EP3265795A1 - Électrode au phosphate et procédé de détermination de la concentration de phosphate - Google Patents

Électrode au phosphate et procédé de détermination de la concentration de phosphate

Info

Publication number
EP3265795A1
EP3265795A1 EP16707431.9A EP16707431A EP3265795A1 EP 3265795 A1 EP3265795 A1 EP 3265795A1 EP 16707431 A EP16707431 A EP 16707431A EP 3265795 A1 EP3265795 A1 EP 3265795A1
Authority
EP
European Patent Office
Prior art keywords
phosphate
coating
electrode
concentration
phosphate electrode
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.)
Withdrawn
Application number
EP16707431.9A
Other languages
German (de)
English (en)
Inventor
Lars H WEGNER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aqseptence Group GmbH
Original Assignee
Aqseptence Group GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Aqseptence Group GmbH filed Critical Aqseptence Group GmbH
Publication of EP3265795A1 publication Critical patent/EP3265795A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333—Ion-selective electrodes or membranes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C03C11/007—Foam glass, e.g. obtained by incorporating a blowing agent and heating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/307—Disposable laminated or multilayered electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/4035—Combination of a single ion-sensing electrode and a single reference electrode
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/182—Specific anions in water

Definitions

  • the present invention relates to a phosphate electrode having a base body and a first coating provided on the base body at least in regions, the base body containing elemental cobalt and the first coating containing a cobalt phosphate.
  • the invention further comprises a method for determining a phosphate concentration with the phosphate electrode.
  • the phosphate content of the water is z.
  • a precise monitoring of the phosphate concentration, especially in the activated sludge tank and in the drain, is required in order to minimize the phosphate effluent load of the plant by controlling the aeration phases and optionally by precipitation.
  • the requirements placed on an analytical process suitable for wastewater treatment plants include simple handling and high reliability at the lowest possible cost.
  • a phosphate electrode which meets these criteria and which can be used for continuous phosphate measurement directly in the activated sludge without further sample preparation is not yet available.
  • Ion-selective electrodes which are already routinely used in sewage treatment plants for the determination of nitrate and ammonium concentrations.
  • Ion-selective electrodes generate a voltage which is specific to the concentration of the ion to be determined in the medium surrounding the electrode. After calibration against media of known phosphate concentration, it is possible to deduce the phosphate content of an unknown aqueous solution (eg a wastewater sample) from the measured potential value.
  • interfering ions cause potential or voltage changes in the electrode. So far, the voltage signal no longer depends exclusively on the concentration of the ion to be determined (also called analyte ion), but is also influenced by the concentration of the interfering ions.
  • interfering ions not only interfering ions but also gases can cause a voltage change by reaction with the electrode surface. Since, in the case of transverse sensitivity to gases, a reaction of the gases which precedes the course of the potential can generally take place upstream of the corresponding anions, in this case the fundamental mechanism is the same as in the case of the interference of interfering ions.
  • Expert measures for reducing the cross-sensitivity of ion-selective electrodes include the use of ion-selective membranes and complex reference measurements, the change in potential of known interfering ions serving as a reference signal at various concentrations.
  • a phosphate electrode is provided with a base body and a first coating provided on the base body at least in regions.
  • the main body contains elemental cobalt, in particular the main body consists of at least 90 wt .-%, preferably at least 95 wt .-%, of cobalt. Cobalt alloys can also be used.
  • the first coating comprises a cobalt phosphate, in particular Co 3 (PO 4 ) 2, CoHPO 4 , or Co (H 2 PO 4 ) 2, preferably CoHPO 4 .
  • a second coating is provided, which binds protons and / or releases hydroxide ions.
  • the second coating essentially serves to ensure a constant, basic pH on the surface of the phosphate electrode.
