EP1315762A1 - Determining the concentration of polyaspartic acid using fluorometry - Google Patents

Determining the concentration of polyaspartic acid using fluorometry

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Publication number
EP1315762A1
EP1315762A1 EP01960679A EP01960679A EP1315762A1 EP 1315762 A1 EP1315762 A1 EP 1315762A1 EP 01960679 A EP01960679 A EP 01960679A EP 01960679 A EP01960679 A EP 01960679A EP 1315762 A1 EP1315762 A1 EP 1315762A1
Authority
EP
European Patent Office
Prior art keywords
concentration
water
systems
range
salts
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Withdrawn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
EP01960679A
Other languages
German (de)
French (fr)
Inventor
Thomas Klein
Thomas Klausa
Andreas Elschner
Ralf-Johann Moritz
Monika Cordes
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.)
Lanxess Deutschland GmbH
Original Assignee
Bayer AG
Bayer Chemicals AG
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Filing date
Publication date
Application filed by Bayer AG, Bayer Chemicals AG filed Critical Bayer AG
Publication of EP1315762A1 publication Critical patent/EP1315762A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1092—Polysuccinimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/10—Alpha-amino-carboxylic acids

Definitions

  • the present invention relates to a method for carrying out concentration determinations or for online determination of the dosing concentration of polyaspartic acids and / or their salts in aqueous systems.
  • Maintaining a constant level of the chemicals used is very important in water treatment. Underdosing a scale inhibitor in a cooling water circuit would possibly result in a reduction in the heat transfer due to calcium salt deposits. The feeding of fresh water makes it necessary to reset the treatment chemicals to the old value and thus also to determine the concentration.
  • the analysis of the scale inhibitor is carried out photometrically or titrimetrically. More economical would be a physical process in which a
  • Measurement parameter that is linear with the concentration e.g. of the scale inhibitor goes, is measured online and is kept at a constant value by a metering device.
  • EP-A 0 485 882 describes the use of a fluorescent label such as e.g. Coumarin or its derivatives labeled polymer described as a scale inhibitor, after correlating the fluorescence intensity with the concentration either automatically or manually corrected to an optimal value.
  • a fluorescent label such as e.g. Coumarin or its derivatives labeled polymer described as a scale inhibitor
  • EP-A 0475 602 describes a ner process for fluorescent labeling of polyacrylic acid esters or amides by transamidation with fluorescent amines such as e.g. Tryptophan. In the latter case, the incorporation is 76%, using 15 mol% tryptophan. Detection was possible down to 1 pp.
  • the object of the present invention was also for polyaspartic acids
  • PASP to develop a ner method for determining the concentration in aqueous systems, which allows the concentration of PASP in aqueous systems to be continuously monitored, in order to prevent the occurrence of undesirable deposits in the form of inorganic or organic scales during operation of the system, and thereby prevent To prevent pollution of the water by excessive entry of PASPals scale inhibitor '.
  • the monitoring of the scale inhibitor should also work on flowing water flows and should be able to be measured online.
  • Fluorometry is a widely used analytical measurement method in which a substance is excited with a light source (xenon lamp) and the intensity of the emitted fluorescent light is measured as a function of the excitation and emission wavelength. Among other things, it is used as fast, cost-effective "on-site analysis”. Fluorescence spectroscopy is a recognized measurement method for measuring entries into water bodies.
  • the substances to be detected (active substances in a formulation) are either marked chemically using a marker or identified as a mixture with an added fluorescent marker. The correlation of the fluorescent marker with the actual active ingredient is not always easy. There are problems in the different degradation behavior on the thermal and microbiological side. The assignment also reflects z. B. by complex formation and thus the passive portion of the active ingredient no direct relationship to the marker. Such systems must therefore always be used in higher concentrations than would actually be necessary. Because underdosing of a scale inhibitor would possibly result in a reduction in heat transfer in a cooling water circuit due to calcium deposits on the transfer surfaces.
