CSC2=C1C=CC=C2 SIZUFDOZCJLMAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 229940059939 kayexalate Drugs 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 2
- 235000000069 L-ascorbic acid Nutrition 0.000 claims 1
- 239000002211 L-ascorbic acid Substances 0.000 claims 1
- 230000008033 biological extinction Effects 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 6
- 238000002835 absorbance Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 201000010099 disease Diseases 0.000 description 6
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002468 redox effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- -1 3- sulphonyl propyl Chemical group 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008366 buffered solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
Abstract
A kind of device and method detecting dissolved organic matter different molecular weight component ETC, including flowing carrier reagent access, reaction reagent access and ultraviolet detection access, flowing carrier reagent access transport flow support agent and sample under oxygen-free environment, gel chromatography column is provided in flowing carrier reagent access, sample is separated by gel chromatography column by molecular weight, reaction reagent access conveys reaction reagent under oxygen-free environment, flowing carrier reagent access is connected to ultraviolet detection access after converging with reaction reagent access, UV detector is provided in ultraviolet detection access, reaction reagent is in certain wave with absorption maximum, sample is after gel chromatography column is separated by molecular weight, redox reaction occurs with reaction reagent, the absorbance change of UV detector test sample, to determine the electronics of different molecular weight component in sample Transfer ability.The present invention is able to achieve the simplicity of the electron transfer capacity of different molecular weight component, Accurate Determining in complex system.
Description
Technical field
The present invention relates to water treatment fields, more particularly to detection dissolved organic matter different molecular weight component ETC
The device and method of (electron transfer capacities, electron transfer capacity).
Background technique
Dissolved organic matter (Dissolved Organic Matter, DOM) is component part important in stain disease, molten
Solution property organic matter plays great role to processes such as the migrations, conversion, degradation of pollutant, and the property of DOM is also and at stain disease
Reason process is closely bound up.In water treatment field, stain disease, such as ozone, Fenton are handled frequently with chemical oxidation method.And it is dirty
The effect of oxidation-reduction quality confrontation chemical oxidation of DOM and the generation of by-product have an important influence in waste water.Electronics transfer
The redox property that ability (electron transfer capacities, ETC) can preferably assess DOM, again may be used
It is divided into electronics supply capacity and electron acceptability.Therefore, it is necessary to the electron transfer capacity of dissolubility component in stain disease
It is evaluated, to reflect the reactivity of organic matter and chemical oxidizing agent in stain disease.
Meanwhile stain disease is by the mixture of different molecular weight material composition, structure, the stabilization of different molecular weight organic matter
Property, degree of humification and armaticity it is different, electron transfer capacity is also different.To dissolved organic matter different molecular weight component
Electron transfer capacity is parsed, and can more optimize for water treatment technology and combination provides guidance.
The method for surveying ETC at present has coulomb Amperometric and central electron mediator method etc..Existing method surveys ETC, and not only step is numerous
It is trivial, limit for height is detected, and the electronics supply capacity or electron acceptability total value of tested sample can only be measured, complexity can not be measured
The electron transfer capacity of different molecular weight component in system can not also judge organic matter composition and distinguish inorganic ions interference.
Therefore, it is necessary to be explored to new ETC measuring method.
Summary of the invention
It is a primary object of the present invention to overcome the deficiencies of the prior art and provide a kind of detection dissolved organic matter difference point
The device and method of son amount component ETC.
To achieve the above object, the invention adopts the following technical scheme:
A kind of device detecting dissolved organic matter different molecular weight component ETC, including flowing carrier reagent access, reaction
Reagent access and ultraviolet detection access, the flowing carrier reagent access are used for the transport flow support agent under oxygen-free environment
And sample, gel chromatography column is provided in the flowing carrier reagent access, the sample presses molecule by the gel chromatography column
Amount is separated, and the reaction reagent access under oxygen-free environment for conveying reaction reagent, the flowing carrier reagent access
It is connected to the ultraviolet detection access after converging with the reaction reagent access, is provided with ultraviolet detection in the ultraviolet detection access
Device, the reaction reagent in certain wave with absorption maximum, the sample after gel chromatography column is separated by molecular weight, with
Redox reaction occurs for the reaction reagent, and the UV detector is used to detect the absorbance change of the sample, so as to
Determine the electron transfer capacity of different molecular weight component in the sample.