  • this has been found to be sufficient because the voltage change measured with the phosphate electrode is caused by reactions on the surface of the electrode.
  • the achievement of a basic pH on the surface can be checked by immersing the phosphate electrode in a small volume, for example 50 ml, of a neutral or weakly buffered solution, in particular a very dilute KCl solution (eg 0.1 10 "3 mol / L), the pH is increased to at least 7.5, in total, by setting a basic pH, the cross-sensitivity reduced a phosphate electrode with a cobalt-based body.
  • the phosphate electrode according to the invention can also be used for determining the phosphate concentration in large volumes, for example with more than 1000 L, are used.
  • the alkaline pH in the environment is adjusted locally around the phosphate electrode, since the determination of the phosphate concentration is based on a chemical reaction on the surface of the electrode and therefore the measurement conditions locally around this electrode essentially depend on it. It is particularly advantageous that in the actual analyte, for example.
  • the activated sludge of a water treatment plant on average, another pH, namely, typically 6.5 to 7.0, may be present. It has also been found that cross sensitivity of the cobalt based phosphate electrode can be reduced by adjusting a basic pH in view of the partial pressure of certain gases, especially oxygen.
  • the cross-sensitivity in particular the oxygen
  • the second coating has a pH of between 7.5 and 9, in particular between 8 and 9, preferably between 8.2 and 9, particularly preferably between 8.6 and 9, in 50 ml of a strongly diluted KCl. Solution (eg 0.1 mM) at 25 ° C.
  • the stated values are given with an accuracy of ⁇ 0.1.
  • This material property of the second coating can be easily checked by immersing the appropriately designed phosphate electrode in 1 L of deionized water at 25 ° C. It has been found that the lowest cross-sensitivity of the phosphate electrode to other anions can be observed in the given pH range, while the sensitivity, ie the sensitivity, of the electrode to the phosphate is hardly impaired.
  • the second coating comprises a, in particular hydrophilic and / or water-permeable, solid buffer system.
  • a buffer system (or even buffer) is a mixture of an acid and the corresponding conjugated base, for example an acetic acid / acetate mixture. Buffers are characterized by the fact that the pH changes only slightly when adding an acid or a base. Therefore, buffers are particularly suitable for the adjustment of a basic environment around the phosphate electrode. It is particularly preferred if the acid strength of the acid of the buffer System corresponds to the pH value to be set by the buffer system.
  • the second coating comprises a borosilicate glass.
  • the borosilicate glass is used as a fixed buffer system.
  • the borosilicate glass is used in particular as a powder, the borosilicate glass preferably has defined particle sizes, it being preferred if the average particle size is 18 ⁇ m and the particle size distribution follows a Gaussian curve. Since borosilicate glasses usually have a basic pH of their own, they are particularly suitable for the present invention. If the pH is to be set to the particularly preferred values between 7.5 and 9, 8 and 9, 8.2 and 9 and / or 8.6 and 9, this is possible with borosilicate glasses, for example by modifying the surface.
  • the borosilicate glass has a modified surface, whereby an adjustment of the pH is achieved by the borosilicate glass.
  • a modification of the surface may, for example, consist in that the borosilicate glass is mixed with a solution of a basic or acidic salt, for example sodium acetate or aluminum chloride, and subjected to a temperature treatment. This results in a connection of the salt to the borosilicate glass surface.
  • a basic or acidic salt for example sodium acetate or aluminum chloride
  • the second coating comprises a carrier material which has been correspondingly functionalized to set a basic pH.
  • a carrier material which has been correspondingly functionalized to set a basic pH.
  • Such functionalization can be achieved, for example, by the chemical coupling of functional groups, in particular aminoalkylene.
  • functionalized carrier materials include functionalized silica gel, functionalized graphene and / or functionalized polystyrene.
  • the second coating comprises microcapsules.
  • volatile, for example liquid, substances for regulation in order to produce a basic environment for the phosphate electrode, while at the same time preventing too rapid removal of the corresponding substances.
