EP1385974A2 - Method for the production of an aqueous acrylamide solution with a bio-catalyst - Google Patents

Method for the production of an aqueous acrylamide solution with a bio-catalyst

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Publication number
EP1385974A2
EP1385974A2 EP02740512A EP02740512A EP1385974A2 EP 1385974 A2 EP1385974 A2 EP 1385974A2 EP 02740512 A EP02740512 A EP 02740512A EP 02740512 A EP02740512 A EP 02740512A EP 1385974 A2 EP1385974 A2 EP 1385974A2
Authority
EP
European Patent Office
Prior art keywords
acrylonitrile
measurement
heat exchanger
pump
acrylamide
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.)
Ceased
Application number
EP02740512A
Other languages
German (de)
French (fr)
Inventor
Olaf Peterson
Peter Kroemker
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.)
Ineos Composites IP LLC
Original Assignee
Stockhausen GmbH
Stockhausen GmbH and Co KG
Chemische Fabrik Stockhausen 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 Stockhausen GmbH, Stockhausen GmbH and Co KG, Chemische Fabrik Stockhausen GmbH filed Critical Stockhausen GmbH
Publication of EP1385974A2 publication Critical patent/EP1385974A2/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
    • C12M41/48—Automatic or computerized control
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
    • C12M41/12—Means for regulation, monitoring, measurement or control, e.g. flow regulation of temperature
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes

Definitions

  • the present invention relates to a method and an apparatus for producing an aqueous acrylamide solution by hydrating acrylonitrile in an aqueous solution in the presence of a biocatalyst.
  • the object of the present invention is therefore to provide a method in which the biocatalyst is damaged as little as possible during the reaction and the batch time is optimized and by-products are minimized.
  • the object is achieved according to the invention by a process for the preparation of an aqueous acrylamide solution by hydrating acrylonitrile in an aqueous solution in the presence of a biocatalyst, in which the course of the reaction is monitored by an online measurement.
  • the entire reaction is preferably carried out isothermally, cooling being required during the entire reaction in order to remove the heat of reaction.
  • the Concentration of the biomass stated in dry matter at the start of the reaction is preferably 0.03-2.5 g / l, particularly preferably 0.05-1 g / l and the pH is preferably 6.0-8.0, particularly preferably 6.5 - 7.5.
  • the conversion of acrylonitrile to acrylamide is monitored using an online measurement.
  • On-line measurement in the sense of the invention is a measurement in which the analysis of the reaction mixture is carried out continuously or semi-continuously directly on the system.
  • This online measurement can be carried out with any suitable measuring device, the reaction mixture preferably flowing continuously through the online measuring device during the entire duration of the reaction.
  • the on-line measurement is preferably carried out using a Fourier transform infrared device (FT-IR). It was surprising to the person skilled in the art that this measuring method, despite the very cloudy reaction mixture, turned out to be particularly suitable.
  • FT-IR Fourier transform infrared device
  • the on-line measurement is preferably carried out in a pumping circuit in which part of the reaction mixture is conveyed from a reactor with a pump in a circuit.
  • this pumping circuit at least one heat exchanger is preferably arranged, with which the heat of reaction which arises during the conversion of acrylonitrile to acrylamide can be removed.
  • the heat exchanger is preferably a shell-and-tube heat exchanger in which the reaction mixture is advantageously not redirected in order to avoid fouling on the heat exchanger surfaces.
  • the pump and the heat exchanger (s) are designed such that, on the one hand, temperature fluctuations in the reactor and, on the other hand, excessive input of energy by the pump is avoided.
  • the pump is preferably a magnetically coupled side channel pump.
  • the heat exchanger is advantageously arranged in the pumping circuit before the online measurement, so that this measurement is as uniform as possible Temperatures occur so that measurement errors due to temperature fluctuations are avoided.
  • At least the acrylonitrile and the acrylamide concentration are determined using the online measurement. These concentrations are preferably determined at least every four minutes, particularly preferably at least every two minutes.
  • the measured values of the on-line measurement are used to regulate the biocatalyzed conversion of acrylonitrile to acrylamide.
  • the biocatalyst concentration, the temperature and / or the acrylonitrile concentration are preferably regulated.