Further:
Infusion pump is each provided in the flowing carrier reagent access and the reaction reagent access；The flowing carrier
Reagent access includes flowing carrier reagent bottle, and the reaction reagent access includes reaction reagent bottle, and described device further includes gas cylinder,
The gas cylinder is provided with helium, is separately connected via current divider and leads to the flowing carrier reagent bottle and the reaction reagent bottle；
Preferably, the flowing carrier reagent bottle and the reaction reagent bottle pass through three hole bottle caps respectively and connect the gas cylinder, respective
The infusion pump and escape pipe；Preferably, the flowing carrier reagent access include be connected to the flowing carrier reagent bottle and
Six-way valve between the gel chromatography column, the sample inject the flowing carrier reagent access by six-way valve.
The flowing carrier reagent access, the reaction reagent access are reacted with the ultraviolet detection access by three way type
Ring connection, the three way type reaction ring include three stainless steel spiral coil pipes and divide with three stainless steel spiral coil pipes
Not Xiang Lian a threeway mixer.
The flowing carrier reagent bottle is provided with the flowing carrier reagent, and the flowing carrier reagent is phosphate-buffered
Solution.
The reaction reagent bottle is provided with the reaction reagent, the reaction reagent be 2,2 '-azine group of oxidant-it is bis--
(3- ethyl benzo thiazoline quinoline -6- sulfonic acid) (AZB·+) or reducing agent N, N '-it is bis--(3- sulphonyl propyl) -4,4 '-bipyridyls
(ZiV·-) solution.
The gel chromatography column is porous methacrylate filler, and the packing material size is 5-10 μm；The gel layer
Analysis column diameter is 5-10mm, long 250-350mm.
A method of dissolved organic matter different molecular weight component electron transfer ability being detected using described device, including
Following steps:
A. reaction reagent is prepared, and is provided into the reaction reagent access under oxygen-free environment, the reaction reagent is specific
Wavelength has absorption maximum；
B. flowing carrier reagent is prepared, and is provided into the flowing carrier reagent access under oxygen-free environment；
C., flowing carrier reagent flow rate, reaction reagent flow velocity, minute and UV detector Detection wavelength etc. are set
Correlated condition parameter；
D. sample is injected into flowing carrier reagent access, sample follows flowing carrier reagent through gel chromatography column by molecule
After amount is separated, converge with the reaction reagent in reaction reagent access, redox reaction occurs, then pass through UV detector
Measure its UV absorption signal；
E. according to the UV absorption signal and standard curve of measurement, the electronics transfer energy of molecular weight analyte distribution is calculated
Power.
Preferably, in step A, reaction reagent preparation method includes: (a) oxidant AZB·+(detection electronics supply capacity)
It prepares: AZB is dissolved in 0.5mmol/L H2SO4, add ultrapure water to be made into AZB aqueous solution, it is molten that sodium hypochlorite be added dropwise with continuous stirring
Liquid makes 2/3rds AZB in system be oxidized to AZB·+, finally obtain 40 μm of ol/L AZB·+；(b) reducing agent ZiV·-(detection
Electron acceptability) it prepares: in electrochemical workstation, electrolyte and 750 μM of ZiV are added, in EHIt is anti-under the conditions of=- 0.49V
It answers, is reduced 2/3rds ZiV, obtains ZiV·-Solution.
Preferably, the flowing carrier reagent is the phosphate buffer solution of 4.0mM pH=7, including 2.4mM
NaH2PO4·2H2O, 1.6mM Na2HPO4·12H2O and 25mM Na2SO4。
Preferably, in the step C, flowing carrier reagent flow rate is 0.2~1.0mL/min, and reaction reagent flow velocity is
0.05~0.2mL/min, minute 1-2h.