  • a matrix encapsulation can be used, wherein the corresponding substance is homogeneously mixed with a substance forming the matrix, thereby achieving a uniform distribution.
  • the rate of release is determined by the diffusion of the substance into the environment or the degradation rate of the matrix.
  • the microcapsules themselves from doped material, for example polymers doped with amino groups.
  • the capsule material itself can be used as a regulator of pH, while the properties of the encapsulated substances and the rate of release of these substances allow additional adjustments.
  • the second coating can be accommodated in filter papers which can be fixed to the electrode base body and / or the first coating. Filter papers made of cellulose are generally suitable for this purpose. However, preferred are non-biodegradable filter papers, as these extend the life of the electrode. Filter papers have proven to be particularly preferred Fiberglass exposed. The filter papers can also be used without binder.
  • Filter bags are suitable for fixing the second coating, in particular microcapsules. These filter bags increase the mechanical stability of the second coating without significantly affecting the exchange of the analyte and the reactions on the surface of the electrode for determining the phosphate. If filter papers made of glass fiber used, can be dispensed with an additional wrapping through a filter bag, since these filter papers already have a high mechanical stability.
  • At least one gas supply connected to a gas source with at least one opening which is associated with the electrode.
  • the at least one opening is arranged such that upon introduction of a gas, for example air into which at least one gas feed line, the main body, in particular the entire phosphate electrode, is lapped by the introduced gas. It is thereby generated a constant partial pressure of the components contained in the gas on the surface of the phosphate electrode. This additionally minimizes cross-sensitivity of the electrode to variable gas partial pressures.
  • the gas which has been introduced to the oxygen it is particularly preferred for the gas which has been introduced to the oxygen to have a high cross-sensitivity of common cobalt-based phosphate electrodes observed. Accordingly, a constant oxygen partial pressure (p (O 2 )) can be set and the cross-sensitivity can be further reduced. This is particularly important in the determination of the phosphate concentration in water treatment plants, since it must be determined under both aerobic and anaerobic conditions, the phosphate concentration.
  • a plurality of openings are provided in a gas line, wherein it is particularly preferred when the openings are distributed so that a uniform distribution of the introduced gas is achieved around the body.
  • a phosphate electrode is used as described above for determining the phosphate concentration in the activated sludge of a water treatment and / or wastewater treatment plant.
  • the object underlying the invention is also achieved by a method for determining the phosphate concentration in an aqueous analyte, in particular activated sludge of a water treatment and / or wastewater treatment plant, having the features of claim 8.
  • a phosphate electrode in particular of the type described above, is immersed in a setting solution before the determination of the phosphate concentration, specifically until the phosphate electrode emits a measurement signal which does not change over time.
  • the setting solution phosphates and interfering ions are added, that is, all anions on which the phosphate electrode can exhibit cross-sensitivity, preferably at a concentration typically expected in the aqueous analyte.
  • the phosphate electrode is already "used” to a similar ion level before the actual determination of the phosphate concentration.
  • the calibration of the phosphate electrode in the adjustment solution is made by the phosphate concentration is selectively varied stepwise.
  • time-invariable measurement signal is understood to mean that the measurement signal changes only slightly at a given time interval.
  • potential change of a phosphate electrode should be less than 1 mV / min, preferably 0.5 mV / min.
  • the pH of the adjusting solution corresponds approximately to the pH of the analyte solution, in particular between 5 and 9, preferably between 7.5 and 9, particularly preferably between 8 and 9, and very particularly preferably between 8.6 and 9 lies.
  • the cross-sensitivity of the phosphate electrode is extremely low, while the sensitivity of the phosphate electrode to the phosphate is maintained.