  • the on-line measurement can be used to determine the point in time at which the implementation is terminated.
  • a subsequent reaction of preferably 4 to 20 minutes, particularly preferably 5 to 10 minutes, is required in order to convert the acrylonitrile as completely as possible.
  • this post-reaction time it is advantageous if the cooling is successively reduced with the bypass.
  • the length of the post-reaction time can also be controlled with the results of the online measurement.
  • the process according to the invention can be carried out with any biocatalyst which catalyzes the conversion of acrylonitrile to acrylamide.
  • the biocatalyst is preferably a Rhodococcus rhodochrous, which is registered under the depository name 14230 at the DSMZ, Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Germany.
  • the process according to the invention has the advantage that the activity of the biocatalyst is largely retained during the conversion of the acrylonitrile to acrylamide, that fewer by-products are obtained, that the conversion of the acrylonitrile takes place at least almost completely and that an up to 50% by weight acrylamide solution can be obtained is.
  • the method according to the invention is simple and inexpensive to carry out. The reaction times can be drastically reduced with the method according to the invention.
  • the biocatalyst is optimally used.
  • the process according to the invention is preferably carried out in a device for producing an aqueous acrylamide solution by hydrating acrylonitrile in an aqueous solution in the presence of a biocatalyst, which has an online measurement.
  • This device is therefore a further subject of the present invention.
  • the device according to the invention has an online measurement.
  • On-line measurement in the sense of the invention is a measurement in which the analysis of the reaction mixture is carried out continuously or semi-continuously directly on the system.
  • This online measurement can be carried out with any suitable measuring device, the reaction mixture preferably flowing continuously through the online measuring device during the entire duration of the reaction.
  • the on-line measurement is preferably carried out using a Fourier transform infrared device (FT-IR), it being surprising to the person skilled in the art that this measuring method has proven to be particularly suitable despite the very cloudy reaction mixture.
  • FT-IR Fourier transform infrared device
  • a resolution of 8 cm "1 should not be exceeded.
  • a resolution of 4.0 cm " 1 is particularly preferred.
  • the on-line measurement is preferably carried out in a pumping circuit, in which part of the reaction mixture is circulated with a pump.
  • the Pumping circuit is preferably connected to a reactor in which the conversion of the acrylonitrile to acrylamide takes place.
  • at least one heat exchanger is preferably arranged, with which the heat of reaction which arises during the conversion of acrylonitrile to acrylamide can be removed.
  • the heat exchanger is preferably a shell-and-tube heat exchanger in which the reaction mixture is advantageously not redirected in order to avoid fouling on the heat exchanger surfaces.
  • the pump and the heat exchanger (s) are designed such that, on the one hand, temperature fluctuations in the reactor and, on the other hand, excessive input of energy by the pump is avoided.
  • the pump is preferably a side channel pump.
  • the heat exchanger is advantageously arranged in the pumping circuit before the on-line measurement, so that this measurement is carried out, if possible, at uniform temperatures, so that measurement errors due to temperature fluctuations are avoided.
  • At least the acrylonitrile and the acrylamide concentration are determined using the online measurement. These concentrations are preferably determined at least every four minutes, particularly preferably at least every two minutes.
  • the measured values of the on-line measurement are used to regulate the biocatalyzed conversion of acrylonitrile to acrylamide.
  • the biocatalyst concentration, the temperature and / or the acrylonitrile concentration are preferred regulated.
  • the on-line measurement can be used to determine the point in time at which the implementation is terminated.
  • a subsequent reaction of preferably 4 to 20 minutes, particularly preferably 5 to 10 minutes, is required in order to convert the acrylonitrile as completely as possible.
  • this post-reaction time it is advantageous if the cooling is successively reduced with the bypass.
  • the length of the post-reaction time can also be controlled by the results of the online measurement.
  • the device according to the invention has the advantage that the activity of the biocatalyst is largely retained during the conversion of the acrylonitrile to acrylamide, that fewer by-products are obtained, that the conversion of the acrylonitrile takes place at least almost completely and that an up to 50% by weight acrylamide solution can be obtained is.