  • thermal polyaspartic acids from maleic anhydride and ammonia have recently been increasingly used as a biodegradable alternative for polyacrylates in many applications. Especially in water treatment, the thermal polyaspartic acid should play a significant role in the
  • thermal polyaspartic acids are used as a dispersant.
  • fluorescence One of the positive physical properties of thermal polyaspartic acids. They should be able to detect the actual active ingredient without detour. Linear dependencies of the fluorescence intensity on the concentration, the degradation (chemical, physical or biological) or the coating as a dispersant or complexing agent would be desirable.
  • the present invention therefore relates to a method for carrying out concentration determinations of polyaspartic acids in aqueous systems by means of fluorometry.
  • the method according to the invention is suitable for determining the concentration of the PASP or its salts produced by thermal condensation starting from d, l-aspartic acid or an isomer of aspartic acid and their salts or by thermal condensation of maleic anhydride, ammonia, sodium hydroxide solution and water, and possible maleic anhydride secondary products such as fumaric acid, maleic acid or their salts.
  • the method according to the invention is particularly suitable for the analysis of PASP or its salts, which according to the Bayer method according to the protective rights EP-A 0 256 366, EP-A 0 604 813, EP-A 0 612 784, EP-A
  • the method according to the invention is suitable for determining the concentration of PASP or its salts in aqueous systems, preferably in aqua desi, tap water, river water, oil / water mixtures and in industrial liquid streams, natural waste water systems, industrial waste water systems such as, for example, paint waste water, building drainage systems and other water systems, such as For example, cleaners, dispersions and formulations with water-based polyaspartic acids, where the deposition or regression of inorganic or organic scales is to be prevented or the removal of which should be sought.
  • the method is also suitable for online determination of the dosing concentration, for example in papermaking or petroleum production.
  • the method according to the invention is suitable for monitoring the PASP concentrations when it is used as a deposit inhibitor in the evaporation of sugar juices.
  • the method according to the invention is also suitable for analyzing polyaspartic acids and / or their salts in aqueous systems or in oil / water systems.
  • Possible salts in the context of the present invention are the alkali or alkaline earth metal salts of PASP, preferably the sodium salt.
  • the method according to the invention is suitable for determining PASP concentrations over a wide concentration range in the respective aqueous system.
  • loading The method is preferably used in the range between 0.1 to 1000 ppm, particularly preferably in the range from 1 to 100 ppm.
  • the method according to the invention shows its advantages in the range between 1 and 100 ppm.
  • the method according to the invention for determining the PASP concentration by means of fluorometry is suitable for use over a wide temperature range.
  • the preferred application range is between 0 and 70 ° C, particularly preferably between 20 and 30 ° C.
  • the method according to the invention is suitable for determining the concentration of
  • the fluctuation range of the pH value in cooling water circuits is in the order of 1.5 units in the neutral range between pH 6.5 and pH 8, that of river water with an annual average of approx. + 0.5 pH units.
  • the signal obtained becomes regular in accordance with its pH and temperature sensitivity converted to a standard value and the actual concentration determined at this corrected value, so that reliable values are obtained even at pH 14.
  • Fig. 4 shows the intensity over the entire pH range.
  • the fluctuations in the specified range are of the order of 5%.
  • the method according to the invention can be operated with any suitable fluorescence spectrometer.
  • the analysis and evaluations were carried out on a fluorescence spectrometer of the type AMINCO-Bowman® Series 2 (AB2) from the company

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention relates to a method for determining, in aqueous solutions, the concentration of polyaspartic acid and/or the salts thereof.

Description

Polyasparaginsäure-Konzentrationsbestimmung mittels FluorometriePolyaspartic acid concentration determination using fluorometry
Die vorliegende Erfindung betrifft ein Nerfahren zur Durchführung von Konzentrationsbestimmungen oder zur Online-Bestimmung der Dosierkonzentration von Poly- asparaginsäuren und/oder ihrer Salze in wässrigen Systemen.The present invention relates to a method for carrying out concentration determinations or for online determination of the dosing concentration of polyaspartic acids and / or their salts in aqueous systems.
