CN115901744A - Rapid determination method and determination device for trace manganese in water - Google Patents
Rapid determination method and determination device for trace manganese in water Download PDFInfo
- Publication number
- CN115901744A CN115901744A CN202310005344.0A CN202310005344A CN115901744A CN 115901744 A CN115901744 A CN 115901744A CN 202310005344 A CN202310005344 A CN 202310005344A CN 115901744 A CN115901744 A CN 115901744A
- Authority
- CN
- China
- Prior art keywords
- manganese
- water
- water sample
- membrane
- mno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 89
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011572 manganese Substances 0.000 title claims abstract description 50
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000001914 filtration Methods 0.000 claims abstract description 89
- 239000012528 membrane Substances 0.000 claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000012190 activator Substances 0.000 claims abstract description 14
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 10
- 230000000007 visual effect Effects 0.000 claims abstract description 10
- 238000004737 colorimetric analysis Methods 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000003093 cationic surfactant Substances 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 10
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 8
- 239000004677 Nylon Substances 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 229920001778 nylon Polymers 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 4
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 claims description 3
- 229960001950 benzethonium chloride Drugs 0.000 claims description 3
- WNBGYVXHFTYOBY-UHFFFAOYSA-N benzyl-dimethyl-tetradecylazanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 WNBGYVXHFTYOBY-UHFFFAOYSA-N 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 238000007306 functionalization reaction Methods 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 238000011002 quantification Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000004067 bulking agent Substances 0.000 claims 1
- 230000000149 penetrating effect Effects 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 19
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 230000000873 masking effect Effects 0.000 abstract description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 229930006000 Sucrose Natural products 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229960004793 sucrose Drugs 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005375 photometry Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002357 osmotic agent Substances 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-M periodate Chemical compound [O-]I(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-M 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
Images
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides a rapid determination method of trace manganese in water, which comprises the following steps: (1) Taking a water sample to be detected, adding a color developing agent into the water sample to be detected, and oxidizing free low-valence manganese ions in the water sample to be detected into red MnO 4 ‑ Developing the color of the water sample to be detected; (2) Dropping functional activator on hydrophilic filtering membrane to make filtering membrane possess trapped MnO 4 ‑ The function of (a); (3) Passing the water sample developed in the step (1) through a filtering membrane, mnO 4 ‑ Is trapped on the filter membrane; (4) And taking out the filtering membrane, and carrying out semi-quantitative determination on the content of manganese in the water sample by a visual colorimetry or quantitatively determining the content of manganese in the water sample by a refractometer. The method can simply, conveniently and quickly determine the content of trace manganese in water, has high sensitivity, and does not need to adopt a drastic methodThe toxic cyanide is used as a masking agent, and has the advantages of high selectivity, quick color development, stable color development, simple and convenient operation and the like. The invention also provides a device for rapidly measuring the trace manganese in the water.
Description
Technical Field
The invention relates to the field of water quality detection, in particular to a rapid determination method and a rapid determination device for trace manganese in water.
Background
Manganese is one of the trace elements essential to living beings. Manganese compounds exist in various forms, and due to oxygen deficiency, manganese exists in soluble divalent manganese form in ground water, while soluble trivalent manganese complexes and tetravalent manganese suspensions also exist in surface water. Manganese is present in water samples from several micrograms/liter to several hundred micrograms/liter, rarely exceeding milligrams/liter. Manganese salt is not toxic, but the manganese content in water is too high, which can cause clothes, textiles and paper to leave unsightly spots, particularly, divalent manganese in tap water can be oxidized into manganese dioxide precipitate due to disinfection, and the manganese dioxide precipitate is adsorbed on a water pipe to color the water pipe, which not only affects the turbidity and the chromaticity of water quality, but also affects the taste of drinking water, and the manganese content specified in the sanitary standard of drinking water must not exceed 0.1mg/L. Most enterprises producing packaged drinking water need to sample in each link of production to test the manganese content of water quality so as to ensure that the chromaticity and the taste of the water in the long-time storage process of the packaged water are not changed, and the manganese content in the final finished product water is generally required to be not more than 10 mug/L.