  • the device according to the invention is simple and inexpensive to carry out. The reaction times can be drastically reduced with the method according to the invention.
  • the biocatalyst is optimally used.
  • FIG. 1 shows a process diagram of the method according to the invention or parts of the device according to the invention.
  • FT-IR device Fourier transformation infrared device
  • the Fourier transformation infrared device (FT-IR device) 9 for online measurement of the acrylonitrile and acrylamide concentration in the circulating stream 18 and thus in the reactor 3 is also measured in the pumping circuit.
  • the sample stream is taken from the pumping circuit 18 and continuously conveyed into the FT-IR device 9 with the piston diaphragm pump 8 and analyzed there.
  • the FT-IR device is an Avatar System 360 from Nicolet (headquarters of the German branch: Offenbach, Germany). The device determines a spectrum with 64 scans within 1.5 minutes. The spectrum obtained in this way is used to determine the respective acrylonitrile or acrylamide concentration. The resolution is 4 cm "1. After 2 minutes, the next spectrum is measured so that an acrylamide and an acrylonitrile concentration measurement value is available every two minutes. The measurement values are used to control the process. Just before the pumping circuit 18 returns to the When reactor 3 enters, the acrylonitrile to be converted is metered into it from the acrylonitrile receiver 10 with the diaphragm metering pump 11.
  • the acrylonitrile receiver 10 and the reactor 3 are connected to one another on the gas side via a pendulum line 19.
  • the line 19 is opened before the start of metering of the acrylonitrile and after the metering has ended
  • the aqueous acrylamide is separated from the biomass using an annular gap centrifuge 12 and the aqueous acrylamide is collected in the receiver 13 and the biomass in the receiver 14.

Abstract

The invention relates to a method and a device for the production of an aqueous acrylamide solution by hydration of acrylnitrile in an aqueous solution in the presence of a bio-catalyst.

Description

Verfahren zur Herstellung einer wassrigen Acrylamidlösung mit einem Process for the preparation of an aqueous acrylamide solution with a
Biokatalysatorbiocatalyst
Die vorliegende Erfindung betrifft ein Verfahren und eine Vorrichtung zur Herstellung einer wassrigen Acrylamidlösung durch Hydratisierung von Acrylnitril in einer wassrigen Lösung in Gegenwart eines Biokatalysators.The present invention relates to a method and an apparatus for producing an aqueous acrylamide solution by hydrating acrylonitrile in an aqueous solution in the presence of a biocatalyst.
Die Umsetzung von Acrylnitril zu Acrylamid in Gegenwart eines geeigneten Biokatalysators in Wasser ist seit vielen Jahren bekannt und wird beispielsweise in der DE 30 17 005 C2 beschrieben, wobei bei diesem Verfahren der Biokatalysator immobilisiert ist. In der DE 44 80 132 C2 und in der EP 0 188 316 B1 werden spezielle Biokatalysatoren zur Umsetzung von Acrylnitril in Acrylamid beschrieben. Die US 5,334,519 lehrt die Hydratisierung von Acrylnitril zu Acrylamid in der Gegenwart von Biokatalysatoren und Kobalt-Ionen. All diese Lehren haben den Nachteil, daß der Biokatalysator bei der Reaktion geschädigt wird, so daß dessen Aktivität vermindert wird bzw. vermehrt ungewünschte Nebenprodukte entstehen.The conversion of acrylonitrile to acrylamide in the presence of a suitable biocatalyst in water has been known for many years and is described, for example, in DE 30 17 005 C2, the biocatalyst being immobilized in this process. DE 44 80 132 C2 and EP 0 188 316 B1 describe special biocatalysts for converting acrylonitrile into acrylamide. US 5,334,519 teaches the hydration of acrylonitrile to acrylamide in the presence of biocatalysts and cobalt ions. All of these teachings have the disadvantage that the biocatalyst is damaged during the reaction, so that its activity is reduced or undesired by-products are increasingly formed.
Aufgabe der vorliegenden Erfindung ist es deshalb, ein Verfahren zur Verfügung zu stellen, bei dem der Biokatalysator während der Reaktion möglichst wenig geschädigt und die Batch-Zeit optimiert wird sowie Nebenprodukte minimiert werden.The object of the present invention is therefore to provide a method in which the biocatalyst is damaged as little as possible during the reaction and the batch time is optimized and by-products are minimized.
