WO2018166881A1 - Procédé de détermination de substances oxydables - Google Patents

Procédé de détermination de substances oxydables Download PDF

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Publication number
WO2018166881A1
WO2018166881A1 PCT/EP2018/055736 EP2018055736W WO2018166881A1 WO 2018166881 A1 WO2018166881 A1 WO 2018166881A1 EP 2018055736 W EP2018055736 W EP 2018055736W WO 2018166881 A1 WO2018166881 A1 WO 2018166881A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
oxalic acid
salt
solid mixture
salts
Prior art date
Application number
PCT/EP2018/055736
Other languages
English (en)
Inventor
Klaus Geick
Helga Guthmann
Original Assignee
Hach Lange 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 Hach Lange Gmbh filed Critical Hach Lange Gmbh
Priority to CN201880007131.9A priority Critical patent/CN110325504A/zh
Publication of WO2018166881A1 publication Critical patent/WO2018166881A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/50—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • 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
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/79—Photometric titration
    • 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
    • G01N33/1813—Specific cations in water, e.g. heavy metals
    • 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
    • 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
    • G01N33/1826—Organic contamination in water

Definitions

  • the present invention relates to a solid mixture and to a method for determining oxidizable substances in a sample.
  • the international ISO standard 8467 describes a method for determining organic contaminants in weakly polluted waters (drinking water, surface water, untreated water) after digestion by means of indirect titration with a defined permanganate solution and an oxalic acid solution, The performance of this method is reserved for an experienced user in a laboratory due to the many working steps and the open handling of dangerous solutions.
  • the water sample is mixed with sulfuric acid and with a defined amount of permanganate solution in excess and digested in a boiling water bath for 10 minutes.
  • the still hot mixture Is subsequently mixed with a defined amount of oxalic acid solution, whereby the solution is completely decolorized,
  • the excess of oxalic acid Is then titrated with the permanganate solution to a pale pink color.
  • the permanganate index is calculated in mg/L based on the consumption of permanganate solution,
  • a pre-titration usually takes place before the actual triple titration in order to estimate the approximate content of organic impurities in advance.
  • AH solutions permanganate solution, oxalic acid solution
  • the oxalic acid solution is in particular unstable. The process also produces significant amounts of aqueous waste which must be disposed of.
  • the content thus determined, calculated as the permanganate index, is nonetheless a common parameter for determining water quality and is widely used In practice.
  • the object is achieved in one aspect by a method for producing a lyophiiized solid mixture comprising the steps:
  • the oxalic acid salts are preferably alkali salts, alkaline earth salts, and ammonium salts.
  • Suitable inventive inorganic salts can include those compounds which are usually purely Inorganic and free of organic impurities in order to avoid any influence on the reaction process. Examples thereof include sulfates, phosphates, chlorides, nitrates. Particularly preferred salts include sodium salts, potassium salts, lithium salts, calcium salts, magnesium salts and ammonium salts.
  • the weight ratio of inorganic salts to oxalic acid or oxalic acid salts is 10 to 100 : 1 in the present invention. Only the anions of the inorganic salt and the oxalate are considered when calculating the weight ratios.
  • the concentration of oxalic acid or oxalic acid salts in the solution prior to lyophilization is preferably in the range of 0.01 to 0,05 mol/I,
  • the concentration of inorganic salts prior to lyophilization is accordingly in the range of 0.1 to 5 moS/S.
  • Lyophilization or also freeze drying is a process for the gentle drying of products which is based on the principle of sublimation, i.e., that ice crystals pass directly into the gaseous state without a liquid phase occurring.
  • Typical freeze-drying includes the steps of freezing, drying, and optionally a post-drying. While freezing typically occurs at atmospheric pressure, the main drying or post-drying occurs under sublimation conditions. Temperature, time and pressure can be adapted to the required quantities and drying parameters and varied over a wide range. Typical parameters can be taken from the following Table.
  • Temperature programs serve to increase the growth of the ice crystals by changing the temperature of the frozen product, which faci!itates freeze- drying,