Preferably, when detecting electronics supply capacity, UV detector Detection wavelength is 415nm；Detect electron acceptability
When, UV detector Detection wavelength is 603nm.
Preferably, the sample in step D before injection, by 0.45 μm of membrane filtration, the DOC concentration model of sample
It encloses for 0.5-200mg/L, Sample injection volume 0.1-2mL.
Preferably, in step E, the measuring method of standard curve includes the following steps: that (a) molecular weight distribution standard curve is surveyed
It is fixed；Kayexalate is chosen as standard sample；Selecting relative molecular mass is 210,3610,7540,32000,
126700 PSS standard specimen, replaces with high purity water for reaction reagent, measures and draws molecular weight distribution standard curve, obtain appearance
Linear relationship between time and molecular weight；(b) electronics supply capacity standard curve determination；Select ascorbic acid (ascorbic
Acid) as standard sample, (known ascorbic acid electronics supply capacity is 2mol e-/ mol), measurement concentration is 1,2,3,4,
The ascorbic acid of 5mol/L obtains the linear relationship between peak area and electronics supply capacity；(c) electron acceptability standard is bent
Line measurement；Selecting anthraquinone -2,6- sodium disulfonate (AQDS) as standard sample, (electron acceptability of known AQDS is 2mol
e-/ mol), the AQDS that measurement concentration is 1,2,3,4,5mol/L obtains the linear pass between peak area and electron acceptability
System.
The invention has the following beneficial effects:
The present invention is able to achieve the simplicity of the electron transfer capacity of different molecular weight component, Accurate Determining in complex system, compared with
The redox property of dissolved organic matter molecular weight distribution in sewage is assessed well, is provided for water treatment technology optimization and combination
Guidance.
The invention has the advantages that it is easy to operate, measurement the period it is short, high sensitivity, detection range is wide, error is lower.
Detailed description of the invention
Fig. 1 is the dress of the detection dissolved organic matter different molecular weight component electron transfer ability of an embodiment of the present invention
Set structural schematic diagram.
Fig. 2 is the dress using the detection dissolved organic matter different molecular weight component electron transfer ability of the embodiment of the present invention
Set the electronics supply capacity chromatogram result with method measurement sewage molecular weight distribution.
Specific embodiment
It elaborates below to embodiments of the present invention.It is emphasized that following the description is only exemplary,
The range and its application being not intended to be limiting of the invention.
Refering to fig. 1, in one embodiment, a kind of device detecting dissolved organic matter different molecular weight component ETC, packet
Flowing carrier reagent access, reaction reagent access and ultraviolet detection access are included, the flowing carrier reagent access is used in nothing
Transport flow support agent and sample under oxygen environment are provided with gel chromatography column 6, the sample in the flowing carrier reagent access
Product are separated by the gel chromatography column 6 by molecular weight, and the reaction reagent access is used to convey reaction under oxygen-free environment
Reagent, the flowing carrier reagent access are connected to the ultraviolet detection access, the purple after converging with the reaction reagent access
UV detector 10 is provided in outer detection path, the reaction reagent is in certain wave with absorption maximum, and the sample is through solidifying
After glue chromatographic column 6 is separated by molecular weight, redox reaction occurs with the reaction reagent, the UV detector 10 is used
In the absorbance change for detecting the sample, to determine the electron transfer capacity of different molecular weight component in the sample.
In a preferred embodiment, it is each provided in the flowing carrier reagent access and the reaction reagent access defeated
Liquid pump 4,7；The flowing carrier reagent access includes flowing carrier reagent bottle 2, and the reaction reagent access includes reaction reagent
Bottle 3, described device further includes gas cylinder 1, and the gas cylinder 1 is provided with helium, is separately connected via current divider and leads to the flowing load
Body reagent bottle 2 and the reaction reagent bottle 3.Preferably, the flowing carrier reagent bottle 2 and the reaction reagent bottle 3 lead to respectively
It crosses three hole bottle caps and connects the gas cylinder 1, the respective infusion pump 4,7 and escape pipe.