Die Aufgabe wird erfindungsgemäß durch ein Verfahren zur Herstellung einer wassrigen Acrylamidlösung durch Hydratisierung von Acrylnitril in einer wassrigen Lösung in Gegenwart eines Biokatalysators gelöst, bei dem der Reaktionsverlauf durch eine On-Line-Messung überwacht wird.The object is achieved according to the invention by a process for the preparation of an aqueous acrylamide solution by hydrating acrylonitrile in an aqueous solution in the presence of a biocatalyst, in which the course of the reaction is monitored by an online measurement.
Zum Reaktionsstart werden in dem Reaktor Wasser und der Biokatalysator vorgelegt und auf eine Temperatur von 15 bis 25 °C, vorzugsweise 16 bis 20 °C, gebracht. Nachdem die Temperatur erreicht ist, wird das Acrylnitril in den Reaktor dosiert und die Umsetzung zu Acrylamid beginnt. Vorzugsweise erfolgt die gesamte Umsetzung isotherm, wobei während der gesamten Umsetzung gekühlt werden muß, um die Reaktionswärme abzuführen. Bezüglich der Kühlung des Reaktionsgemisches wird auf die Parallelanmeldung mit dem internen Aktenzeichen ST0031 verwiesen, die hiermit als Referenz eingeführt wird und somit als Teil der Offenbarung gilt. Die Konzentration der Biomasse angegeben in Trockensubstanz beträgt bei Reaktionsbeginn vorzugsweise 0,03 - 2,5 g/l, besonders bevorzugt 0,05 - 1 g/l und der pH- Wert vorzugsweise 6,0 - 8,0, besonders bevorzugt 6,5 - 7,5.At the start of the reaction, water and the biocatalyst are placed in the reactor and brought to a temperature of 15 to 25 ° C., preferably 16 to 20 ° C. After the temperature is reached, the acrylonitrile is metered into the reactor and the conversion to acrylamide begins. The entire reaction is preferably carried out isothermally, cooling being required during the entire reaction in order to remove the heat of reaction. With regard to the cooling of the reaction mixture, reference is made to the parallel application with the internal file number ST0031, which is hereby introduced as a reference and is therefore considered part of the disclosure. The Concentration of the biomass stated in dry matter at the start of the reaction is preferably 0.03-2.5 g / l, particularly preferably 0.05-1 g / l and the pH is preferably 6.0-8.0, particularly preferably 6.5 - 7.5.
Erfindungsgemäß wird die Umsetzung von Acrylnitril zu Acrylamid mit einer On-Line- Messung überwacht. Eine On-Line-Messung im Sinne der Erfindung ist eine Messung, bei der die Analyse des Reaktionsgemisches kontinuierlich oder semikontinuierlich direkt an der Anlage erfolgt. Diese On-Line-Messung kann mit jedem geeigneten Meßgerät durchgeführt werden, wobei das Reaktionsgemisch das On-Line-Meßgerät vorzugsweise während der gesamten Dauer der Umsetzung kontinuierlich durchströmt. Vorzugsweise wird die On-Line-Messung jedoch mit einem Fourier-Transformations-Infrarot-Gerät (FT-IR) durchgeführt. Es war für den Fachmann erstaunlich, daß sich diese Meßmethode trotz des sehr trüben Reaktionsgemisches als besonders geeignet herausgestellt hat. Bei der On-Line- Messung mit einem FT-IR sollte eine Auflösung von 8 cm"1 nicht überschritten werden. Besonders bevorzugt ist eine Auflösung von 4,0 cm"1.According to the invention, the conversion of acrylonitrile to acrylamide is monitored using an online measurement. On-line measurement in the sense of the invention is a measurement in which the analysis of the reaction mixture is carried out continuously or semi-continuously directly on the system. This online measurement can be carried out with any suitable measuring device, the reaction mixture preferably flowing continuously through the online measuring device during the entire duration of the reaction. However, the on-line measurement is preferably carried out using a Fourier transform infrared device (FT-IR). It was surprising to the person skilled in the art that this measuring method, despite the very cloudy reaction mixture, turned out to be particularly suitable. For online measurement with an FT-IR, a resolution of 8 cm "1 should not be exceeded. A resolution of 4.0 cm " 1 is particularly preferred.
