EP0807696A1 - Alkalizing agent for water conditioning - Google Patents

Alkalizing agent for water conditioning Download PDF

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EP0807696A1
EP0807696A1 EP96810289A EP96810289A EP0807696A1 EP 0807696 A1 EP0807696 A1 EP 0807696A1 EP 96810289 A EP96810289 A EP 96810289A EP 96810289 A EP96810289 A EP 96810289A EP 0807696 A1 EP0807696 A1 EP 0807696A1
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Prior art keywords
alkalizing agent
agent according
boiler
steam
alkalizing
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German (de)
French (fr)
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EP0807696B1 (en
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Anton Graf
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Faborga SA
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Faborga SA
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Priority to DE59602547T priority patent/DE59602547D1/en
Priority to AT96810289T priority patent/ATE182633T1/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14Nitrogen-containing compounds
    • C23F11/141Amines; Quaternary ammonium compounds

Definitions

  • the present invention relates to an alkalizing agent for aqueous media in the form of a mixture of amines.
  • the alkalizing agent is particularly intended for use in water-steam cycles of power plants which have a once-through boiler as the steam generator.
  • a very widely used possibility for conditioning is the alkalization of the water-steam cycle, which is based on the fact that the dissolution of iron from the apparatus parts, which is observed at high temperatures, is reduced by raising the pH.
  • An overview of the conditioning of feed water with alkalizing agents can be found in the VGB guideline for boiler feed water, boiler water and Steam from steam generators over 68 bar permissible operating pressure (VGB-R 450 L), published by the VGB technical association of large power plant operators eV, Essen 1988.
  • Forced-flow boiler systems are found particularly in power plants of the electricity supply companies and in large industrial plants because they allow in large units, even under supercritical conditions, i.e. to generate steam at very high pressures and high temperatures. It is known that the thermal efficiency of power plants improves with increasing operating temperature.
  • Ammonia has been widely used as a volatile alkalizing agent.
  • it has turned out to be disadvantageous that, due to its high volatility and its unfavorable distribution between water and steam, it is not possible to achieve a uniform alkalization of all parts of the circuit.
  • One has therefore searched for less volatile bases and has already used mixtures of differently volatile amines in order to use the special conditions of Phase transition during evaporation, condensation and in the two-phase area of wet steam to inhibit the respective forms of corrosion.
  • European Patent Application No. 0'134'365 discloses a means for corrosion inhibition in steam generators or for conditioning boiler feed water for power plants with a circulation boiler and operating conditions of 35 bar / 320 ° C in the boiler.
  • the agent consists of a "film-forming" amine and at least one alkalizing amine.
  • the object of the invention was to provide an alkalizing agent that meets the requirements specified above and is particularly suitable for use as a water conditioning agent in high-performance steam boiler systems for corrosion protection.
  • the corrosion protection effect in the steam boiler should be achieved, and on the other hand, all downstream components, in particular the turbine, should be protected against corrosion.
  • the agent is composed of at least three different types of amines, namely (a) a monoalkanolamine, (b) optionally substituted cyclohexylamine and (c) at least one film-forming long-chain aliphatic polyamine, also known as fatty polyamine.
  • the role of the first component namely the monoalkanolamine, is seen in the fact that it primarily serves to permanently alkalize the aqueous phase including the condensate.
  • the amino alcohol used is in particular one which has a boiling point between 150 and 190 ° C., for example monoethanolamine (1-aminoethanol) or isopropanolamine (2-amino-2-methyl-1-propanol).
  • monoethanolamine 1-aminoethanol
  • isopropanolamine 2-amino-2-methyl-1-propanol
  • other amino alcohols can also be used, provided that they have the properties described above.
  • the second component of the alkalizing agent according to the invention is optionally substituted cyclohexylamine. It is an amine volatile with water vapor, which forms an amine-containing, ie basic, protective layer and stabilizes the magnetite protective layer. It was found that the layer mentioned consists predominantly of dicyclohexylamine, which, under the conditions of use in a steam boiler, was formed from two molecules of cyclohexylamine according to the following scheme: 2 C 6 H 11 NH 2nd ⁇ (C 6 H 11 ) 2nd NH + NH 3rd
  • the present invention proposes to use unsubstituted cyclohexylamine; but there are also inert substituted cyclohexylamines, such as. B. dicyclohexylamine, methylcyclohexylamine, ethylcyclohexylamine, dimethylcyclohexylamine and others. Such compounds are by hydrogenation of the corresponding aromatic amines or nitro compounds easily accessible.
  • the optionally substituted cyclohexylamine acts as a hydrotrope in the preparation of the composition according to the invention and also has the property of increasing the volatility of the third component described below and of bringing it to the turbine in larger amounts than hitherto.
  • the alkalizing agent according to the invention accordingly not only acts to set the desired pH value in the feed water and in the steam boiler, but also forms corrosion protection layers in all parts of the system.
  • Examples of such polyamines are Dodecylaminomethylenamin, Dodecylaminodimethylenamin, Dodecylaminotrimethylenamin, the corresponding tetradecyl, hexadecyl and octadecylamine, Octadecenylaminotrimethylenamin, Octadecenylaminodi- (trimethylamino) -trimethylenamin, Palmitylaminotrimethylenamin, Hexadecenylaminotrimethylenamin, Dodecenylaminotrimethylenamin, etc.
  • the N-oleyl-1,3-propanediamine ie octadecen (9) ylaminotrimethyleneamine
  • the proportions of the three components of the alkalizing agent according to the invention described above can vary within wide limits depending on the conditions of use and the individual substances chosen in each case. If, for example, component (a) monoethanolamine, component (b) cyclohexylamine and component (c) oleylaminopropyleneamine are chosen, the weight fractions of components (a), (b) and (c) are pure, i.e. 100% related connections, such as (40-70) :( 30-50) :( 4-10), the sum of the three components adding up to 100.
  • the alkalizing agent according to the invention can also contain other constituents, generally in very small amounts, so as not to impair the effect. For example, you can stain the labeling agent.
  • the alkalizing agent according to the invention is preferably formulated as an aqueous, relatively concentrated solution which can be easily metered into the system to be conditioned.
  • An aqueous mixture containing about 4 to 25% by weight of the alkalizing agent is a clear, stable solution, although it contains up to about 4% by weight of fatty alkyl polyamine, which is only slightly water-soluble per se.
  • the cyclohexylamine is an effective solubilizer, that is to say a hydrotropic substance, for the fatty polyamine.
  • the procedure is advantageously firstly to prepare a relatively concentrated aqueous solution of monoethanolamine, which is freely miscible with water, and then to stir in a previously prepared mixture of the fatty aminoalkylene amine and the cyclohexylamine.
  • a relatively concentrated aqueous solution is obtained in this way, which can then be diluted without restriction with water, preferably pure, demineralized and non-carbonated water, preferably to an approximately 15% solution.
  • the latter has a pH of about 12 to 12.5.
  • the alkalizing agent according to the invention is generally used in proportions which correspond to an active ingredient concentration in the water of about 0.5 to 5 ppm. Higher shares can also be provided, should this be necessary in special cases. Since the agent of the invention can be provided as an aqueous solution, it is possible to dose easily and precisely.
  • the alkalizing agent according to the invention was tested in a large-scale test for its effectiveness.
  • a solution of the above-described alkalizing agent was added to the feed water in the metering station for conditioning agent of a power plant block, containing a once-through boiler, operating pressure 180 bar (18 MPa), main steam temperature 540 ° C, and a steam turbine with an output of 311 MW, such that a Concentration of 1 to 2 mg / l (1 to 2 ppm) was set and maintained.
  • Steam samples were continuously taken from the live steam line, the samples through Cooling condenses, the condensate is passed through a strongly acidic ion exchanger and finally the conductance is measured in the outlet of the ion exchanger.
  • the pH value of the condensate (in front of the ion exchanger) was in the range from 8.7 to 9.5 with a most common value of 9.4.
  • the conductivity was approximately 0.15 to 0.16 ⁇ S ⁇ cm -1 . It must be said that the guidelines of the VGB (Technical Association of Large Power Plant Operators eV) for boiler feed water for corresponding power plants have a pH value of 9.5 ⁇ 0.2 and for conductivity a value of ⁇ 0.2 ⁇ S ⁇ cm -1 provide.
  • alkalizing agent of the invention is not limited to a once-through boiler; it is clear to the person skilled in the art that the concept of the invention can be applied to all boiler and power plant systems, e.g. also circulation boiler.
  • the alkalizing agent according to the invention can not only be used as a water conditioning agent for high-performance steam boilers, but it can also be used wherever a mixture of amines is to be used, for example as a neutralizing agent, for the production of soil waxes based on fatty acid amides and imides, complexing agents and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Steam Or Hot-Water Central Heating Systems (AREA)
  • Jet Pumps And Other Pumps (AREA)