In a preferred embodiment, the flowing carrier reagent access includes being connected to 2 He of flowing carrier reagent bottle
Six-way valve between the gel chromatography column 6, the sample inject the flowing carrier reagent access by six-way valve.
In a preferred embodiment, the flowing carrier reagent access, the reaction reagent access and the ultraviolet detection
Access reacts ring connection by three way type, three way type reaction ring include three stainless steel spiral coil pipes and with described three
The threeway mixer that stainless steel spiral coil pipe is respectively connected with.
Referring to Fig.1, the present invention provides a kind of system and device for detecting organic matter different molecular weight component electron transfer ability,
Including gas cylinder 1, flowing carrier reagent bottle 2, reaction reagent bottle 3, infusion pump 4,7, six-way valve 5, gel chromatography column 6, three way type it is anti-
Ying Huan, UV detector 10, waste liquid cylinder 11, by connection as shown in the figure.
Gas cylinder 1 is provided with helium, is separately connected via current divider and leads to flowing carrier reagent bottle 2 and reaction reagent bottle 3, with
It ensures that detection process carries out in oxygen-free atmosphere, avoids air oxidation reagent to have an impact to result.
Reaction reagent is housed in reaction reagent bottle 3.Reaction reagent be oxidant 2,2 '-azine group-it is bis--(3- ethyl benzo
Thiazoline quinoline -6- sulfonic acid) AZB·+(detection electronics supply capacity) or reducing agent N, N '-be bis--and (3- sulphonyl propyl) -4,4 '-join
Pyridine ZiV·-(detection electron acceptability).
Flowing carrier is housed in flowing carrier reagent bottle 2.Flowing carrier is phosphate buffer solution.
In a preferred embodiment, 6 filler of gel chromatography column is porous methacrylate, and the packing material size is 5-10
μm；The gel chromatography column diameter is 5-10mm, long 250-350mm.Most preferably, packing material size is 7 μm.Chromatographing column diameter is
7.8mm, long 300mm.
Three way type reaction ring is connected to a Stainless steel tee mixer 8 by three stainless steel spiral coil pipes 9 and forms.Instead
Ring one end is answered to connect 6 flow path of gas cylinder 1- flowing carrier reagent bottle 2- infusion pump 4- six-way valve 5- gel chromatography column, other end connection
7 flow path of gas cylinder 1- reaction reagent bottle 3- infusion pump, two flow paths enter 1mL reactor coil pipe after mixing in mixer 8, then
Into UV detector 10, waste liquid cylinder 11 is finally flowed into.
It is shifted the present invention also provides a kind of using described device detection dissolved organic matter different molecular weight component electron
The method of ability comprising following steps:
Step A. prepares reaction reagent, and provides into the reaction reagent access under oxygen-free environment, and the reaction reagent exists
Certain wave is with absorption maximum；
Step B. prepares flowing carrier reagent, and provides into the flowing carrier reagent access under oxygen-free environment；
Step C. is arranged flowing carrier reagent flow rate, reaction reagent flow velocity, minute and UV detector 10 and detects
The correlated conditions parameter such as wavelength；
Step D. injects sample into flowing carrier reagent access, and sample follows flowing carrier reagent through gel chromatography column 6
After being separated by molecular weight, converge with the reaction reagent in reaction reagent access, redox reaction occurs, then by ultraviolet
Detector 10 measures its UV absorption signal；
E. according to the UV absorption signal and standard curve of measurement, the electronics transfer energy of molecular weight analyte distribution is calculated
Power.