The laboratory methods commonly used for measuring manganese include potassium periodate oxidation, formaldoxime color development, PAN color development, catalytic kinetics photometry, graphite furnace atomic absorption method and the like. The graphite furnace atomic absorption method is simple and convenient to operate and high in sensitivity, but expensive instruments and equipment are needed, and the graphite furnace atomic absorption method is not easy to popularize and apply on site; the rapid detection reagent prepared based on the oxidation method or the color development method has the advantages of low price, simple and convenient operation, low analysis cost, relative environmental protection, convenient popularization and application and the like, and is an analysis method with development prospect at present. The catalytic kinetics photometry has the advantages of high sensitivity, strong anti-interference capability and the like, but has long color development time (about 30 minutes is needed for measuring 1 sample), unstable color development, harsh reaction conditions, extremely easy influence by temperature and pH, higher requirements on the preparation of reagents and the operation level of field testers, and relative difficulty in application. The formaldehyde oxime color development method has low sensitivity and poor interference resistance, and is not suitable for the rapid detection of trace manganese in surface water or drinking water. The PAN color development method has the advantages of rapid color development (only 2 minutes are needed for measuring 1 sample), stability, simple and convenient operation and the like, but the method has poor interference resistance, needs virulent potassium cyanide as a masking agent and is not beneficial to industrial production. The potassium periodate oxidation method has high selectivity on manganese ions, has the advantages of rapid color development (only 2 minutes are needed for measuring 1 sample), stable color development, simple and convenient operation and the like, but the method has low test sensitivity, and the lowest visual detection limit of the existing kit on the market is 0.1mg/L.
Disclosure of Invention
The invention aims to overcome the problem of low sensitivity of the existing permanganate oxidation method, improves the existing permanganate oxidation method on the basis of the periodate oxidation method, and provides a method and a device for quickly measuring the trace manganese in water, which can simply, conveniently and quickly measure the trace manganese content in water, have high sensitivity, do not need to adopt virulent cyanide as a masking agent, and have the advantages of high selectivity, quick color development, stable color development, simple and convenient operation and the like.
In order to achieve the above object, in one aspect, the present invention provides a method for rapidly determining trace manganese in water, comprising the steps of:
(1) Oxidation of low-valent manganese
Taking a water sample to be detected, adding a color developing agent into the water sample to be detected, and oxidizing free low-valence manganese ions in the water sample to be detected into red MnO 4 - Developing the color of the water sample to be detected;
(2) Functionalization of filtration membranes
Dropping a functional activating agent on the hydrophilic filtering membrane so as to enable the filtering membrane to capture MnO 4 - The function of (a);
（3）MnO 4 - is collected by
Will be described in step (1)The developed water sample passes through the filtering membrane, and MnO 4 - Is trapped on the filter membrane;
(4) Quantification of manganese
And taking out the filtering membrane, and carrying out semi-quantitative determination on the manganese content in the water sample by a visual colorimetry or quantitatively determining the manganese content in the water sample by a refractometer.
The test principle of the method is as follows:
the free ions in water are firstly oxidized into red permanganate ions (MnO) by using a color developing agent 4 - ) And adding a functional activator to the hydrophilic filtration membrane to functionalize the filtration membrane so that the filtration membrane can trap MnO 4 - Then passing a certain amount of oxidized water sample through a filtering membrane, mnO 4 - The manganese ion concentration measuring device is characterized in that the manganese ion concentration measuring device is trapped on a filtering membrane, manganese ions contained in a water sample are highly concentrated, the color of the filtering membrane is observed through naked eyes, and the manganese content in the water sample can be measured semi-quantitatively through a visual colorimetry or quantitatively through a refractometer.
In some embodiments, the developer includes an oxidizing agent for oxidizing free low-valence manganese ions in the sample of water to be tested to the MnO 4 - . Illustratively, the oxidizing agent is potassium periodate, but is not limited thereto.
In some embodiments, the color developer further comprises a pH regulator for regulating the pH of the water sample to be tested to be neutral, and the pH regulator can be at least one of anhydrous potassium pyrophosphate, disodium hydrogen phosphate and citric acid. The combination of anhydrous potassium pyrophosphate, disodium hydrogen phosphate and citric acid is preferably adopted, and a ternary buffer system with strong buffer capacity is adopted, so that most of water samples can be buffered to the optimal color development pH value; the anhydrous potassium pyrophosphate can enable a water sample to develop color rapidly at room temperature.