Abstract

An alkalisation agent especially for use in conditioning boiler feed water comprises three different amines: (A) an alkanolamine; (B) an optionally substituted cyclohexylamine; and (C) a long-chain aliphatic polyamine.

Description

Die vorliegende Erfindung betrifft ein Alkalisierungsmittel für wässrige Medien in Form eines Gemisches von Aminen. Das Alkalisierungsmittel ist insbesondere zur Verwendung In Wasser-Dampf-Kreislaufen von Kraftwerken vorgesehen, die als Dampferzeuger einen Zwangsdurchlaufkessel besitzen.The present invention relates to an alkalizing agent for aqueous media in the form of a mixture of amines. The alkalizing agent is particularly intended for use in water-steam cycles of power plants which have a once-through boiler as the steam generator.

Es ist bekannt, dass Dampferzeugungsanlagen gegen Korrosion geschützt werden müssen, um einen sicheren und störungsfreien Dauerbetrieb zu gewährleisten. Das Speisewasser für Durchlaufkessel, das Speise- und das Kesselwasser von Umlaufkesseln sowie Einspritzwasser zur Dampftemperaturregelung müssen bestimmte Qualitätsanforderungen erfüllen, damit sowohl die Dampferzeuger sicher und wirtschaftlich betrieben werden können als auch die für Überhitzer und nachgeschaltete Turbinen erforderliche Dampfreinheit erzielt wird. Wenn das Betriebsmittel im Kreislauf geführt wird, dürfen Wasser und Dampfqualität nicht im Hinblick auf einzelne Anlagenteile betrachtet werden, sondern stets nur im Zusammenhang mit dem gesamten Wasser-Dampf-Kreislauf.It is known that steam generating plants must be protected against corrosion in order to ensure safe and trouble-free continuous operation. The feed water for once-through boilers, the feed and boiler water of circulation boilers and the injection water for steam temperature control must meet certain quality requirements so that both the steam generator can be operated safely and economically and the steam cleanliness required for superheaters and downstream turbines can be achieved. If the equipment is circulated, water and steam quality must not be considered with regard to individual system parts, but always only in connection with the entire water-steam cycle.