Vorzugsweise erfolgt die On-Line-Messung in einem Umpumpkreislauf, in dem ein Teil des Reaktionsgemisches aus einem Reaktor mit einer Pumpe im Kreis gefördert wird. In diesem Umpumpkreislauf ist vorzugsweise mindestens ein Wärmetauscher angeordnet, mit dem die Reaktionswärme, die bei der Umsetzung von Acrylnitril zu Acrylamid entsteht, abgeführt werden kann. Vorzugsweise ist der Wärmetauscher ein Rohrbündelwärmetauscher, in dem das Reaktionsgemisch vorteilhafterweise nicht umgelenkt wird, um Fouling an den Wärmetauscheroberflächen zu vermeiden. In einer bevorzugten Ausführungsform der vorliegenden Erfindung werden die Pumpe und der/die Wärmetauscher so ausgelegt, daß zum einen Temperaturschwankungen im Reaktor und zum anderen ein zu starker Energieeintrag durch die Pumpe vermieden wird. Vorzugsweise ist die Pumpe eine magnetisch gekuppelte Seitenkanalpumpe.The on-line measurement is preferably carried out in a pumping circuit in which part of the reaction mixture is conveyed from a reactor with a pump in a circuit. In this pumping circuit, at least one heat exchanger is preferably arranged, with which the heat of reaction which arises during the conversion of acrylonitrile to acrylamide can be removed. The heat exchanger is preferably a shell-and-tube heat exchanger in which the reaction mixture is advantageously not redirected in order to avoid fouling on the heat exchanger surfaces. In a preferred embodiment of the present invention, the pump and the heat exchanger (s) are designed such that, on the one hand, temperature fluctuations in the reactor and, on the other hand, excessive input of energy by the pump is avoided. The pump is preferably a magnetically coupled side channel pump.
Vorteilhafterweise wird der Wärmetauscher in dem Umpumpkreislauf vor der On- Line-Messung angeordnet, damit diese Messung möglichst bei gleichmäßigen Temperaturen erfolgt, so daß Meßfehler durch Temperaturschwankungen vermieden werden.The heat exchanger is advantageously arranged in the pumping circuit before the online measurement, so that this measurement is as uniform as possible Temperatures occur so that measurement errors due to temperature fluctuations are avoided.
In einer bevorzugten Ausführungsform werden mit der On-Line-Messung zumindest die Acrylnitril- und die Acrylamidkonzentration bestimmt. Diese Konzentrationen werden vorzugsweise jeweils mindestens alle vier Minuten, besonders bevorzugt jeweils mindestens alle zwei Minuten, bestimmt.In a preferred embodiment, at least the acrylonitrile and the acrylamide concentration are determined using the online measurement. These concentrations are preferably determined at least every four minutes, particularly preferably at least every two minutes.
In diesem Zeitfenster wird vorzugsweise 1 Spektrum mit 32 oder 64 Scans, besonders bevorzugt 64 Scans - wobei die Interferrogramme aufaddiert und dann durch die Anzahl der Meßungen dividiert werden - genommen und durch das Backgroundspektrum dividiert. Das so erhaltene Spektrum wird zur Bestimmung der jeweiligen Acrylnitril- bzw. Acrylamidkonzentration herangezogen.In this time window, preferably 1 spectrum with 32 or 64 scans, particularly preferably 64 scans - with the interferrograms added up and then divided by the number of measurements - is taken and divided by the background spectrum. The spectrum obtained in this way is used to determine the respective acrylonitrile or acrylamide concentration.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung werden die Meßwerte der On-Line-Messung zur Regelung der biokatalysierten Umsetzung von Acrylnitril zu Acrylamid eingesetzt. Vorzugsweise werden die Biokatalysatorkonzentration, die Temperatur und/oder die Acrylnitrilkonzentration geregelt. Außerdem kann mit der On-Line-Messung der Zeitpunkt bestimmt werden, zu dem die Umsetzung abgebrochen wird.In a preferred embodiment of the present invention, the measured values of the on-line measurement are used to regulate the biocatalyzed conversion of acrylonitrile to acrylamide. The biocatalyst concentration, the temperature and / or the acrylonitrile concentration are preferably regulated. In addition, the on-line measurement can be used to determine the point in time at which the implementation is terminated.