  • the determination of the phosphate concentration at a constant gas partial pressure is performed.
  • the total concentration of the interfering ions is not more than 100 mM, preferably not more than 50 mM, more preferably not more than 30 mM and most preferably not more than 20 mM.
  • 3a shows the change in the potential difference as a function of the addition of interfering ions and the phosphate concentration for a starting concentration of 0.52 mM sulfate, 2.82 mM chloride and 0.01 mM phosphate,
  • 3b shows the change in the potential difference as a function of the addition of interfering ions and the phosphate concentration for a starting concentration of 2.08 mM sulfate, 7.05 mM chloride and 0.01 mM phosphate,
  • Fig. 5a shows the change of the potential difference of an inventive
  • Phosphate electrode as a function of the addition of phosphate for a starting concentration of 0.52 mM sulfate, 2.82 mM chloride and 0.01 mM phosphate
  • Fig. 1 shows the potential difference change ⁇ measured with a phosphate electrode according to DE 1 0 2009 051 1 69 as a function of different interference ion concentrations at a pH of 7.4 and 8.8.
  • the potential difference is determined to be a reference electrode whose half-cell potential is not influenced by the phosphate concentration.
  • the analyzed analyte solutions contained dipotassium hydrogen phosphate (K 2 HPO 4 ) at a concentration of 0.01 mM.
  • the interfering ions nitrate (a, b), chloride (c, d) and sulphate (e, f) were added in the indicated concentrations.
  • ⁇ 0
  • AAV - - -
  • K L is the binding constant for the investigated interference ion
  • AAV max is the maximum deflection of the potential difference
  • c A is the concentration of the interference ion.
  • Two lonenmillieus (a, b) were tested, for example, can simulate the situation in the sewage water of a water treatment plant.
  • a, b Two lonenmillieus
  • 5 a shows the potential change during the measurement time of a phosphate electrode according to the invention at an interference ion concentration of 0.52 mM K 2 SO 4 and 2.82 mM KCl with a change in the phosphate concentration (upper axis). It is clear that the phosphate electrode according to the invention is suitable for determining the phosphate concentration.
  • the insertion shows the calibration curve of the phosphate electrode according to the invention obtained from the measured data. From a measurement time of about 200 minutes, the phosphate electrode was transferred to another solution with the starting concentration of 0.01 mM phosphate, wherein an increase in the measured potential difference (in mV) can be observed.
  • FIG. 5 b shows the potential change of a phosphate electrode according to the invention at an interference ion concentration of 2.08 mM sulfate and 7.05 mM chloride as a function of the concentration of KNO 3, KCl and K 2 SO 4 . It becomes clear that the addition of further interfering ions only leads to negligible potential changes. The highest remaining cross-sensitivity for the divalent sulfate is observed. An addition of 1.02 mM K 2 SO 4 (to a total of 3.1) leads to a potential change of less than 10 mV, which only leads to a small measurement error with regard to the phosphate concentration.
  • Fig. 6 a and b the potential change of a phosphate electrode according to the invention is shown at a higher interference ion concentration analogous to FIG.
  • interfering ions 2.5 mM K 2 SO and 14.1 mM KCl were initially charged in the analyte solution.
  • Fig. 6a again shows the change in potential with changing phosphate concentration.
  • the reversibility of the potential change was again tested by converting the phosphate electrode according to the invention into a solution having a concentration of 0.01 mM phosphate from a measurement time of 275 min.
  • the starting value is reached at 0 min measuring time.
  • Fig. 6b shows the change of the potential at the same output interference ion concentration as Fig. 6a and the indicated interference ion concentrations. Again, the low influence of the Störionen on the potential of the phosphate electrode according to the invention is clear.
  • Fig. 7 shows schematically the structure of a base body 1 made of cobalt of a phosphate electrode according to the invention with a first coating 1 a and second coating 1 b.
  • the second coating 1 b is preferably hydrophilic and permeable to water, which facilitates the diffusion of phosphate onto the base body or the first coating 1 a.
  • the second coating 1 b produce a basic pH in the electrode environment and should quickly compensate for changes in pH in the electrode surface interface.