In der Wasserbehandlung ist die Beibehaltung eines konstanten Levels der eingesetzten Chemikalien von großer Bedeutung. Eine Unterdosierung eines Scale- Inhibitors würde gegebenenfalls in einem Kühlwasserkreislauf eine Reduktion des Wärmeübergangs durch Calciumsalzablagerungen nach sich ziehen. Die Einspeisung von Frischwasser macht ein Wiedereinstellen der Behandlungschemikalien auf den alten Wert und damit auch eine Konzentrationsbestimmung notwendig.Maintaining a constant level of the chemicals used is very important in water treatment. Underdosing a scale inhibitor in a cooling water circuit would possibly result in a reduction in the heat transfer due to calcium salt deposits. The feeding of fresh water makes it necessary to reset the treatment chemicals to the old value and thus also to determine the concentration.
Die Analytik des Scale-Inhibitors wird je nach Substanz photometrisch oder titri- metrisch durchgeführt. Ökonomischer wäre ein physikalisches Verfahren, in dem einDepending on the substance, the analysis of the scale inhibitor is carried out photometrically or titrimetrically. More economical would be a physical process in which a
Messparameter, der linear mit der Konzentration z.B. des Scale-Inhibitors geht, online gemessen und durch eine Dosiereinrichtung auf einem konstanten Wert gehalten wird.Measurement parameter that is linear with the concentration e.g. of the scale inhibitor goes, is measured online and is kept at a constant value by a metering device.
In EP-A 0 485 882 wird die Verwendung eines mit einem Fluoreszenzmarker wie z.B. Cumarin oder seine Derivate markierten Polymers als Scale-Inhibitor beschrieben, wobei nach Korrelation der Fluoreszenzintensität mit der Konzentration entweder automatisch oder manuell diese auf einen optimalen Wert korrigiert wird.EP-A 0 485 882 describes the use of a fluorescent label such as e.g. Coumarin or its derivatives labeled polymer described as a scale inhibitor, after correlating the fluorescence intensity with the concentration either automatically or manually corrected to an optimal value.
EP-A 0475 602 beschreibt ein Nerfahren zur Fluoreszenzmarkierung von Polyacryl- säureestern oder -amiden durch Umamidierung mit fluoreszierenden Aminen wie z.B. Tryptophan. In dem letzteren Fall beträgt der Einbau 76 %, wobei 15 Mol % Tryptophan verwendet wurden. Die Detektion konnte bis 1 pp hinunter erfolgen.EP-A 0475 602 describes a ner process for fluorescent labeling of polyacrylic acid esters or amides by transamidation with fluorescent amines such as e.g. Tryptophan. In the latter case, the incorporation is 76%, using 15 mol% tryptophan. Detection was possible down to 1 pp.
In dem Patent US-A 4 813 973 wird die Herstellung von fluoreszenzmarkierten Polymeren für Anwendungen im Bereich Flockungsmittel, Papierherstellung und Erdöl- bohrungen beschrieben. Amidhaltige Polymere wie Polyacrylamid werden dabei mit wasserlöslichen Farbstoffen wie 9-Xanthydrol in Essigsäure umgesetzt.US Pat. No. 4,813,973 describes the production of fluorescence-labeled polymers for applications in the fields of flocculants, paper production and petroleum holes described. Polymers containing amide such as polyacrylamide are reacted with water-soluble dyes such as 9-xanthohydrol in acetic acid.
Thermische Polyasparaginsäure aus Maleinsäureanhydrid und Ammoniak wird in der jüngsten Zeit verstärkt als biologisch abbaubare Alternative für Polyacrylate in vielenThermal polyaspartic acid from maleic anhydride and ammonia has recently been intensified as a biodegradable alternative for polyacrylates in many
Anwendungen eingesetzt. In einigen Fällen ist eine schnelle und spezifische Methode zur Konzentrationsbestimmung gesucht, wie sie etwa von fluoreszenzmarkierten Polyacrylsäuren bekannt ist.Applications. In some cases, a fast and specific method for determining the concentration, such as is known from fluorescence-labeled polyacrylic acids, is sought.