Eine sehr verbreitet genutzte Möglichkeit zur Konditionierung ist die Alkalisierung des Wasser-Dampf-Kreislaufs, welche auf der Tatsache beruht, dass die Auflösung von Eisen aus den Apparateteilen, die bei hohen Temperaturen beobachtet wird, durch Anheben des pH-Wertes vermindert wird. Eine Übersicht über die Konditionierung von Speisewasser mit Alkalisierungsmitteln findet sich in der VGB-Richtlinie für Kesselspeisewasser, Kesselwasser und Dampf von Dampferzeugern über 68 bar zulässigem Betriebsdruck (VGB-R 450 L), herausgegeben von der VGB technischen Vereinigung der Grosskraftwerkbetreiber e.V., Essen 1988.A very widely used possibility for conditioning is the alkalization of the water-steam cycle, which is based on the fact that the dissolution of iron from the apparatus parts, which is observed at high temperatures, is reduced by raising the pH. An overview of the conditioning of feed water with alkalizing agents can be found in the VGB guideline for boiler feed water, boiler water and Steam from steam generators over 68 bar permissible operating pressure (VGB-R 450 L), published by the VGB technical association of large power plant operators eV, Essen 1988.

Zwangsdurchlauf-Kesselanlagen finden sich besonders in Kraftwerken der Elektrizitäts-Versorgungsunternehmen und in grossen Industrieanlagen, weil sie in grossen Einheiten erlauben, auch unter überkritischen Bedingungen, d.h. bei sehr hohen Drücken und hohen Temperaturen, Dampf zu erzeugen. Es ist bekannt, dass sich der thermische Wirkungsgrad von Kraftwerken mit steigender Betriebstemperatur verbessert.Forced-flow boiler systems are found particularly in power plants of the electricity supply companies and in large industrial plants because they allow in large units, even under supercritical conditions, i.e. to generate steam at very high pressures and high temperatures. It is known that the thermal efficiency of power plants improves with increasing operating temperature.

Wegen der konstruktiven Gegebenheiten solcher Dampferzeuger und aus Gründen der Anforderungen, die die nachgeschalteten Turbinen erfüllen müssen, ist es notwendig, zur Kesselspeisung salzfreies Wasser zu verwenden, welches durch Vollentsalzung von natürlichem Süsswasser gewonnen wird. Alle Konditionierungsmittel, die zur Korrosionsinhibierung dem Wasser-Dampf-Kreislauf zugesetzt werden, müssen im Falle von Zwangsdurchlaufkesseln vollständig wasserdampfflüchtig sein, d.h. die Konditionierung erfolgt mit flüchtigen Alkalisierungsmitteln.Because of the design of such steam generators and because of the requirements that the downstream turbines have to meet, it is necessary to use salt-free water for the boiler feed, which is obtained by the complete desalination of natural fresh water. All conditioning agents that are added to the water-steam cycle to inhibit corrosion must be completely steam-volatile in the case of once-through boilers, i.e. conditioning is carried out with volatile alkalizing agents.

Vielfach ist Ammoniak als flüchtiges Alkalisierungsmittel verwendet worden. Es hat sich jedoch als nachteilig herausgestellt, dass es wegen seiner hohen Flüchtigkeit und seiner ungünstigen Verteilung zwischen Wasser und Dampf nicht möglich ist, eine gleichmässige Alkalisierung aller Teile des Kreislaufs zu erreichen. Man hat deshalb nach weniger flüchtigen Basen gesucht und auch schon Mischungen von unterschiedlich flüchtigen Aminen eingesetzt, um unter den besonderen Bedingungen des Phasenübergangs beim Verdampfen, bei der Kondensation und im Zweiphasengebiet des Nassdampfes die jeweiligen Formen der Korrosion zu inhibieren.Ammonia has been widely used as a volatile alkalizing agent. However, it has turned out to be disadvantageous that, due to its high volatility and its unfavorable distribution between water and steam, it is not possible to achieve a uniform alkalization of all parts of the circuit. One has therefore searched for less volatile bases and has already used mixtures of differently volatile amines in order to use the special conditions of Phase transition during evaporation, condensation and in the two-phase area of wet steam to inhibit the respective forms of corrosion.

So offenbart beispielsweise die europäische Patentanmeldung Nr. 0'134'365 ein Mittel zur Korrosionsinhibierung in Dampferzeugern bzw. zur Konditionierung von Kesselspeisewasser für Kraftwerke mit einem Umlaufkessel und Betriebsbedingungen von 35 bar/320°C im Kessel. Das Mittel besteht aus einem "filmbildenden" Amin und mindestens einem alkalisierenden Amin.For example, European Patent Application No. 0'134'365 discloses a means for corrosion inhibition in steam generators or for conditioning boiler feed water for power plants with a circulation boiler and operating conditions of 35 bar / 320 ° C in the boiler. The agent consists of a "film-forming" amine and at least one alkalizing amine.

Eine Verwendung der sogenannten "filmbildenden" Amine, welche besondere Eigenschaften der Korrosionsinhibierung im "kalten" Teil des Kreislaufs auch in Anwesenheit von Sauerstoff zeigen, ist unter den überaus strengen Anforderungen für Zwangsdurchlaufkessel im Hochdruck- und Hochtemperaturbereich bisher nicht vorgeschlagen und auch nicht bekannt geworden. So erreicht man mit den in obiger Patentanmeldung vorgeschlagenen Mitteln längst nicht die maximale Leitfähigkeit von 0,2 µScm-1 im Kondensat, die von den VGB-Richtlinien gefordert wird (s.u.).The use of the so-called "film-forming" amines, which show special properties of corrosion inhibition in the "cold" part of the circuit even in the presence of oxygen, has not been proposed and has not been disclosed under the extremely strict requirements for once-through boilers in the high-pressure and high-temperature range. Thus, the means proposed in the above patent application do not achieve the maximum conductivity of 0.2 µScm -1 in the condensate, which is required by the VGB guidelines (see below).