In certain embodiments, this method comprises the following steps:
Step A. prepares reaction reagent.Reaction reagent is the preparation method is as follows: (a) oxidant AZB·+(detection electronics supplies energy
Power) it prepares: AZB is dissolved in 0.5mmol/L H2SO4, add ultrapure water to be made into AZB aqueous solution, hypochlorous acid be added dropwise with continuous stirring
Sodium solution makes 2/3rds AZB in system be oxidized to AZB·+, finally obtain 40 μm of ol/L AZB·+.The reaction equation of the process
For HOCl+2AZB+H+→Cl-+2AZB·+H2O.(b) reducing agent ZiV·-(detection electron acceptability) is prepared: in electrochemical operation
In standing, electrolyte and 750 μ are added as auxiliary electrode as reference electrode, vitreous carbon as working electrode, Ag/AgCl in platinum guaze
M ZiV, in EHIt is reacted under the conditions of=- 0.49V, is reduced 2/3rds ZiV, obtains ZiV·-Solution.The examination that configuration is obtained
Agent helium injection gas is after 15 minutes loaded in reaction reagent bottle.
Step B. prepares flowing carrier reagent, and flowing carrier reagent is the phosphate buffer solution of 4.0mM pH=7, including
2.4mM NaH2PO4·2H2O, 1.6mM Na2HPO4·12H2O and 25mM Na2SO4.The reagent helium injection gas 15 that configuration is obtained
Loaded in flowing carrier reagent bottle after minute.
Step C. attachment device pipeline opens gas cylinder valve, and it is 0.2~1.0mL/ that flowing carrier reagent flow rate, which is arranged,
Min, reaction reagent flow velocity is 0.05~0.2mL/min, minute 1-2h, and UV detector Detection wavelength is 415nm (inspection
Survey electronics supply capacity) or 603nm (detection electron acceptability).
Step D. device is run to UV detector signal stabilization, and sample is injected into flow path by six-way valve with needle tubing
Product measure its UV absorption signal.
The ETC of molecular weight analyte distribution is calculated according to standard curve in step E..
The sample in the step D before injection, should pass through 0.45 μm of membrane filtration, the DOC concentration model of sample
It encloses for 0.5-200mg/L, Sample injection volume 0.1-2mL.
In the step E, the measuring method of standard curve is as follows: (a) molecular weight distribution standard curve determination.Choose polyphenyl
Vinyl sulfonic acid sodium (sodium polystyrene sulfonate, PSS) is used as standard sample.Select relative molecular mass be
210,3610,7540,32000,126700 PSS standard specimen, replaces with high purity water for reaction reagent, measures and draws molecular weight point
Cloth standard curve obtains the linear relationship between appearance time and molecular weight.(b) electronics supply capacity standard curve determination.Choosing
Ascorbic acid (ascorbic acid) is selected as standard sample, and (known ascorbic acid electronics supply capacity is 2mol e-/ mol),
The ascorbic acid that concentration is 1,2,3,4,5mol/L is measured, the linear relationship between peak area and electronics supply capacity is obtained.(c)
Electron acceptability standard curve determination.Select anthraquinone -2,6- sodium disulfonate (AQDS) as the standard sample (electricity of known AQDS
Sub- ability to accept is 2mol e-/ mol), the AQDS that measurement concentration is 1,2,3,4,5mol/L, obtains peak area and electronics receives
Linear relationship between ability.
It should be noted that the method need to be measured under the conditions of 30 DEG C.
The principle of the method detection dissolved organic matter different molecular weight component electron transfer ability is the reaction examination
Agent is in certain wave with absorption maximum, and with reaction reagent oxygen occurs for sample after gel chromatography column is separated by molecular weight
Change reduction reaction, causes the absorbance of system to change, absorbance change value is directly proportional to the electron transfer capacity of sample.
Method of the invention is described further combined with specific embodiments below:
AZB is dissolved in 0.5mmol/L H2SO4, it is made into the AZB solution of 1g/L, is added on 16.4mL in 483mL ultrapure water
AZB solution is stated, with continuous stirring, 1mL 10mmol/L liquor natrii hypochloritis is added, generates 40 μm of ol/L AZB·++
0.02mmol/L H2SO4Solution.Reagent helium injection gas 15 minutes that reaction is obtained, are fitted into reaction reagent bottle.