Nach Beendigung der Acrylnitrildosierung ist eine Nachreaktion von vorzugsweise 4 bis 20 Minuten, besonders bevorzugt 5 bis 10 Minuten, erforderlich, um das Acrylnitril möglichst vollständig umzusetzen. Während dieser Nachreaktionszeit ist es vorteilhaft, wenn die Kühlung mit dem Bypass sukzessive reduziert wird. Die Länge der Nachreaktionszeit kann ebenfalls mit den Ergebnissen der On-Line-Messung gesteuert werden.After the acrylonitrile metering has ended, a subsequent reaction of preferably 4 to 20 minutes, particularly preferably 5 to 10 minutes, is required in order to convert the acrylonitrile as completely as possible. During this post-reaction time, it is advantageous if the cooling is successively reduced with the bypass. The length of the post-reaction time can also be controlled with the results of the online measurement.
Das erfindungsgemäße Verfahren kann mit jedem Biokatalysator durchgeführt werden, der die Umsetzung von Acrylnitril zu Acrylamid katalysiert. Vorzugsweise ist der Biokatalysator jedoch ein Rhodococcus rhodochrous, der unter der Hinterlegungsbezeichnung 14230 bei der DSMZ, Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Deutschland, hinterlegt ist.The process according to the invention can be carried out with any biocatalyst which catalyzes the conversion of acrylonitrile to acrylamide. However, the biocatalyst is preferably a Rhodococcus rhodochrous, which is registered under the depository name 14230 at the DSMZ, Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Germany.
Das erfindungsgemäße Verfahren hat den Vorteil, daß die Aktivität des Biokatalysator während der Umsetzung des Acrylnitrils zu Acrylamid weitgehend erhalten bleibt, daß weniger Nebenprodukte anfallen, daß die Umsetzung des Acrylnitrils zumindest nahezu vollständig erfolgt und daß eine bis zu 50 Gew.-%ige Acrylamidlösung erzielbar ist. Das erfindungsgemäße Verfahren ist einfach und kostengünstig durchzuführen. Die Reaktionszeiten können mit dem erfindungsgemäßen Verfahren drastisch reduziert werden. Der Biokatalysator wird optimal ausgenutzt.The process according to the invention has the advantage that the activity of the biocatalyst is largely retained during the conversion of the acrylonitrile to acrylamide, that fewer by-products are obtained, that the conversion of the acrylonitrile takes place at least almost completely and that an up to 50% by weight acrylamide solution can be obtained is. The method according to the invention is simple and inexpensive to carry out. The reaction times can be drastically reduced with the method according to the invention. The biocatalyst is optimally used.
Das erfindungsgemäße Verfahren wird vorzugsweise in einer Vorrichtung zur Herstellung einer wassrigen Acrylamidlösung durch Hydratisierung von Acrylnitril in einer wassrigen Lösung in Gegenwart eines Biokatalysators durchgeführt, die eine On- Line-Messung aufweist. Diese Vorrichtung ist deshalb ein weiterer Gegenstand der vorliegenden Erfindung.The process according to the invention is preferably carried out in a device for producing an aqueous acrylamide solution by hydrating acrylonitrile in an aqueous solution in the presence of a biocatalyst, which has an online measurement. This device is therefore a further subject of the present invention.