Was die heissen Teile des Kreislaufes, also insbesondere den Kessel mit seinen Siederohren und den Überhitzer betrifft, so ist es jahrelange Betriebserfahrung, dass durch die spontane Magnetitbildung entsprechend der Schikorr-Reaktion bei Temperaturen über 200 °C die betreffenden Stahloberflächen während des Betriebes vor Korrosion in Reinstwasser geschützt sind.As for the hot parts of the circuit, in particular the boiler with its boiler tubes and the superheater, it has been years of operating experience that the steel surfaces in question spontaneously develop during operation due to the spontaneous magnetite formation corresponding to the Schikorr reaction at temperatures above 200 ° C Ultrapure water are protected.

Die wichtigsten Anforderungen an ein gutes Konditionierungsmittel für einen Wasser-Dampf-Kreislauf in Zwangsdurchlaufkesseln mit nachgeschalteter Turbine und Rückführung des Kondensats sind die folgenden:

  • 1) Alkalisierung des gesamten Kreislaufs, besonders bei Phasenübergängen und im Zweiphasengebiet, um die Korrosionsanfälligkeit von Stahloberflächen auf ein Minimum zu bringen;
  • 2) Bildung einer korrosionsinhibierenden Membran bei Temperaturen unter 200 °C;
  • 3) Ausreichende Temperaturbeständigkeit bis 560 °C, um in der Turbine und im Kondensat nach Passieren des Überhitzers wirksam zu sein;
  • 4) Maximale Leitfähigkeit des aus der Turbine abströmenden Kondensats gemäss VGB-Richtlinie von 0,2 µS·cm-1;
  • 5) Ökotoxikologische Unbedenklichkeit bei bestimmungsgemässem Einsatz; und
  • 6) Annehmbarer Preis bzw. optimales Kosten-Nutzen-Verhältnis.
The most important requirements for a good conditioning agent for a water-steam circuit in once-through boilers with a downstream turbine and return of the condensate are the following:
  • 1) Alkalization of the entire circuit, especially during phase transitions and in the two-phase area, in order to minimize the susceptibility to corrosion of steel surfaces;
  • 2) formation of a corrosion-inhibiting membrane at temperatures below 200 ° C;
  • 3) Sufficient temperature resistance up to 560 ° C to be effective in the turbine and in the condensate after passing through the superheater;
  • 4) Maximum conductivity of the condensate flowing out of the turbine according to the VGB guideline of 0.2 µS · cm -1 ;
  • 5) Ecotoxicological harmlessness when used as intended; and
  • 6) Acceptable price or optimal cost-benefit ratio.

Aufgabe der Erfindung war es, ein Alkalisierungsmittel anzugeben, das die oben angegebenen Anforderungen erfüllt und insbesondere zum Einsatz als Wasserkonditionierungsmittel in Hochleistungs-Dampfkesselanlagen zum Korrosionsschutz geeignet ist. Einerseits soll die Korrosionsschutzwirkung im Dampfkessel erreicht werden, und andererseits sollen alle nachgeschalteten Bestandteile, insbesondere die Turbine, vor Korrosion geschützt werden.The object of the invention was to provide an alkalizing agent that meets the requirements specified above and is particularly suitable for use as a water conditioning agent in high-performance steam boiler systems for corrosion protection. On the one hand, the corrosion protection effect in the steam boiler should be achieved, and on the other hand, all downstream components, in particular the turbine, should be protected against corrosion.

Es wurde nun gefunden, dass ein Gemisch aus bestimmten Aminen die oben Aufgabe der Erfindung erfüllt und darüber hinaus weitere vorteilhafte Eigenschaften besitzt. Erfindungsgemäss ist das Mittel aus mindestens drei unterschiedlichen Arten von Aminen zusammengesetzt, nämlich (a) einem Monoalkanolamin, (b) gegebenenfalls substituiertem Cyclohexylamin und (c) mindestens einem filmbildenden langkettigen aliphatischen Polyamin, auch als Fettpolyamin bezeichnet.It has now been found that a mixture of certain amines fulfills the object of the invention above and also has further advantageous properties. According to the invention, the agent is composed of at least three different types of amines, namely (a) a monoalkanolamine, (b) optionally substituted cyclohexylamine and (c) at least one film-forming long-chain aliphatic polyamine, also known as fatty polyamine.

Die Rolle der ersten Komponente, nämlich des Monoalkanolamins, wird darin gesehen, dass es in erster Linie zur permanenten Alkalisierung der wässrigen Phase einschliesslich des Kondensats dient.The role of the first component, namely the monoalkanolamine, is seen in the fact that it primarily serves to permanently alkalize the aqueous phase including the condensate.

Als Aminoalkohol wird insbesondere ein solcher verwendet, der einen Siedepunkt zwischen 150 und 190 °C aufweist, beispielsweise Monoethanolamin (1-Aminoethanol) oder Isopropanolamin (2-Amino-2-methyl-1-propanol). Gegenwärtig bevorzugt ist die Verwendung von Monoethanolamin. Aber auch andere Aminoalkohole sind verwendbar, sofern sie die oben beschriebenen Wirkungseigenschaften haben.The amino alcohol used is in particular one which has a boiling point between 150 and 190 ° C., for example monoethanolamine (1-aminoethanol) or isopropanolamine (2-amino-2-methyl-1-propanol). The use of monoethanolamine is currently preferred. However, other amino alcohols can also be used, provided that they have the properties described above.