  • pulverized borosilicate glass is used for the second coating 1b, as offered, for example, by Trovotech GmbH (Edisonstr. 3, D-06766 Bitterfeld-Wolfen).
  • Fig. 7 and 8 show a preferred, already tested structure of the base body 1 with coatings 1 a and 1 b of a phosphate electrode according to the invention schematically again.
  • the other test setup corresponds to the information in DE 10 2009 051 169 and is typical for ion-selective electrodes.
  • the borosilicate glass powder was suspended in water and the suspension was applied with a pasteur pipette to a filter paper made of glass fiber (which was adapted to the dimensions of the electrode; MN85 / 70, Macherey-Nagel, Düren).
  • the glass particles are transported with the penetrating water into the filter pores and fixed therein. Powder remaining on the surface is gently spread with a spatula and powder residues are removed.
  • the filter paper thus prepared is then applied in the wet state on both sides of the base body 1 and the first coating 1 a and then immediately introduced into a filter bag 2 made of cellulose.
  • Two hard plastic grids 3 which are firmly connected to each other by clamps 3a and mechanically stabilize the coatings 1 a and 1 b, are finally attached as an outer boundary.
  • the base body 1 and the first coating 1 a of the second coating 1 b in particular a borosilicate layer, separated by a fine-pored, hydrophilic membrane of a few ⁇ strength (eg synthetic fiber) (not shown).
  • non-biodegradable material is used, which has a favorable effect on the stability and lifetime of the electrode.
  • filter bags 2 of synthetic fiber are used instead of those of cellulose.
  • glass fiber filter papers e.g. Munkteil 3.1 101 .047 strength 250 ⁇ from the company Munkteil Filter AB. If a glass fiber filter paper is used, an additional covering by a filter bag can be dispensed with, which allows a more cost-effective production of the electrode. In addition, the fluid exchange between the electrode surface and analyte solution can be improved.
  • microparticles are used whose surface has been doped with amino groups in order to buffer the local pH value in the basic range. These microcapsules may be coated and / or filled such that they continuously release hydroxy ion.
  • FIG. 9 schematically shows a main body 1 (with coatings) according to FIG. 8 and additional gas line 4 with a corresponding opening 5 in two perspectives.
  • both an opening 5 for each gas line 4 and a plurality of openings 5 may be provided for a gas line 4.
  • a gas line 4 for example.
  • a commercial PVC hose an oxygen-containing gas, here air, supplied and distributed through the opening 5 in the vicinity of the phosphate electrode according to the invention. This is illustrated schematically in FIG. 9 by the circles.
  • a commercially available aquarium pump can be used for introducing the air.
  • a supply of oxygen-containing gas to the phosphate electrode is particularly advantageous if the oxygen partial pressure at the electrode surface of that in the analyte deviates strongly (eg. Under anaerobic conditions in the final sedimentation of a sewage treatment plant).
  • FIGS 10 and 11 schematically show a preferred embodiment of the phosphate electrode.
  • FIG. 10 shows a plan view of a phosphate electrode according to the invention with additional gas feed line (PVC hose) with openings 5, reference electrode 6, additional temperature sensor 7 and phosphate electrode measuring head 8.
  • PVC hose additional gas feed line
  • Fig. 1 1 shows a cross section of the phosphate electrode shown in Fig. 10.
  • the base body 1 has two coatings as described above, is arranged horizontally in the image plane and forms the reactive surface of the phosphate electrode on a side facing the analyte. Around this surface, a basic pH of above 7.4 (namely between 7.5 and 9) is produced by the second coating (not shown). In addition, air is released via the gas line 4 at the reactive surface of the main body 1, whereby a constant partial pressure of oxygen in the phosphate electrode environment is generated.
  • Both the reference electrode 6 and the phosphate electrode measuring head 8 are connected via BNC sockets 9 and cable 10 to a preamplifier 11, which amplifies the measuring signal and to an amplifier (not shown). outputs.
  • a preamplifier 11 which amplifies the measuring signal and to an amplifier (not shown). outputs.
  • a plurality of seals 12 are provided which prevent penetration of the analyte into the electrode.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Pathology (AREA)
  • Immunology (AREA)
  • General Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)