In some embodiments, the color developer comprises, by weight, 21-55% of a pH adjuster, 5-25% of an oxidizing agent, and 20-74% of a filler. The filler is illustratively, but not limited to, anhydrous sodium sulfate.
In some embodiments, the developer comprises, by weight, 5-20% of anhydrous potassium pyrophosphate, 15-30% of disodium hydrogen phosphate, 1-5% of citric acid, 5-25% of potassium periodate, and 20-74% of anhydrous sodium sulfate. In a specific embodiment, each reagent is dried and then passes through at least 40 meshes, and after being uniformly mixed, the reagent is quantitatively packaged by an aluminum foil bag, wherein the weight of each reagent is 0.10-0.20 g/bag, but not limited to.
In some embodiments, the color developer comprises 10% anhydrous potassium pyrophosphate, 20% disodium hydrogen phosphate, 3% citric acid, 20% potassium periodate, 47% anhydrous sodium sulfate.
In some embodiments, the functional activator comprises a benzyl-containing macromolecular cationic surfactant. The benzyl-containing macromolecular cationic surfactant can generate stronger adsorption with a hydrophilic filtering membrane through acting forces such as hydrogen bonds, pi electron polarization and the like, has better association effect with permanganate radicals, and can capture permanganate ions on the filtering membrane to the maximum extent. Illustratively, the benzyl-containing macromolecular cationic surfactant is selected from at least one of benzyldimethyltetradecylammonium, dodecyldimethylbenzylammonium chloride, benzethonium chloride.
In some embodiments, the functional activator comprises, in weight percent, 15-30% of a benzyl-containing macromolecular cationic surfactant, 25-40% of a penetrant, 10-20% of a thickener, and the balance water. The addition of the penetrant can reduce the surface tension of the functional activator, so that the macromolecular cationic surfactant can permeate into the interior of the membrane; the thickening agent is added to properly reduce the permeation speed, and the action time of the macromolecular cationic surfactant and the filtering membrane is prolonged, so that the macromolecular cationic surfactant and the filtering membrane are fully adsorbed on the filtering membrane. By way of example, the osmotic agent may be, but is not limited to, ethanol; the thickener may be, but is not limited to, sucrose or carboxymethylcellulose. In addition, the functional activating agent is in the form of bottled liquid reagent, which is convenient for use, but not limited to this.
In some embodiments, the functional activator comprises dodecyl dimethyl benzyl ammonium chloride 18%, ethanol 30%, sucrose 15%, and water 37%.
In some embodiments, the filtering membrane is selected from a hydrophilic membrane such as a nylon membrane or a cellulose acetate membrane, and preferably, the material of the filtering membrane is a nylon membrane. Further, the aperture of the filtering membrane is 0.2-2.0 μm, the aperture is too small, the filtering is too slow, the testing speed is influenced, the aperture is too large, the filtering is too fast, the capture efficiency of the substance to be tested is influenced, and preferably, the aperture of the filtering membrane is 1.2 μm.
On the other hand, the invention also provides a measuring device for realizing the rapid measuring method of the trace manganese in the water, which comprises an injector, a filtering device and a connector positioned between the injector and the filtering device, wherein the connector is of a hollow structure so as to communicate the injector and the filtering device, the filtering membrane is arranged in the filtering device, and the connector, the injector and the filtering device are all detachable devices. It will be appreciated that the upper end bore of the connector matches the outer diameter of the outlet of the syringe and the lower end bore of the connector matches the inlet of the filter unit. Illustratively, the syringe may be, but is not limited to, a polypropylene syringe and the connector may be, but is not limited to, a polyethylene hollow connector.
In some embodiments, the filtering apparatus includes a hollow casing, a bearing portion and the filtering membrane are sequentially disposed in the casing from a direction away from the connector to a direction close to the connector, the bearing portion has a plurality of holes and can position the filtering membrane. It will be appreciated that the lower end of the connector directly abuts the filter membrane, which can improve test sensitivity. The bearing part is provided with a plurality of holes for filtering filtrate, the upper end surface of the bearing part can be a plane for placing the filtering membrane, and the bearing part can also be a positioning groove for placing the filtering membrane without limitation.
The invention has the following beneficial effects:
(1) According to the invention, after the filtering membrane is subjected to functionalization treatment, the manganese in water is highly enriched on the filtering membrane by combining a potassium permanganate oxidation method, and higher test sensitivity can be achieved.