Die zweite Komponente des erfindungsgemässen Alkalisierungsmittels ist gegebenenfalls substituiertes Cyclohexylamin. Es ist ein mit Wasserdampf flüchtiges Amin, welches eine aminhaltige, d.h. basische schützende Schicht bildet sowie die Magnetitschutzschicht stabilisiert. Es wurde gefunden, dass die erwähnte Schicht überwiegend aus Dicyclohexylamin besteht, das bei den Bedingungen der Anwendung im Dampfkessel aus zwei Molekülen Cyclohexylamin nach folgendem Schema entstanden ist: 2 C 6 H 11 NH 2 ⇒ (C 6 H 11 ) 2 NH + NH 3

Figure imgb0001
The second component of the alkalizing agent according to the invention is optionally substituted cyclohexylamine. It is an amine volatile with water vapor, which forms an amine-containing, ie basic, protective layer and stabilizes the magnetite protective layer. It was found that the layer mentioned consists predominantly of dicyclohexylamine, which, under the conditions of use in a steam boiler, was formed from two molecules of cyclohexylamine according to the following scheme: 2 C 6 H 11 NH 2nd ⇒ (C 6 H 11 ) 2nd NH + NH 3rd
Figure imgb0001

Normalerweise schlägt die vorliegende Erfindung vor, unsubstituiertes Cyclohexylamin einzusetzen; es kommen aber auch inert substituierte Cyclohexylamine in Betracht, wie z. B. Dicyclohexylamin, Methylcyclohexylamin, Ethylcyclohexylamin, Dimethylcyclohexylamin und andere. Derartige Verbindungen sind durch Hydrierung der entsprechenden aromatischen Amine oder Nitroverbindungen leicht zugänglich.Normally, the present invention proposes to use unsubstituted cyclohexylamine; but there are also inert substituted cyclohexylamines, such as. B. dicyclohexylamine, methylcyclohexylamine, ethylcyclohexylamine, dimethylcyclohexylamine and others. Such compounds are by hydrogenation of the corresponding aromatic amines or nitro compounds easily accessible.

Weiterhin wirkt das gegebenenfalls substituierte Cyclohexylamin als Hydrotrop bei der Herstellung des erfindungsgemässen Mittels und hat ausserdem die Eigenschaft, die Wasserdampfflüchtigkeit der nachstehend beschriebenen dritten Komponente zu erhöhen und diese in grösseren Mengen als bisher auf die Turbine zu bringen.Furthermore, the optionally substituted cyclohexylamine acts as a hydrotrope in the preparation of the composition according to the invention and also has the property of increasing the volatility of the third component described below and of bringing it to the turbine in larger amounts than hitherto.

Die dritte Komponente des erfindungsgemässen Alkalisierungsmittels ist ein langkettiges aliphatisches Polyamin. Geeignete Polyamine sind in grosser Zahl bekannt und im Handel erhältlich. Die im Rahmen der Erfindung verwendbaren Fettpolyamine entsprechen der allgemeinen Formel

        R―[NH―(CH2)p―]n―NH2

   worin bedeuten:

  • R einen aliphatischen Kohlenwasserstoffrest mit 12 bis 24 Kohlenstoffatomen,
  • p eine ganze Zahl von 1 bis 6, vorzugsweise 3, und
  • n eine ganze Zahl von 1 bis 6, vorzugsweise 1.
The third component of the alkalizing agent according to the invention is a long-chain aliphatic polyamine. Suitable polyamines are known in large numbers and are commercially available. The fatty polyamines which can be used in the context of the invention correspond to the general formula

R― [NH― (CH 2 ) p -] n ―NH 2

in which mean:
  • R is an aliphatic hydrocarbon radical having 12 to 24 carbon atoms,
  • p is an integer from 1 to 6, preferably 3, and
  • n is an integer from 1 to 6, preferably 1.

Die Wirkung dieser langkettigen Fettpolyamine beruht auf der Ausbildung einer hydrophoben, festhaftenden schützenden Membran auf der Unterlage, welche normalerweise eine sehr dünne Magnetitschicht ist. Diese Wirkungsweise ist bereits aus der Literatur bekannt. Zusätzlich wurde jedoch eine weitere Eigenschaft gefunden: das Fettpolyamin komplexiert aus dem Metall austretende Eisen(II)-ionen, und dieser Komplex begünstigt bei seiner Oxidation die Bildung von Magnetit. Gegebenenfalls anwesender Sauerstoff wird auf diese Weise gebunden.The effect of these long-chain fatty polyamines is based on the formation of a hydrophobic, firmly adhering protective membrane on the base, which is normally a very thin layer of magnetite. This mode of action is already known from the literature. In addition, however, another property has been found: the fatty polyamine complexes iron (II) ions emerging from the metal, and this complex promotes formation when it is oxidized from Magnetit. Any oxygen present is bound in this way.

Das erfindungsgemässe Alkalisierungsmittel wirkt demgemäss nicht nur zur Einstellung des gewünschten pH-Wertes im Speisewasser und im Dampfkessel, sondern bildet Korrosionsschutzschichten in allen Teilen der Anlage aus.The alkalizing agent according to the invention accordingly not only acts to set the desired pH value in the feed water and in the steam boiler, but also forms corrosion protection layers in all parts of the system.

Beispiele solcher Polyamine sind Dodecylaminomethylenamin, Dodecylaminodimethylenamin, Dodecylaminotrimethylenamin, die entsprechenden Tetradecyl-, Hexadecyl- und Octadecylamine, Octadecenylaminotrimethylenamin, Octadecenylaminodi-(trimethylamino)-trimethylenamin, Palmitylaminotrimethylenamin, Hexadecenylaminotrimethylenamin, Dodecenylaminotrimethylenamin, usw. Gegenwärtig wird das N-Oleyl-1,3-propandiamin (d.h. Octadecen(9)ylaminotrimethylenamin) bevorzugt.Examples of such polyamines are Dodecylaminomethylenamin, Dodecylaminodimethylenamin, Dodecylaminotrimethylenamin, the corresponding tetradecyl, hexadecyl and octadecylamine, Octadecenylaminotrimethylenamin, Octadecenylaminodi- (trimethylamino) -trimethylenamin, Palmitylaminotrimethylenamin, Hexadecenylaminotrimethylenamin, Dodecenylaminotrimethylenamin, etc. At present, the N-oleyl-1,3-propanediamine (ie octadecen (9) ylaminotrimethyleneamine) is preferred.