Configure the phosphate buffer solution of 4.0mM pH=7, including 2.4mM NaH2PO4·2H2O, 1.6mM Na2HPO4·
12H2O and 25mM Na2SO4.Reagent helium injection gas 15 minutes that configuration is obtained, are fitted into flowing carrier reagent bottle.
By 0.45 μm of membrane filtration of sewage sample.
Attachment device pipeline, opens gas cylinder valve, and setting flowing carrier reagent flow rate is 0.2mL/min, reactant stream
Speed is 0.05mL/min, and minute 1.5h, UV detector Detection wavelength is 415nm.
After UV detector signal is steady, 0.1Ml sewage sample is injected into flow path by six-way valve with needle tubing, is measured
Its UV absorption signal, as shown in Figure 2.
According to standard curve, the electronics supply capacity of sample sewage molecular weight distribution can be calculated.
The above content is combine it is specific/further detailed description of the invention for preferred embodiment, cannot recognize
Fixed specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs,
Without departing from the inventive concept of the premise, some replacements or modifications can also be made to the embodiment that these have been described,
And these substitutions or variant all shall be regarded as belonging to protection scope of the present invention.
Claims (10)
1. a kind of device for detecting dissolved organic matter different molecular weight component ETC, which is characterized in that including flowing carrier reagent
Access, reaction reagent access and ultraviolet detection access, the flowing carrier reagent access are used for the transport Stream under oxygen-free environment
Support agent and sample are moved, is provided with gel chromatography column in the flowing carrier reagent access, the sample is by the gel layer
Analysis column is separated by molecular weight, and the reaction reagent access is carried for conveying reaction reagent, the flowing under oxygen-free environment
Body reagent access is connected to the ultraviolet detection access after converging with the reaction reagent access, be arranged in the ultraviolet detection access
Have a UV detector, the reaction reagent in certain wave with absorption maximum, the sample through gel chromatography column by molecular weight into
After row separation, redox reaction occurs with the reaction reagent, the UV detector is used to detect the extinction of the sample
Degree variation, to determine the electron transfer capacity of different molecular weight component in the sample.
2. the device of detection dissolved organic matter different molecular weight component ETC according to claim 1, which is characterized in that
Infusion pump is each provided in the flowing carrier reagent access and the reaction reagent access；The flowing carrier reagent access
Including flowing carrier reagent bottle, the reaction reagent access includes reaction reagent bottle, and described device further includes gas cylinder, the gas cylinder
It is provided with helium, is separately connected via current divider and leads to the flowing carrier reagent bottle and the reaction reagent bottle；Preferably, institute
It states flowing carrier reagent bottle and passes through three hole bottle caps respectively with the reaction reagent bottle and connect the gas cylinder, the respective infusion pump
And escape pipe；Preferably, the flowing carrier reagent access includes being connected to the flowing carrier reagent bottle and the gel layer
The six-way valve between column is analysed, the sample injects the flowing carrier reagent access by six-way valve.
3. the device of detection dissolved organic matter different molecular weight component ETC according to claim 1 or 2, feature exist
In the flowing carrier reagent access, the reaction reagent access react ring by three way type with the ultraviolet detection access and connect
It connects, the three way type reaction ring includes three stainless steel spiral coil pipes and distinguishes phase with three stainless steel spiral coil pipes
A threeway mixer even.
4. the device of detection dissolved organic matter different molecular weight component ETC according to any one of claims 1 to 3,
It is characterized in that, the flowing carrier reagent bottle is provided with the flowing carrier reagent, and the flowing carrier reagent is slow for phosphate
Rush solution.
5. the device of detection dissolved organic matter different molecular weight component ETC according to any one of claims 1 to 4,
Be characterized in that, the reaction reagent bottle is provided with the reaction reagent, the reaction reagent be 2,2 '-azine group of oxidant-it is bis--
(3- ethyl benzo thiazoline quinoline -6- sulfonic acid) (AZB·+) or reducing agent N, N '-it is bis--(3- sulphonyl propyl) -4,4 '-bipyridyls
(ZiV·-) solution.