  • the solution to be lyophilized is transferred to suitable containers and is lyophilized in these containers.
  • the container thereby receives a precisely metered amount of oxalic acid.
  • the permanganate index is determined by titration as it was previously, whereby, however, instead of adding a liquid oxalic acid solution or a liquid oxalic acid salt solution, the previously prepared, defined amount of oxalic acid in solid form is added.
  • a suitable method therefor is to introduce a corresponding opened vessel with the solid mixture into the titration flask,
  • the resulting product of the lyophilization is solid, homogeneous and free from crumbs. This facilitates further processing.
  • a small amount of an organic polymer may be added to the product to be lyophilized.
  • Such polymers usually improve the strength of the lyophilizate.
  • they are an organic component which can influence the measurement. No organic polymers are preferably used.
  • the invention also relates to the lyophilized solid mixture obtainable by the process according to the inventive method.
  • the production in the form of solids in the factory can produce, dose and package precisely dosed quantities.
  • the production and dosage of the reagents to be added on site is no longer required. This also allows staff which is less well trained to be considered for implementation.
  • the described solid mixture can in particular be used for the qualitative and quantitative determination of organic Impurities in water.
  • the solid mixture is in particular suitable for the determination of organic impurities in waters analogous to ISO 8467. Only weakly contaminated samples can generally be examined for their organic impurities; these first and foremost include drinking water, surface water, untreated water, and mineral water.
  • the solid mixture according to the invention is in particular suitable for detecting organic contaminants of aqueous samples by optical methods.
  • Photometry hereby in particular comes into consideration.
  • the aqueous sample is prepared for optical measurement by digesting the aqueous sample with sulfuric acid and with a permanganate solution in a cuvette for 10 minutes at 100 °C, for example, in a metal block thermostat.
  • the aqueous sample is advantageously cooled to room temperature after digestion, preferably to 20 °C via a metal block thermostat, a water bath, or in the air.
  • the aqueous sample is subsequently mixed with the inventive solid mixture to react with the excess of unused permanganate soiution.
  • a precisely defined amount of permanganate solution is dosed into the reaction cuvette and is photometrically measured at the latest after 5 minutes, preferably after 1 minute, whereby the photometric measurement serves to calculate the organic load.
  • the samples and reaction volumes can be significantly reduced so that fewer waste solutions arise which must be disposed of.
  • the inventive solid mixture has the advantage that it can be produced and distributed as a ready to use test kit in a pre-dosed form.
  • the invention accordingly also relates to a test kit which comprises the above-described solid mixture, a permanganate solution and instructions for use.
  • the test kits comprise a device for storing reagents and for introducing the reagents into reaction containers filled with the water sample to be analyzed in order to carry out qualitative and quantitative analyzes and to close the reaction containers.
  • the device is preferably a device with at least two spatially separated closure regions as described in DE 198 50 934 Al.
  • a further possibility of arranging the section which serves to close the reaction container is to provide a one-sided open container as a closure element as is described in DE 8703659 Ul.
  • a further possibility of arranging the container is to introduce the inventive solid mixture in a separate container as Is sold, for example, under the MicroCap brand,
  • the device described can be used so that the reaction container Is first filled with the sample to be examined and a digestion reaction is carried out, and that the reagents present in the device are then introduced therewith.
  • the focus of the investigations was the optimization of the carrier components in terms of durability, mechanical strength and function.
  • freeze-drying program used was as follows:
  • the recovery rate for corresponding products was determined immediately after bottling and after storage for 1, 6 and 12 months. Ten respective vessels were thereby examined in parallel. Solid homogenates thereby showed less variation in the recovery rate. Compositions containing borates were less stable of the oxalic acid. No significant improvements via organic additives was achieved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Investigating Or Analysing Biological Materials (AREA)