(2) Periodate Ion (IO) 4 - ) And the common anions in water may form ion association with the cationic surfactant to be adsorbed on the filtering membrane, but the association does not show color and does not interfere the measurement, so the method has the measurement of manganese ionsGood selectivity.
(3) The ternary buffer system has strong buffer capacity and can buffer most of water samples to the optimal color development pH value; the anhydrous potassium pyrophosphate can enable a water sample to develop color rapidly at room temperature.
(4) The functional activator is added with a macromolecular cationic surfactant containing benzyl, can generate stronger adsorption with a hydrophilic nylon membrane or a cellulose acetate membrane through the acting forces of hydrogen bonds, pi electron polarization and the like, has better association effect with permanganate and can capture the permanganate ions on a filter membrane to the maximum extent; the penetrant is added to reduce the surface tension, so that the macromolecular cationic surfactant can permeate into the membrane; the thickening agent is added, so that the permeation speed can be properly reduced, and the action time of the macromolecular cationic surfactant and the filtering membrane is prolonged, so that the macromolecular cationic surfactant and the filtering membrane are fully adsorbed on the filtering membrane.
(5) According to the measuring device, the lower end of the connector is connected with the filtering device, wherein the caliber of the lower end of the connector is set to be 3-4mm, so that the measuring sensitivity can be ensured, and the measuring by visual colorimetry and photometry of a refractometer can be facilitated.
Drawings
FIG. 1 is a schematic view of the apparatus for rapid determination of trace manganese in water according to the present invention.
FIG. 2 is a standard color chart obtained in example 4 of the present invention.
Detailed Description
Referring to fig. 1, a device for rapidly measuring trace manganese in water is shown, which includes an injector 1, a filtering device 3, and a connector 2 located between the injector 1 and the filtering device 3, wherein the connector 2 is a hollow structure to communicate the injector 1 and the filtering device 3, and a filtering membrane 4 is disposed in the filtering device 3. The connector 2 is detachably connected with the syringe 1 and the filter device 3, for example, by clipping, screwing, etc. It will be appreciated that the upper end bore of the connector 2 matches the outer diameter of the outlet of the syringe 1 and the lower end bore of the connector 2 matches the inlet of the filter means 3. Illustratively, the syringe 1 may be, but is not limited to, a polypropylene syringe 1 and the connector 2 may be, but is not limited to, a polyethylene hollow connector.
In the techniqueIn the embodiment, the hydrophilic filtration membrane 4 is functionalized with the functional activator to make the filtration membrane 4 have MnO trapping function 4 - The water sample after a certain amount of oxidation passes through a filtering membrane 4 4 - Is caught on filtering membrane 4, and the manganese ion that contains in the water sample is highly concentrated, through the colour of naked eye observation filtering membrane 4, and accessible visual colorimetry carries out the content of semi-quantitative determination manganese in the water sample, or passes through the content of manganese in the refractometer quantitative determination water sample.
Illustratively, the diameter of the lower end of the connector 2 is 3-4mm, the length is about 1cm, and the diameter of the filter membrane 4 is about 7mm, so that the test sensitivity can be improved, and the visual colorimetry and refractometry measurement can be conveniently carried out.
In some embodiments, the filtering device 3 includes a hollow housing 6, a supporting portion 5 and a filtering membrane 4 are sequentially disposed in the housing 6 from a direction away from the connector 2 to a direction close to the connector 2, and the supporting portion 5 has a plurality of holes and can position the filtering membrane 4. It will be appreciated that the lower end of the connector 2 directly abuts the filter membrane 4, which can improve the sensitivity of the test. The bearing part 5 is provided with a plurality of holes for filtering the filtrate, the upper end surface of the bearing part 5 can be a plane for placing the filtering membrane 4, and can also be a positioning groove for placing the filtering membrane 4 without limitation.
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparing a color developing agent: weighing 10g of anhydrous potassium pyrophosphate, 20g of disodium hydrogen phosphate, 3g of citric acid, 5g of potassium periodate and 62g of anhydrous sodium sulfate, drying the reagents, sieving the reagents with 40 meshes, uniformly mixing, and quantitatively sealing and packaging the reagents on an automatic packaging machine by adopting an aluminum foil bag, wherein each bag is 0.10 g.