6. the device of detection dissolved organic matter different molecular weight component ETC according to any one of claims 1 to 5,
It is characterized in that, the gel chromatography column is porous methacrylate filler, and the packing material size is 5-10 μm；The gel layer
Analysis column diameter is 5-10mm, long 250-350mm.
7. a kind of using such as any one of claim 1 to 6 described device detection dissolved organic matter different molecular weight component ETC
Method, which comprises the steps of:
A. reaction reagent is prepared, and is provided into the reaction reagent access under oxygen-free environment, the reaction reagent is in specific wavelength
There is absorption maximum；
B. flowing carrier reagent is prepared, and is provided into the flowing carrier reagent access under oxygen-free environment；
C., the correlations such as flowing carrier reagent flow rate, reaction reagent flow velocity, minute and UV detector Detection wavelength are set
Conditional parameter；
D. inject sample into flowing carrier reagent access, sample follow flowing carrier reagent through gel chromatography column by molecular weight into
After row separation, converge with the reaction reagent in reaction reagent access, redox reaction occurs, then measure by UV detector
Its UV absorption signal；
E. according to the UV absorption signal and standard curve of measurement, the electron transfer capacity of molecular weight analyte distribution is calculated.
8. the method for detection dissolved organic matter different molecular weight component ETC according to claim 7, it is characterised in that:
Preferably, in step A, reaction reagent preparation method includes: (a) oxidant AZB·+(detection electronics supply capacity) is prepared:
AZB is dissolved in 0.5mmol/L H2SO4, add ultrapure water to be made into AZB aqueous solution, liquor natrii hypochloritis be added dropwise with continuous stirring, make
2/3rds AZB are oxidized to AZB in system·+, finally obtain 40 μm of ol/L AZB·+；(b) reducing agent ZiV·-(detection electronics
Ability to accept) it prepares: in electrochemical workstation, electrolyte and 750 μM of ZiV are added, in EHIt is reacted under the conditions of=- 0.49V,
2/3rds ZiV are reduced, ZiV is obtained·-Solution；
Preferably, the flowing carrier reagent is the phosphate buffer solution of 4.0mM pH=7, including 2.4mM NaH2PO4·
2H2O, 1.6mM Na2HPO4·12H2O and 25mM Na2SO4；
Preferably, in the step C, flowing carrier reagent flow rate be 0.2~1.0mL/min, reaction reagent flow velocity be 0.05~
0.2mL/min, minute 1-2h.
Preferably, when detecting electronics supply capacity, UV detector Detection wavelength is 415nm；It is purple when detecting electron acceptability
External detector Detection wavelength is 603nm.
9. the method for detection dissolved organic matter different molecular weight component ETC according to claim 7 or 8, feature exist
In before injection, by 0.45 μm of membrane filtration, the DOC concentration range of sample is 0.5- to the sample in step D
200mg/L, Sample injection volume 0.1-2mL.
10. the method for detection dissolved organic matter different molecular weight component ETC according to any one of claims 7 to 9,
It is characterized in that, in step E, the measuring method of standard curve includes the following steps: (a) molecular weight distribution standard curve determination；Choosing
Take kayexalate as standard sample；Selecting relative molecular mass is 210,3610,7540,32000,126700
Reaction reagent is replaced with high purity water by PSS standard specimen, measures and draw molecular weight distribution standard curve, is obtained appearance time and is divided
Linear relationship between son amount；(b) electronics supply capacity standard curve determination；Ascorbic acid (ascorbic acid) is selected to make
For standard sample, (known ascorbic acid electronics supply capacity is 2mol e-/ mol), measurement concentration is 1,2,3,4,5mol/L
Ascorbic acid obtains the linear relationship between peak area and electronics supply capacity；(c) electron acceptability standard curve determination；
Selecting anthraquinone -2,6- sodium disulfonate (AQDS) as standard sample, (electron acceptability of known AQDS is 2mol e-/ mol),
The AQDS that concentration is 1,2,3,4,5mol/L is measured, the linear relationship between peak area and electron acceptability is obtained.
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