Die Aufgabe der vorliegenden Erfindung bestand darin auch für PolyasparaginsäurenThe object of the present invention was also for polyaspartic acids
(PASP) ein Nerfahren zur Konzentrationsbestimmung in wässrigen Systemen zu entwickeln, das es erlaubt, die Konzentration an PASP in wässrigen Systemen permanent zu überwachen, um somit während des Betriebes von Anlagen das Auftreten unerwünschter Ablagerungen in Form anorganischer oder organischer Scales zu verhindern und dabei eine Belastung des Gewässers durch übermäßigen Eintrag von PASPals Scale-Inhibitor' zu verhindern. Die Überwachung des Scale-Inhibitors sollte zudem an fließenden Wasserströmen funktionieren und online gemessen werden können.(PASP) to develop a ner method for determining the concentration in aqueous systems, which allows the concentration of PASP in aqueous systems to be continuously monitored, in order to prevent the occurrence of undesirable deposits in the form of inorganic or organic scales during operation of the system, and thereby prevent To prevent pollution of the water by excessive entry of PASPals scale inhibitor '. The monitoring of the scale inhibitor should also work on flowing water flows and should be able to be measured online.
Die Fluorometrie ist eine weit verbreitete analytische Meßmethode, bei der eine Substanz mit einer Lichtquelle (Xenon-Lampe) angeregt und die Intensität des emittierten Fluoreszenzlichts als Funktion der Anregungs- und Emissionswellenlänge gemessen wird. Sie wird unter anderem als schnelle, kostengünstige "Nor-Ort- Analytik" eingesetzt. Für die Messung von Einträgen in Gewässer ist die Fluores- zenzspektroskopie eine anerkannte Messmethodik. Dabei werden die zu detektie- renden Substanzen (Wirkstoffe in einer Formulierung) entweder chemisch mittels eines Markers markiert oder als Gemisch mit einem zugesetzten Fluoreszenzmarker identifiziert. Die Korrelationen des Fluoreszenzmarkers zum eigentlichen aktiven Wirkstoff ist nicht immer ganz einfach. Probleme gibt es im unterschiedlichen Ab- bauverhalten auf thermischer und mikrobiologischer Seite. Auch spiegelt die Belegung z. B. durch Komplexbildung und damit der passive Anteil des Wirkstoffes kein direktes Verhältnis zum Marker. Daher müssen solche Systeme immer in höheren Konzentrationen eingesetzt werden, als eigentlich nötig wäre. Denn eine Unterdosierung eines Scale-Inhibitors würde gegebenenfalls in einem Kühlwasserkreislauf eine Reduktion des Wärmeübergangs durch Calciumablagerungen an den Übertragungsflächen nach sich ziehen.Fluorometry is a widely used analytical measurement method in which a substance is excited with a light source (xenon lamp) and the intensity of the emitted fluorescent light is measured as a function of the excitation and emission wavelength. Among other things, it is used as fast, cost-effective "on-site analysis". Fluorescence spectroscopy is a recognized measurement method for measuring entries into water bodies. The substances to be detected (active substances in a formulation) are either marked chemically using a marker or identified as a mixture with an added fluorescent marker. The correlation of the fluorescent marker with the actual active ingredient is not always easy. There are problems in the different degradation behavior on the thermal and microbiological side. The assignment also reflects z. B. by complex formation and thus the passive portion of the active ingredient no direct relationship to the marker. Such systems must therefore always be used in higher concentrations than would actually be necessary. Because underdosing of a scale inhibitor would possibly result in a reduction in heat transfer in a cooling water circuit due to calcium deposits on the transfer surfaces.