(2) Configuration of functional activator: weighing 18g of benzethonium chloride, adding 37g of pure water and 30g of ethanol, ultrasonically dissolving, finally adding 15g of cane sugar, and quantitatively subpackaging by using a 15mL dropping bottle after complete dissolution, wherein each 10mL bottle is used.
(3) Taking 2mL of water sample into a clean glass tube, adding a bag of color developing agent, shaking uniformly, standing for reaction for 2 minutes, dropwise adding 2 drops of functional activating agent on a nylon filtering membrane (with the aperture of 0.45 mu m) in a filtering device, completely absorbing the developed water sample into a 2 mL-specification injector, installing a hollow connector with the aperture of 4mm at the lower end of the injector, connecting the filtering device to the lower end of the connector, slowly pushing the developed water sample through the filtering membrane by an injector push rod, taking down the filtering device, and directly measuring the content of manganese in the water sample by a visual colorimetry.
Example 2
(1) Preparing a color developing agent: weighing 10g of anhydrous potassium pyrophosphate, 20g of disodium hydrogen phosphate, 3g of citric acid, 10g of potassium periodate and 57g of anhydrous sodium sulfate, drying the reagents, sieving the reagents with 40 meshes, uniformly mixing, and quantitatively sealing and packaging the reagents on an automatic packaging machine by adopting an aluminum foil bag, wherein each bag is 0.10 g.
(2) Preparation of functional activator: weighing 18g of dodecyl dimethyl benzyl ammonium chloride, adding 37g of pure water and 30g of ethanol, ultrasonically dissolving, finally adding 15g of sucrose, and quantitatively subpackaging by using 15mL dropping bottles after complete dissolution, wherein each bottle is 10 mL.
(3) Taking 4mL of water sample into a clean glass tube, adding a bag of color developing agent, shaking uniformly, standing for reaction for 2 minutes, dropwise adding 2 drops of functional activating agent on a nylon filtering membrane (with the aperture of 1.2 mu m) in a filtering device, completely absorbing the developed water sample into a 5 mL-specification injector, installing a hollow connector with the aperture of 4mm at the lower end of the injector, connecting the filtering device to the lower end of the connector, slowly pushing the developed water sample through the filtering membrane by an injector push rod, taking down the filtering device, and directly measuring the content of manganese in the water sample by a visual colorimetry.
Example 3
(1) Preparing a color developing agent: weighing 10g of anhydrous potassium pyrophosphate, 20g of disodium hydrogen phosphate, 3g of citric acid, 20g of potassium periodate and 47g of anhydrous sodium sulfate, drying the reagents, sieving the reagents with 40 meshes, uniformly mixing, and quantitatively sealing and packaging the reagents on an automatic packaging machine by adopting an aluminum foil bag, wherein each bag is 0.10 g.
(2) Configuration of functional activator: weighing 18g of benzyldimethyltetradecylammonium, adding 42g of pure water and 35g of ethanol, ultrasonically dissolving, finally adding 5g of carboxymethyl cellulose, and quantitatively subpackaging by using 15mL dropping bottles after complete dissolution, wherein each 10mL bottle is used.
(3) Taking 10mL of water sample into a clean glass tube, adding a bag of color developing agent, shaking uniformly, standing for reacting for 2 minutes, dropwise adding 2 drops of functional activating agent on a nylon filtering membrane (with the aperture of 2.0 microns) in a filtering device, completely absorbing the color developed water sample into a 10mL specification syringe, arranging a hollow connector with the aperture of 4mm at the lower end of the syringe, connecting the filtering device to the lower end of the connector, slowly pushing the color developed water sample through the filtering membrane by a syringe push rod, taking down the filtering device, taking out the filtering membrane, and quantitatively determining by a refractometer.