Abstract

L'invention concerne un procédé de préparation d'un mélange solide comprend les étapes consistant à : - préparer une solution comprenant de l'acide oxalique ou des sels d'acide oxalique, - un ou plusieurs sels inorganiques, - lyophiliser la solution.
PCT/EP2018/055736 2017-03-13 2018-03-08 Procédé de détermination de substances oxydables WO2018166881A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201880007131.9A CN110325504A (zh) 2017-03-13 2018-03-08 用于测定可氧化物质的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017105266.6 2017-03-13
DE102017105266.6A DE102017105266B4 (de) 2017-03-13 2017-03-13 Verfahren zur Bestimmung oxidierbarer Stoffe

Publications (1)

Publication Number Publication Date
WO2018166881A1 true WO2018166881A1 (fr) 2018-09-20

Family

ID=61599168

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/055736 WO2018166881A1 (fr) 2017-03-13 2018-03-08 Procédé de détermination de substances oxydables

Country Status (3)

Country Link
CN (1) CN110325504A (fr)
DE (1) DE102017105266B4 (fr)
WO (1) WO2018166881A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110058037A (zh) * 2019-05-28 2019-07-26 上海安杰环保科技股份有限公司 一种高锰酸盐指数分析仪多功能多通道加样装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019135489A1 (de) * 2019-12-20 2021-06-24 Endress+Hauser Conducta Gmbh+Co. Kg Verfahren zur Bestimmung eines von der Konzentration mindestens eines Analyten in einer Probenflüssigkeit abhängigen Parameters

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE8703659U1 (fr) 1986-11-26 1987-09-10 Dr. Bruno Lange Gmbh, 1000 Berlin, De
RU2146820C1 (ru) * 1998-06-15 2000-03-20 Сибирский государственный технологический университет Способ определения содержания этилового спирта
DE19850934A1 (de) 1998-11-05 2000-05-18 Lange Gmbh Dr Bruno Vorrichtung zum Aufbewahren von Reagenzien und zum Verschließen von Behältnissen
CN101475158A (zh) * 2009-01-09 2009-07-08 北京工业大学 一种锂离子电池正极材料LiFePO4的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873651A (en) 1972-05-12 1975-03-25 Atomic Energy Commission Freeze drying method for preparing radiation source material
GB2480299B (en) 2010-05-12 2016-08-10 Gea Pharma Systems Ltd A method for monitoring and/or controlling process parameters of a lyophilization process
CN102012362B (zh) 2010-10-15 2012-02-22 宁波市环境监测中心 一种分光光度法快速测定水中高锰酸盐指数的方法
CN103926239B (zh) * 2013-01-11 2018-11-27 丹纳赫（上海）工业仪器技术研发有限公司 水性样品中的可氧化污染物的检测方法
CN106093019A (zh) * 2016-05-31 2016-11-09 贵州大学 一种分析铝酸钠溶液中有机物含量的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE8703659U1 (fr) 1986-11-26 1987-09-10 Dr. Bruno Lange Gmbh, 1000 Berlin, De
RU2146820C1 (ru) * 1998-06-15 2000-03-20 Сибирский государственный технологический университет Способ определения содержания этилового спирта
DE19850934A1 (de) 1998-11-05 2000-05-18 Lange Gmbh Dr Bruno Vorrichtung zum Aufbewahren von Reagenzien und zum Verschließen von Behältnissen
CN101475158A (zh) * 2009-01-09 2009-07-08 北京工业大学 一种锂离子电池正极材料LiFePO4的制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110058037A (zh) * 2019-05-28 2019-07-26 上海安杰环保科技股份有限公司 一种高锰酸盐指数分析仪多功能多通道加样装置

Also Published As

Publication number Publication date
DE102017105266A1 (de) 2018-09-13
DE102017105266B4 (de) 2023-08-31
CN110325504A (zh) 2019-10-11

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