Die Mengenverhältnisse der oben beschriebenen drei Komponenten des erfindungsgemässen Alkalisierungsmittel können je nach den Anwendungsbedingungen und den jeweils gewählten individuellen Substanzen in weiten Grenzen schwanken. Falls beispielsweise als Komponente (a) Monoethanolamin, als Komponente (b) Cyclohexylamin und als Komponente (c) Oleylaminopropylenamin gewählt werden, so verhalten sich die Gewichtsanteile der Komponenten (a), (b) und (c), auf reine, also 100 %ige Verbindungen bezogen, wie (40-70):(30-50):(4-10), wobei die Summe der drei Bestandteile sich zu 100 ergänzt.The proportions of the three components of the alkalizing agent according to the invention described above can vary within wide limits depending on the conditions of use and the individual substances chosen in each case. If, for example, component (a) monoethanolamine, component (b) cyclohexylamine and component (c) oleylaminopropyleneamine are chosen, the weight fractions of components (a), (b) and (c) are pure, i.e. 100% related connections, such as (40-70) :( 30-50) :( 4-10), the sum of the three components adding up to 100.

Das erfindungsgemässe Alkalisierungsmittel kann im übrigen weitere Bestandteile enthalten, im allgemeinen in sehr geringen Mengen, um die Wirkung nicht zu beeinträchtigen. Beispielsweise kann man das Mittel zur Kennzeichnung anfärben.The alkalizing agent according to the invention can also contain other constituents, generally in very small amounts, so as not to impair the effect. For example, you can stain the labeling agent.

Das erfindungsgemässe Alkalisierungsmittel wird vorzugsweise als wässrige, relativ konzentrierte Lösung formuliert, die dem zu konditionierenden System leicht zudosiert werden kann. Eine wässrige Mischung, welche etwa 4 bis 25 Gew.-% des Alkalisierungsmittels enthält, stellt eine klare, stabile Lösung dar, obwohl sie bis zu etwa 4 Gew.-% an Fettalkylpolyamin enthält, welches an sich nur geringfügig wasserlöslich ist. Wie oben schon erwähnt wurde, hat es sich nämlich überraschend erwiesen, dass das Cyclohexylamin einen wirksamen Lösungsvermittler, also eine hydrotrope Substanz, für das Fettpolyamin darstellt. Zur Herstellung der wässrigen Lösung des Mittels geht man vorteilhafterweise so vor, dass man zunächst eine relativ konzentrierte wässrige Lösung an Monoethanolamin herstellt, welches unbeschränkt mit Wasser mischbar ist, und dann ein zuvor bereitetes Gemisch aus dem Fettaminoalkylenamin und dem Cyclohexylamin einrührt. Man erhält auf diese Weise eine relativ konzentrierte wässrige Lösung, die dann unbeschränkt mit Wasser, bevorzugt reinem, entmineralisiertem und kohlensäurefreiem Wasser, verdünnbar ist, vorzugsweise zu einer etwa 15 %igen Lösung. Diese letztere weist einen pH-Wert von etwa 12 bis 12,5 auf.The alkalizing agent according to the invention is preferably formulated as an aqueous, relatively concentrated solution which can be easily metered into the system to be conditioned. An aqueous mixture containing about 4 to 25% by weight of the alkalizing agent is a clear, stable solution, although it contains up to about 4% by weight of fatty alkyl polyamine, which is only slightly water-soluble per se. As already mentioned above, it has surprisingly been found that the cyclohexylamine is an effective solubilizer, that is to say a hydrotropic substance, for the fatty polyamine. To prepare the aqueous solution of the agent, the procedure is advantageously firstly to prepare a relatively concentrated aqueous solution of monoethanolamine, which is freely miscible with water, and then to stir in a previously prepared mixture of the fatty aminoalkylene amine and the cyclohexylamine. A relatively concentrated aqueous solution is obtained in this way, which can then be diluted without restriction with water, preferably pure, demineralized and non-carbonated water, preferably to an approximately 15% solution. The latter has a pH of about 12 to 12.5.