Example 4
Preparing a series of manganese standard solutions: 0.0 mg/L, 0.01 mg/L, 0.02 mg/L, 0.05 mg/L, 0.10 mg/L, 0.20 mg/L and 0.50mg/L, the water sample is subjected to color development and filtration treatment according to the method of the embodiment 2, a filter device is taken out to obtain a standard color development series, colors of all color gradation points are subjected to color matching and printing through a computer to prepare a standard color comparison card (as shown in figure 2), and the on-site rapid measurement of the actual water sample can be carried out through the comparison of the standard color comparison card.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it is not limited to the embodiments, and those skilled in the art should understand that the technical solutions of the present invention can be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A method for rapidly measuring trace manganese in water is characterized by comprising the following steps:
(1) Oxidation of low-valent manganese
Taking a water sample to be detected, adding a color developing agent into the water sample to be detected, and oxidizing free low-valence manganese ions in the water sample to be detected into red MnO 4 - Developing the color of the water sample to be detected;
(2) Functionalization of filtration membranes
Dropping functional activator on hydrophilic filtering membrane to make the filtering membrane possess trapping MnO 4 - The function of (c);
（3）MnO 4 - is collected by
Passing the water sample developed in the step (1) through the filtering membrane, wherein MnO is added 4 - Is trapped on the filter membrane;
(4) Quantification of manganese
And taking out the filtering membrane, and carrying out semi-quantitative determination on the manganese content in the water sample by a visual colorimetry or quantitatively determining the manganese content in the water sample by a refractometer.
2. The method for rapidly determining trace manganese in water according to claim 1, wherein said color-developing agent comprises a pH regulator for regulating the pH of the water sample to be tested to neutrality and an oxidizing agent for oxidizing free low-valence manganese ions in the water sample to be tested to said MnO 4 - 。
3. The method for rapidly measuring trace manganese in water as claimed in claim 2, wherein said color developing agent comprises 21-55% of pH adjusting agent, 5-25% of oxidizing agent and 20-74% of bulking agent by weight percentage.
4. The method for rapidly determining trace manganese in water as claimed in claim 3, wherein said developer comprises, by weight, 5-20% of anhydrous potassium pyrophosphate, 15-30% of disodium hydrogen phosphate, 1-5% of citric acid, 5-25% of potassium periodate, and 20-74% of anhydrous sodium sulfate.
5. The method for rapidly determining trace manganese in water according to claim 1, wherein said functional activator comprises a benzyl-containing macromolecular cationic surfactant.
6. The method for rapidly determining trace manganese in water according to claim 5, wherein said benzyl-containing macromolecular cationic surfactant is at least one selected from the group consisting of benzyldimethyltetradecylammonium, dodecyldimethylbenzylammonium chloride and benzethonium chloride.
7. The method for rapidly determining trace manganese in water according to claim 5, wherein the functional activator comprises 15-30% of benzyl-containing macromolecular cationic surfactant, 25-40% of penetrating agent, 10-20% of thickening agent and the balance of water in percentage by weight.
8. The method for rapidly measuring trace manganese in water according to claim 1, wherein said filtration membrane is selected from a nylon membrane or a cellulose acetate membrane.
9. An apparatus for rapidly determining trace manganese in water according to any one of claims 1 to 8, comprising a syringe, a filtering apparatus and a connector between the syringe and the filtering apparatus, wherein the connector is of a hollow structure to connect the syringe and the filtering apparatus, and the filtering membrane is disposed in the filtering apparatus.
10. The measuring device according to claim 9, wherein the filter device further comprises a hollow housing, a support part and the filter membrane are sequentially arranged in the housing from a direction away from the connector to a direction close to the connector, and the support part has a plurality of holes and can position the filter membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310005344.0A CN115901744A (en) | 2023-01-04 | 2023-01-04 | Rapid determination method and determination device for trace manganese in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310005344.0A CN115901744A (en) | 2023-01-04 | 2023-01-04 | Rapid determination method and determination device for trace manganese in water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115901744A true CN115901744A (en) | 2023-04-04 |