Die thermischen Polyasparaginsäuren aus Malemsäureanhydrid und Ammoniak werden in der jüngsten Zeit verstärkt als biologisch abbaubare Alternative für Polyacrylate in vielen Anwendungen eingesetzt. Gerade in der Wasserbehandlung soll die thermischen Polyasparaginsäuren eine nicht unwesentliche Rolle in derThe thermal polyaspartic acids from maleic anhydride and ammonia have recently been increasingly used as a biodegradable alternative for polyacrylates in many applications. Especially in water treatment, the thermal polyaspartic acid should play a significant role in the
Komplexierung von Metallen und als Dispergiermittel einnehmen. Eine der positiven physikalischen Eigenschaften der thermischen Polyasparaginsäuren ist die Fluoreszenz. Durch sie sollte es möglich sein den eigentlichen aktiven Wirkstoff ohne Umweg zu detektieren. Lineare Abhängigkeiten der Fluoreszenzintensität von der Konzentration, dem Abbau (chemisch, physikalisch oder biologisch) oder der Belegung als Dispergiermittel oder Komplexbildner wären dabei wünschenswert.Use complexing of metals and as a dispersant. One of the positive physical properties of thermal polyaspartic acids is fluorescence. They should be able to detect the actual active ingredient without detour. Linear dependencies of the fluorescence intensity on the concentration, the degradation (chemical, physical or biological) or the coating as a dispersant or complexing agent would be desirable.
Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Durchführung von Konzentrationsbestimmungen von Polyasparaginsäuren in wässrigen Systemen mittels Fluorometrie.The present invention therefore relates to a method for carrying out concentration determinations of polyaspartic acids in aqueous systems by means of fluorometry.
Durch die Anwendung dieser Methode wird eine genaue Erfassung von Polyaspara- ginsäure Konzentrationen in wässrigen Systhemen sowie eine gleichmäßige Dosierung von Produkten zur Wasserbehandlung ermöglicht. Die Anregungs- und Emissionswellenlängen von Polyasparaginsäure sind bekannt und liegen für dieThe use of this method enables an exact determination of polyaspartic acid concentrations in aqueous systems as well as an even dosage of products for water treatment. The excitation and emission wavelengths of polyaspartic acid are known and lie for that
Excitation bei 336 nm und für die Emission bei 411 nm (siehe Fig. 1: Ex = Excitationspeak E (max-): 336 nm; Em = Emisionspeak Em (max) : 411 nm).Excitation at 336 nm and for the emission at 411 nm (see Fig. 1: Ex = excitation peak E (max - ) : 336 nm; Em = emission peak Em (max) : 411 nm).
Das erfindungsgemäße Verfahren ist geeignet zur Konzentrationsbestimmung der PASP oder deren Salze hergestellt durch thermische Kondensation ausgehend von d,l-Asparaginsäure oder einem Isomeren der Asparaginsäure sowie deren Salze oder durch thermische Kondensation von Maleinsäureanhydrid, Ammoniak, Natronlauge und Wasser, sowie mögliche Maleinsäureanhydrid-Folgeprodukte wie Fumarsäure, Maleinsäure oder deren Salze. Besonders geeignet ist das erf ndungsgemäße Verfahren zur Analyse von PASP oder deren Salze, die nach dem Bayer- Verfahren ge- maß der Schutzrechte EP-A 0 256 366, EP-A 0 604 813, EP-A 0 612 784, EP-AThe method according to the invention is suitable for determining the concentration of the PASP or its salts produced by thermal condensation starting from d, l-aspartic acid or an isomer of aspartic acid and their salts or by thermal condensation of maleic anhydride, ammonia, sodium hydroxide solution and water, and possible maleic anhydride secondary products such as fumaric acid, maleic acid or their salts. The method according to the invention is particularly suitable for the analysis of PASP or its salts, which according to the Bayer method according to the protective rights EP-A 0 256 366, EP-A 0 604 813, EP-A 0 612 784, EP-A
0 650 995, WO 94/03526 oder nach US-A 5 408 028, US-A 5 488 088 oder US-A 5 484 860 hergestellt werden.0 650 995, WO 94/03526 or according to US-A 5 408 028, US-A 5 488 088 or US-A 5 484 860.