Bei der Anwendung des erfindungsgemässen Alkalisierungsmittels in Hochleistungs-Dampferzeugern und Kraftwerken, d.h. mit einem Betriebsdruck weit über 68 bar, beispielsweise über 150 bar, und bei Betriebstemperaturen über 500 °C, hat sich überraschend herausgestellt, dass der in der oben genannten VGB-Richtlinie geforderte Grenzwert der Leitfähigkeit im Dampf und Kondensat, nämlich 0,2 µS·cm-1, der nach einem stark saurer Ionenaustauscher bestimmt wird, im Dauerbetrieb erreicht und unterschritten werden konnte. Damit steht zum ersten Mal ein Alkalisierungsmittel zur Verfügung, dass die eingangs aufgezählten Anforderungen sowie die Erfordernisse und nach der VGB-Richtlinie erfüllt. Dabei wurde weiterhin festgestellt, dass die Verwendung von besonders reinen oder gereinigten Ausgangsprodukten sehr günstig ist und zu noch niedrigeren Leitfähigkeitswerten führt. Der Grund dafür wird darin gesehen, dass sich Verunreinigungen im Konditionierungsmittel beim Betrieb in Hochleistungs-Kraftwerken unter Bildung saurer Substanzen zersetzen bzw. zu diesen oxidiert werden, welche die Leitfähigkeit des Wassers erhöhen und auch einen Teil des Alkalisierungsmittels unwirksam machen. Daher wird bei der Herstellung des Amingemisches empfohlen, möglichst reine Ausgangsstoffe zu verwenden und unter Schutzgas zu arbeiten, welches die Luftkohlensäure fernhält.When using the alkalizing agent according to the invention in high-performance steam generators and power plants, that is to say with an operating pressure of well over 68 bar, for example over 150 bar, and at operating temperatures above 500 ° C., it has surprisingly been found that the requirement specified in the above-mentioned VGB guideline Limit value of the conductivity in the steam and condensate, namely 0.2 µS · cm -1 , which is determined after a strongly acidic ion exchanger, could be reached and fallen below in continuous operation. This is the first time that an alkalizing agent is available that meets the requirements listed above and the requirements and after of the VGB guideline. It was also found that the use of particularly pure or purified starting products is very cheap and leads to even lower conductivity values. The reason for this is seen in the fact that impurities in the conditioning agent decompose or are oxidized to form acidic substances during operation in high-performance power plants, which increase the conductivity of the water and also render some of the alkalizing agent ineffective. For this reason, when producing the amine mixture, it is recommended to use raw materials that are as pure as possible and to work under a protective gas that keeps the carbon dioxide away.

Als Dosiermenge für den Einsatz als Wasserkonditionierungsmittel in Hochleistungsdampfkesseln setzt man das erfindungsgemässe Alkalisierungsmittel in der Regel in Anteilen ein, die einer Wirkstoffkonzentration im Wasser von etwa 0,5 bis 5 ppm entsprechen. Auch höhere Anteile können vorgesehen werden, falls dies in Sonderfällen erforderlich sein sollte. Da das Mittel der Erfindung als wässrige Lösung bereitgestellt werden kann, ist es möglich, einfach und genau zu dosieren.As a dosing quantity for use as a water conditioning agent in high-performance steam boilers, the alkalizing agent according to the invention is generally used in proportions which correspond to an active ingredient concentration in the water of about 0.5 to 5 ppm. Higher shares can also be provided, should this be necessary in special cases. Since the agent of the invention can be provided as an aqueous solution, it is possible to dose easily and precisely.

Das erfindungsgemässe Alkalisierungsmittel wurde in einem Grossversuch auf seine Wirksamkeit getestet. In die Dosierstation für Konditionierungsmittel eines Kraftwerkblockes, enthaltend einen Zwangsdurchlaufkessel, Betriebsdruck 180 bar (18 MPa), Frischdampftemperatur 540 °C, sowie eine Dampfturbine mit einer Leistung von 311 MW, wurde dem Speisewasser eine Lösung des oben beschriebenen Alkalisierungsmittels zugegeben, derart, dass eine Konzentration von 1 bis 2 mg/l (1 bis 2 ppm) eingestellt und aufrechterhalten wurde. Aus der Frischdampfleitung wurden laufend Dampfproben entnommen, die Proben durch Abkühlen kondensiert, das Kondensat durch einen stark sauren Ionenaustauscher geleitet und schliesslich im Ablauf des Ionenaustauschers der Leitwert gemessen. Der pH-Wert des Kondensats (vor dem Ionenaustauscher) bewegte sich im Bereich von 8,7 bis 9,5 mit einem häufigsten Wert von 9,4. Die Leitfähigkeit betrug etwa 0,15 bis 0,16 µS·cm-1. Dazu ist zu sagen, dass die Richtlinien der VGB (Technische Vereinigung der Grosskraftwerksbetreiber e.V.) für Kesselspeisewasser für entsprechende Kraftwerke einen pH-Wert von 9,5 ± 0,2 und für die Leitfähigkeit einen Wert von <0,2 µS·cm-1 vorsehen.The alkalizing agent according to the invention was tested in a large-scale test for its effectiveness. A solution of the above-described alkalizing agent was added to the feed water in the metering station for conditioning agent of a power plant block, containing a once-through boiler, operating pressure 180 bar (18 MPa), main steam temperature 540 ° C, and a steam turbine with an output of 311 MW, such that a Concentration of 1 to 2 mg / l (1 to 2 ppm) was set and maintained. Steam samples were continuously taken from the live steam line, the samples through Cooling condenses, the condensate is passed through a strongly acidic ion exchanger and finally the conductance is measured in the outlet of the ion exchanger. The pH value of the condensate (in front of the ion exchanger) was in the range from 8.7 to 9.5 with a most common value of 9.4. The conductivity was approximately 0.15 to 0.16 µS · cm -1 . It must be said that the guidelines of the VGB (Technical Association of Large Power Plant Operators eV) for boiler feed water for corresponding power plants have a pH value of 9.5 ± 0.2 and for conductivity a value of <0.2 µS · cm -1 provide.

Die Verwendung des Alkalisierungsmittels der Erfindung ist nicht auf Zwangsdurchlaufkessel beschränkt; dem Fachmann ist klar, dass sich das Konzept der Erfindung auf alle Kessel- und Kraftwerksanlagen anwenden lässt, z.B. auch Umlaufkessel.The use of the alkalizing agent of the invention is not limited to a once-through boiler; it is clear to the person skilled in the art that the concept of the invention can be applied to all boiler and power plant systems, e.g. also circulation boiler.