Family
ID=86474723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310005344.0A Pending CN115901744A (en) | 2023-01-04 | 2023-01-04 | Rapid determination method and determination device for trace manganese in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115901744A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1255061A (en) * | 1983-11-30 | 1989-06-06 | James A. Jagodzinski | Separation membranes |
| CN101144782A (en) * | 2007-10-18 | 2008-03-19 | 上海交通大学 | Quick test strip for detecting hydrogen peroxide in food |
| CN101639448A (en) * | 2009-09-04 | 2010-02-03 | 广东环凯微生物科技有限公司 | Rapid measurement reagent for manganese concentration in water and use method thereof |
| CN102279182A (en) * | 2011-05-12 | 2011-12-14 | 大连理工大学 | Preparation method of detection membrane for iron pollution on surface of austenitic stainless steel |
| JP2012047714A (en) * | 2010-08-30 | 2012-03-08 | Kyoritsu Rikagaku Kenkyusho:Kk | Method for simply determining low concentration manganese |
| CN102507554A (en) * | 2011-10-26 | 2012-06-20 | 华南理工大学 | Method for detecting beryllium content in water |
| CN109060698A (en) * | 2018-10-31 | 2018-12-21 | 成都海兰天澄科技股份有限公司 | Manganese rapid assay methods in water quality |
-
2023
- 2023-01-04 CN CN202310005344.0A patent/CN115901744A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1255061A (en) * | 1983-11-30 | 1989-06-06 | James A. Jagodzinski | Separation membranes |
| CN101144782A (en) * | 2007-10-18 | 2008-03-19 | 上海交通大学 | Quick test strip for detecting hydrogen peroxide in food |
| CN101639448A (en) * | 2009-09-04 | 2010-02-03 | 广东环凯微生物科技有限公司 | Rapid measurement reagent for manganese concentration in water and use method thereof |
| JP2012047714A (en) * | 2010-08-30 | 2012-03-08 | Kyoritsu Rikagaku Kenkyusho:Kk | Method for simply determining low concentration manganese |
| CN102279182A (en) * | 2011-05-12 | 2011-12-14 | 大连理工大学 | Preparation method of detection membrane for iron pollution on surface of austenitic stainless steel |
| CN102507554A (en) * | 2011-10-26 | 2012-06-20 | 华南理工大学 | Method for detecting beryllium content in water |
| CN109060698A (en) * | 2018-10-31 | 2018-12-21 | 成都海兰天澄科技股份有限公司 | Manganese rapid assay methods in water quality |
Non-Patent Citations (1)
| Title |
|---|
| 刘硕 等: "自然地理与资源环境专业实验教程", 哈尔滨工程大学出版社, pages: 171 - 174 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ramon-Marquez et al. | Novel optical sensing film based on a functional nonwoven nanofibre mat for an easy, fast and highly selective and sensitive detection of tryptamine in beer | |
| JP3740466B2 (en) | Reagent for optical emission measurement of analyte | |
| Suah et al. | A novel polymer inclusion membranes based optode for sensitive determination of Al3+ ions | |
| CN105388149A (en) | Reagent and method for fast detecting water quality total hardness | |
| CN113717716A (en) | Silicon nanoparticle probe and preparation method and application thereof | |
| US4300905A (en) | Rapid test for ascorbic acid determination | |
| CN115901744A (en) | Rapid determination method and determination device for trace manganese in water | |
| US5858797A (en) | Test composition, device and method for the colorimetric determination of phosphorus | |
| Alghamdi | Determination of allura red in some food samples by adsorptive stripping voltammetry | |
| CN109916893A (en) | A kind of dry chemistry reagent piece of quantitative detection albumin content and preparation method thereof | |
| Felix et al. | Measurements of ambient ozone using indigo blue-coated filters | |
| CN108195830B (en) | Visual detection method for trace copper ions | |
| Alghamdi | A square-wave adsorptive stripping voltammetric method for the determination of Amaranth, a food additive dye | |
| US20040161366A1 (en) | Devices, tests and methods for the analysis of wine samples | |
| US20140170037A1 (en) | Dye entrapped sol-gel film based test strip sensor for nitrite and a process of preparing said strip sensor | |
| RU2374639C1 (en) | Method of detecting iron (ii) | |
| Lu et al. | Optical fibre fluorosensor for cadmium with diethylaminoethyl-Sephadex as a substrate | |
| Scheggi et al. | pH sensing by fibre optics | |
| WO2002090975A2 (en) | Method and device for identifying volatile substances in solution | |
| CN109900691B (en) | Test paper for rapidly detecting mercury ions, preparation method and application thereof | |
| Ebdelli et al. | Ion sensing film optodes based on chromogenic calix [4] arene: application to the detection of Hg 2+, Ni 2+ and Eu 3+ ions | |
| JPH09133678A (en) | Method for measuring specific gravity of liquid sample, testing tool and test piece | |
| RU2374637C1 (en) | Method of detecting copper (i) | |
| CN112577948A (en) | Copper ion rapid detection method and device | |
| Garcia et al. | Determination of iron at ng/ml level by solid phase spectrophotometry after preconcentration on cation exchange filters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230404 |