Das erfindungsgemäße Verfahren ist geeignet zur Konzentrationsbestimmung von PASP oder deren Salze in wässrigen Systemen, bevorzugt in Aqua desi, Leitungswasser, Flusswasser, Öl/Wasser-Gemischen sowie in industriellen Flüssigkeitsströmen, natürlichen Abwassersystemen, industriellen Abwassersystemen wie beispielsweise Lackierabwasser, Bauwerksentwässerungssystemen und anderen Wassersystemen, wie beispielsweise Reiniger, Dispersionen und Formulierungen mit Poly- asparaginsäuren auf Wasserbasis, wo die Ablagerung oder Rückbildung von anorganischen oder organischen Scales verhindert oder deren Entfernung angestrebt werden soll.The method according to the invention is suitable for determining the concentration of PASP or its salts in aqueous systems, preferably in aqua desi, tap water, river water, oil / water mixtures and in industrial liquid streams, natural waste water systems, industrial waste water systems such as, for example, paint waste water, building drainage systems and other water systems, such as For example, cleaners, dispersions and formulations with water-based polyaspartic acids, where the deposition or regression of inorganic or organic scales is to be prevented or the removal of which should be sought.
Weiterhin ist das Verfahren zur Online-Bestimmung der Dosierkonzentration, bei- spielsweise bei der Papierherstellung oder der Erdölgewinnung geeignet. Außerdem eignet sich das erfindungsgemäße Verfahren zur Überwachung der PASP-Konzentrationen, wenn diese als Belagsverhinderer bei der Eindampfung von Zuckersäften eingesetzt wird.The method is also suitable for online determination of the dosing concentration, for example in papermaking or petroleum production. In addition, the method according to the invention is suitable for monitoring the PASP concentrations when it is used as a deposit inhibitor in the evaporation of sugar juices.
Das erfindungsgemäße Verfahren ist ferner geeignet, Polyasparaginsäuren und/oder ihre Salze in wässrigen Systemen oder in Öl/Wasser-Systemen zu analysieren. Als Salze im Rahmen der vorliegenden Erfindung kommen dabei die Alkali- oder Erdkalkalisalze der PASP in Frage, bevorzugt das Natriumsalz.The method according to the invention is also suitable for analyzing polyaspartic acids and / or their salts in aqueous systems or in oil / water systems. Possible salts in the context of the present invention are the alkali or alkaline earth metal salts of PASP, preferably the sodium salt.
Das erfindungsgemäße Verfahren ist geeignet, PASP-Konzentrationen über einen weiten Konzentrationsbereich im jeweiligen wässrigen System zu bestimmen. Be- vorzugt wird das Verfahren im Bereich zwischen 0,1 bis 1000 ppm eingesetzt, insbesondere bevorzugt im Bereich von 1 bis 100 ppm.The method according to the invention is suitable for determining PASP concentrations over a wide concentration range in the respective aqueous system. loading The method is preferably used in the range between 0.1 to 1000 ppm, particularly preferably in the range from 1 to 100 ppm.
Fig. 2 zeigt die Abhängigkeit des Fluoreszenzsignals von der PASP Konzentration in ppm in Form einer linearen Intensitätszunahme mit steigender Konzentration.2 shows the dependence of the fluorescence signal on the PASP concentration in ppm in the form of a linear increase in intensity with increasing concentration.
Insbesondere beim Einsatz der PASP in der industriellen Wasserbehandlung in Kühlwassersystemen zeigt das erfindungsgemäße Verfahren im Bereich zwischen 1 bis 100 ppm seine Vorzüge.In particular when using the PASP in industrial water treatment in cooling water systems, the method according to the invention shows its advantages in the range between 1 and 100 ppm.
Das erfindungsgemäße Verfahren zur PASP-Konzentrationsbestimmung mittels Fluormetrie ist geeignet, über einen weiten Temperaturbereich angewandt zu werden. Der bevorzugte Anwendungsbereich liegt bei Temperaturen zwischen 0 und 70°C, besonders bevorzugt bei Temperaturen zwischen 20 und 30°C.The method according to the invention for determining the PASP concentration by means of fluorometry is suitable for use over a wide temperature range. The preferred application range is between 0 and 70 ° C, particularly preferably between 20 and 30 ° C.