Das erfindungsgemässe Alkalisierungsmittel kann nicht nur als Wasserkonditionierungsmittel für Hochleistungsdampfkessel eingesetzt werden, sondern es ist auch überall dort brauchbar, wo ein Gemisch von Aminen einzusetzen ist, beispielsweise als Neutralisationsmittel, zur Herstellung von Bodenwachsen auf der Basis von Fettsäureamiden und -imiden, Komplexierungsmitteln und dergleichen.The alkalizing agent according to the invention can not only be used as a water conditioning agent for high-performance steam boilers, but it can also be used wherever a mixture of amines is to be used, for example as a neutralizing agent, for the production of soil waxes based on fatty acid amides and imides, complexing agents and the like.

Claims (12)

Alkalisierungsmittel für wässrige Medien in Form eines Gemisches von Aminen, dadurch gekennzeichnet, dass es aus mindestens drei unterschiedlichen Arten von Aminen zusammengesetzt ist, nämlich (a) mindestens einem Alkanolamin, (b) gegebenenfalls substituiertem Cyclohexylamin und (c) mindestens einem langkettigen aliphatischen Polyamin.Alkalizing agent for aqueous media in the form of a mixture of amines, characterized in that it is composed of at least three different types of amines, namely (a) at least one alkanolamine, (b) optionally substituted cyclohexylamine and (c) at least one long-chain aliphatic polyamine. Alkalisierungsmittel nach Anspruch 1, dadurch gekennzeichnet, dass es als wässrige Lösung vorliegt.Alkalizing agent according to claim 1, characterized in that it is present as an aqueous solution. Alkalisierungsmittel nach Anspruch 2, dadurch gekennzeichnet, dass die Konzentration der Lösung an Amingemisch 10 bis 18 Gew.-%, insbesondere etwa 15 Gew.-% beträgt.Alkalizing agent according to Claim 2, characterized in that the concentration of the amine mixture in the solution is 10 to 18% by weight, in particular approximately 15% by weight. Alkalisierungsmittel nach Anspruch 1, dadurch gekennzeichnet, dass es als Komponente (a) Monoethanolamin enthält.Alkalizing agent according to claim 1, characterized in that it contains as component (a) monoethanolamine. Alkalisierungsmittel nach Anspruch 4, dadurch gekennzeichnet, dass es als Komponente (b) Cyclohexylamin enthält.Alkalizing agent according to Claim 4, characterized in that it contains cyclohexylamine as component (b). Alkalisierungsmittel nach Anspruch 1, dadurch gekennzeichnet, dass es als Komponente (c) ein Polyamin der Formel

        R―[NH―(CH2)p―]n―NH2

   enthält, worin bedeuten: R einen aliphatischen Kohlenwasserstoffrest mit 12 bis 24 Kohlenstoffatomen, p eine ganze Zahl von 1 bis 6 und n eine ganze Zahl von 1 bis 6.
Alkalizing agent according to claim 1, characterized in that it is as component (c) a polyamine of the formula

R― [NH― (CH 2 ) p -] n ―NH 2

contains, in which mean: R is an aliphatic hydrocarbon radical having 12 to 24 carbon atoms, p is an integer from 1 to 6 and n is an integer from 1 to 6.
Alkalisierungsmittel nach Anspruch 4 und 5, dadurch gekennzeichnet, dass es als Komponente (c) N-Oleyl-1,3-propandiamin enthält.Alkalizing agent according to Claims 4 and 5, characterized in that it contains N-oleyl-1,3-propanediamine as component (c). Alkalisierungsmittel nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Bestandteile (a), (b) und (c), als Trockensubstanz gerechnet, im Gewichtsverhältnis von (40-70):(30-50):(4-25) stehen, wobei die Summe der drei Bestandteile sich zu 100 ergänzt.Alkalizing agent according to one of the preceding claims, characterized in that the components (a), (b) and (c), calculated as dry matter, are in a weight ratio of (40-70) :( 30-50) :( 4-25) , where the sum of the three components adds up to 100. Verfahren zur Konditionierung von Kesselspeisewasser, insbesondere für Hochleistungskesselanlagen, dadurch gekennzeichnet, dass man dem Speisewasser ein Alkalisierungsmittel nach einem der Ansprüche 1 bis 8 zudosiert.Process for conditioning boiler feed water, in particular for high-performance boiler systems, characterized in that an alkalizing agent according to one of claims 1 to 8 is metered into the feed water. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass man das Mittel nach Anspruch 8 verwendet.A method according to claim 9, characterized in that one uses the agent according to claim 8. Verfahren nach Anspruch 9 oder 10, dadurch gekennzeichnet, dass die Menge des Mittels derart dosiert wird, um im Kessel eine Konzentration von 0,5 bis 5 ppm des Mittels einzustellen und aufrechtzuerhalten.A method according to claim 9 or 10, characterized in that the amount of the agent is metered so as to adjust and maintain a concentration of 0.5 to 5 ppm of the agent in the boiler. Verfahren nach einem der Ansprüche 9 bis 11, dadurch gekennzeichnet, dass es als Konditionierungsmittel für das Kesselspeisewasser eines Durchlaufkessels mit nachgeschalteter Turbine verwendet wird, wobei der Betriebsdruck über 150 bar und die Dampftemperatur über 500 °C liegen.Method according to one of claims 9 to 11, characterized in that it is used as a conditioning agent for the boiler feed water of a once-through boiler with a downstream turbine, the operating pressure above 150 bar and the steam temperature above 500 ° C.
EP96810289A 1996-05-06 1996-05-06 Process for condirioning the feed water of once-through forced flow steam generators. Expired - Lifetime EP0807696B1 (en)

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DE59602547T DE59602547D1 (en) 1996-05-06 1996-05-06 Process for conditioning feed water for forced flow boiler systems
AT96810289T ATE182633T1 (en) 1996-05-06 1996-05-06 METHOD FOR CONDITIONING FEED WATER FOR FORCED CONTINUOUS BOILER SYSTEMS

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