Abstract

L'invention concerne une électrode au phosphate comportant un corps de base (1) et un premier revêtement (1a) prévu au moins par endroits sur le corps de base, le corps de base contenant du cobalt élémentaire et le premier revêtement (1a) contenant un phosphate de cobalt. Un deuxième revêtement (1b) est prévu au moins par endroits sur le corps de base et/ou le premier revêtement, le deuxième revêtement liant les protons et/ou libérant des ions hydroxyde. L'invention concerne également un procédé de détermination de la concentration de phosphate au moyen de l'électrode au phosphate.
EP16707431.9A 2015-03-02 2016-03-02 Électrode au phosphate et procédé de détermination de la concentration de phosphate Withdrawn EP3265795A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015102945.6A DE102015102945B3 (de) 2015-03-02 2015-03-02 Phosphatelektrode und Verfahren zur Bestimmung der Phosphatkonzentration
PCT/EP2016/054360 WO2016139218A1 (fr) 2015-03-02 2016-03-02 Électrode au phosphate et procédé de détermination de la concentration de phosphate

Publications (1)

Publication Number Publication Date
EP3265795A1 true EP3265795A1 (fr) 2018-01-10

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EP16707431.9A Withdrawn EP3265795A1 (fr) 2015-03-02 2016-03-02 Électrode au phosphate et procédé de détermination de la concentration de phosphate

Country Status (8)

Country Link
US (1) US20180106752A1 (fr)
EP (1) EP3265795A1 (fr)
JP (1) JP2018507423A (fr)
CN (1) CN107430084A (fr)
AU (1) AU2016227740B2 (fr)
CA (1) CA2976835A1 (fr)
DE (2) DE102015102945B3 (fr)
WO (1) WO2016139218A1 (fr)

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CN114942262B (zh) * 2022-02-25 2024-03-08 南京农业大学 用于磷酸根离子检测的激光诱导石墨烯电极及制备方法
CN115184416A (zh) * 2022-06-23 2022-10-14 南通海星电子股份有限公司 制备铝电极箔所用槽液的磷酸根离子测定系统及测定方法

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Publication number Priority date Publication date Assignee Title
JPS5920662Y2 (ja) * 1979-01-12 1984-06-15 株式会社明電舎 水質測定装置
JPS63228054A (ja) * 1987-03-17 1988-09-22 Fuji Photo Film Co Ltd 炭酸濃度測定用イオン選択電極
JPH04130262A (ja) * 1990-09-21 1992-05-01 Nippon Parkerizing Co Ltd リン酸イオン選択性電極
JP4448243B2 (ja) * 2000-09-13 2010-04-07 株式会社堀場製作所 リン酸イオン選択性電極およびその作製方法
CN101666772B (zh) * 2008-09-04 2013-06-05 北京金达清创环境科技有限公司 检测磷酸盐的丝网印刷钴传感器的制备方法
JP5382573B2 (ja) * 2009-02-19 2014-01-08 国立大学法人三重大学 リチウム空気電池
DE102009051169B4 (de) 2009-10-29 2013-10-17 Passavant - Geiger Gmbh Phosphatelektrode, Elektrodensystem hiermit und deren Verwendung
DE102011011884B4 (de) 2011-02-21 2017-11-23 Trovotech Gmbh Verwendung dotierter poröser, amorpher Glaspartikel aus kontinuierlich erzeugtem Glasschaum
MY181674A (en) * 2011-05-12 2020-12-31 Mimos Berhad A phosphate sensor and method of formation thereof
GB2503689B (en) * 2012-07-04 2016-12-07 Compact Instr Ltd Phosphate detection
CN104267080A (zh) * 2014-10-09 2015-01-07 无锡百灵传感技术有限公司 检测污水中磷酸盐的电化学传感器

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Publication number Publication date
JP2018507423A (ja) 2018-03-15
CN107430084A (zh) 2017-12-01
DE102015102945B3 (de) 2016-06-16
AU2016227740B2 (en) 2018-07-05
AU2016227740A1 (en) 2017-09-21
DE202015102072U1 (de) 2015-06-03
US20180106752A1 (en) 2018-04-19
WO2016139218A1 (fr) 2016-09-09
CA2976835A1 (fr) 2016-09-09

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