Technisch wäre man in der Lage zu messende Wasserströme mittels Wärmetauscher auf eine konstante Temperatur im Bereich von 20 bis 30°C, zu regeln, da die Schwankungsbreite des Signals in diesem Bereich bei lediglich 5 % liegt.Technically, one would be able to regulate the water flows to be measured using a heat exchanger to a constant temperature in the range of 20 to 30 ° C, since the fluctuation range of the signal in this range is only 5%.
Fig. 3 zeigt die lineare Temperaturabhängigkeit der Fluoreszenzaktivität einer PASP-3 shows the linear temperature dependence of the fluorescence activity of a PASP
Lösung (10 ppm), die von 70 auf 0°C abgekühlt und anschließend wieder auf 70°C erwärmt wird, um Hysterese-Effekte auszuschließen. Diese konnten jedoch nicht nachgewiesen werden. Mit zunehmender Temperatur fallt das Signal stetig monoton.Solution (10 ppm), which is cooled from 70 to 0 ° C and then reheated to 70 ° C to exclude hysteresis effects. However, these could not be proven. As the temperature rises, the signal drops monotonously.
Das erfindungsgemäße Verfahren ist geeignet zur Konzentrationsbestimmung vonThe method according to the invention is suitable for determining the concentration of
PASP in wässrigen Lösungen über einen weiten pH-Bereich hinweg, bevorzugt 0 bis 14, insbesondere 0 bis 13. Üblicherweise liegt der Schwankungsbereich des pH- Wertes in Kühlwasserkreisläufen in Größenordnungen von 1,5 Einheiten im Neutralen zwischen pH 6,5 und pH 8, der von Flusswasser im Jahresmittel von ca. + 0,5 pH-Einheiten. Bei der Durchführung der Konzentrationsbestimmungen wird das erhaltene Signal gemäß dessen pH- und Temperaturempfindlichkeit regelmäßig auf einen Normwert umgerechnet und an diesem korrigierten Wert die tatsächliche Konzentration bestimmt, so dass auch bei pH 14 zuverlässige Werte erhalten werden.PASP in aqueous solutions over a wide pH range, preferably 0 to 14, in particular 0 to 13. Usually the fluctuation range of the pH value in cooling water circuits is in the order of 1.5 units in the neutral range between pH 6.5 and pH 8, that of river water with an annual average of approx. + 0.5 pH units. When carrying out the concentration determinations, the signal obtained becomes regular in accordance with its pH and temperature sensitivity converted to a standard value and the actual concentration determined at this corrected value, so that reliable values are obtained even at pH 14.
Fig. 4 gibt die Intensität über den gesamten pH- Wert-Bereich wieder. Die Schwan- kungen im angegebenen Bereich liegen in der Größenordnung von 5 %.Fig. 4 shows the intensity over the entire pH range. The fluctuations in the specified range are of the order of 5%.
Das erfindungsgemäße Verfahren kann mit jedem geeigneten Fluoreszenzspektrometer betrieben werden. Für die erfindungsgemäß bevorzugt eingesetzte PASP nach dem Bayer-Verfahren wurde die Analytik und Auswertungen an einem Fluoreszenzspektrometer des Typs AMINCO-Bowman® Series 2 (AB2) der FirmaThe method according to the invention can be operated with any suitable fluorescence spectrometer. For the PASP according to the invention, which is preferably used according to the Bayer method, the analysis and evaluations were carried out on a fluorescence spectrometer of the type AMINCO-Bowman® Series 2 (AB2) from the company
Polytec GmbH mit der Software „AB2 Luminescence Spectrometer Version 5.0 Beta 1.45" durchgeführt. Die Anregung erfolgte durch eine 150 W Ozon-freie Xenon- Lampe (Continiuous Wave). Zwei leistungsfähige Monocliromatoren sorgten mit einer Focusierlänge von 200 mm sowohl auf der Seite der Excitations als auch bei der Emission für präzises Scannen und hohe Auflösung. Der Photomultiplier (PMT) wandelt das optische in ein elektrisches Signal um, welches durch die Elektronik verstärkt und ausgewertet wird. Polytec GmbH with the software "AB2 Luminescence Spectrometer Version 5.0 Beta 1.45" carried out. The excitation was carried out by a 150 W ozone-free xenon lamp (Continiuous Wave). Two powerful monocliromators with a focusing length of 200 mm ensured both on the excitation side as well as for emission for precise scanning and high resolution The photomultiplier (PMT) converts the optical into an electrical signal, which is amplified and evaluated by the electronics.

Claims

Patentansprüche claims
1. Verfahren zur Durchführung von Konzentrationsbestimmungen wässriger Lösungen oder zur Online-Bestimmung der Dosierkonzentration von Poly- asparaginsäuren und/oder ihrer Salze, dadurch gekennzeichnet, dass dieses mittels Fluorometrie erfolgt.1. A method for carrying out concentration determinations of aqueous solutions or for online determination of the dosing concentration of polyaspartic acids and / or their salts, characterized in that this is carried out by means of fluorometry.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass dieses in Aqua dest., Leitungswasser, Flusswasser, industriellen Flüssigkeitsströmen, natür- liehen Abwassersystemen, industriellen Abwassersystemen, Bauwerksentwässerungssystemen, Öl/Wasser-Gemischen und anderen Wassersystemen zur Verhinderung oder Rückbildung oder Entfernung anorganischer oder organischer Scales angewandt wird.2. The method according to claim 1, characterized in that it in aqua dest., Tap water, river water, industrial liquid streams, natural wastewater systems, industrial wastewater systems, building drainage systems, oil / water mixtures and other water systems to prevent or regress or remove inorganic or organic scales is applied.
3. Verfahren gemäß der Ansprüche 1 und 2, dadurch gekennzeichnet, dass Polyasparaginsäuren im Bereich 0,1 bis 1000 ppm fluorometrisch bestimmt werden.3. The method according to claims 1 and 2, characterized in that polyaspartic acids in the range 0.1 to 1000 ppm are determined fluorometrically.
4. Verfahren gemäß der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass dieses in einem Temperaturbereich von 0 bis 70°C angewandt wird.4. The method according to claims 1 to 3, characterized in that this is applied in a temperature range from 0 to 70 ° C.
5. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass dieses im pH- Bereich von 0 bis 14 angewandt wird.5. The method according to claim 1, characterized in that this is applied in the pH range from 0 to 14.
6. Verwendung des Verfahrens zur Konzentrationsbestimmung oder zur Online-6. Use of the procedure for determining the concentration or for online
Bestimmung der Dosierkonzentration von Polyasparaginsäuren und/oder ihrer Salze in industriellen Flüssigkeitssrömen, natürlichen oder industriellen Abwassersystemen, Reinigern, Dispersionen und Formulierungen mit Poly- asparaginsäure auf Wasserbasis, in der Papierherstellung, bei der Erdöl- gewinnung oder beim Eindampfen von Zuckersäften. Determination of the dosing concentration of polyaspartic acids and / or their salts in industrial liquid flows, natural or industrial waste water systems, cleaners, dispersions and formulations with water-based polyaspartic acid, in paper manufacture, in oil production or in the evaporation of sugar juices.
EP01960679A 2000-08-30 2001-08-20 Determining the concentration of polyaspartic acid using fluorometry Withdrawn EP1315762A1 (en)

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DE10042498A DE10042498A1 (en) 2000-08-30 2000-08-30 Polyaspartic acid concentration determination using fluorometry
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PCT/EP2001/009557 WO2002018458A1 (en) 2000-08-30 2001-08-20 Determining the concentration of polyaspartic acid using fluorometry

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WO2002018458A1 (en) 2002-03-07

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