Erfindungsgemäß weist die erfindungsgemäße Vorrichtung eine On-Line-Messung auf. Eine On-Line-Messung im Sinne der Erfindung ist eine Messung, bei der die Analyse des Reaktionsgemisches kontinuierlich oder semikontinuierlich direkt an der Anlage erfolgt. Diese On-Line-Messung kann mit jedem geeigneten Meßgerät erfolgen, wobei das Reaktionsgemisch das On-Line-Meßgerät vorzugsweise während der gesamten Dauer der Umsetzung kontinuierlich durchströmt. Vorzugsweise wird die On-Line-Messung jedoch mit einem Fourier-Transformations- Infrarot-Gerät (FT-IR) durchgeführt, wobei es für den Fachmann erstaunlich war, daß sich diese Meßmethode trotz des sehr trüben Reaktionsgemisches als besonders geeignet herausgestellt hat. Bei der On-Line-Messung mit einem FT-IR sollte eine Auflösung von 8 cm"1 nicht überschritten werden. Besonders bevorzugt ist eine Auflösung von 4,0 cm"1.According to the invention, the device according to the invention has an online measurement. On-line measurement in the sense of the invention is a measurement in which the analysis of the reaction mixture is carried out continuously or semi-continuously directly on the system. This online measurement can be carried out with any suitable measuring device, the reaction mixture preferably flowing continuously through the online measuring device during the entire duration of the reaction. However, the on-line measurement is preferably carried out using a Fourier transform infrared device (FT-IR), it being surprising to the person skilled in the art that this measuring method has proven to be particularly suitable despite the very cloudy reaction mixture. For online measurement with an FT-IR, a resolution of 8 cm "1 should not be exceeded. A resolution of 4.0 cm " 1 is particularly preferred.
Vorzugsweise erfolgt die On-Line-Messung in einem Umpumpkreislauf, in dem ein Teil des Reaktionsgemisches mit einer Pumpe im Kreis gefördert wird. Der Umpumpkreislauf ist vorzugsweise mit einem Reaktor, in dem die Umsetzung des Acrylnitrils zu Acrylamid stattfindet, verbunden. In diesem Umpumpkreislauf ist vorzugsweise mindestens ein Wärmetauscher angeordnet, mit dem die Reaktionswärme, die bei der Umsetzung von Acrylnitril zu Acrylamid entsteht, abgeführt werden kann. Vorzugsweise ist der Wärmetauscher ein Rohrbündelwärmetauscher, in dem das Reaktionsgemisch vorteilhafterweise nicht umgelenkt wird, um Fouling an den Wärmetauscheroberflächen zu vermeiden. In einer bevorzugten Ausführungsform der vorliegenden Erfindung werden die Pumpe und der/die Wärmetauscher so ausgelegt, daß zum einen Temperaturschwankungen im Reaktor und zum anderen ein zu starker Energieeintrag durch die Pumpe vermieden wird. Vorzugsweise ist die Pumpe eine Seitenkanalpumpe.The on-line measurement is preferably carried out in a pumping circuit, in which part of the reaction mixture is circulated with a pump. The Pumping circuit is preferably connected to a reactor in which the conversion of the acrylonitrile to acrylamide takes place. In this pumping circuit, at least one heat exchanger is preferably arranged, with which the heat of reaction which arises during the conversion of acrylonitrile to acrylamide can be removed. The heat exchanger is preferably a shell-and-tube heat exchanger in which the reaction mixture is advantageously not redirected in order to avoid fouling on the heat exchanger surfaces. In a preferred embodiment of the present invention, the pump and the heat exchanger (s) are designed such that, on the one hand, temperature fluctuations in the reactor and, on the other hand, excessive input of energy by the pump is avoided. The pump is preferably a side channel pump.
Vorteilhafterweise wird der Wärmetauscher in dem Umpumpkreislauf vor der On- Line-Messung angeordnet, damit diese Messung möglichst bei gleichmäßigen Temperaturen erfolgt, so daß Meßfehler durch Temperaturschwankungen vermieden werden.The heat exchanger is advantageously arranged in the pumping circuit before the on-line measurement, so that this measurement is carried out, if possible, at uniform temperatures, so that measurement errors due to temperature fluctuations are avoided.
In einer bevorzugten Ausführungsform werden mit der On-Line-Messung zumindest die Acrylnitril- und die Acrylamidkonzentration bestimmt. Diese Konzentrationen werden vorzugsweise jeweils mindestens alle vier Minuten, besonders bevorzugt jeweils mindestens alle zwei Minuten, bestimmt.In a preferred embodiment, at least the acrylonitrile and the acrylamide concentration are determined using the online measurement. These concentrations are preferably determined at least every four minutes, particularly preferably at least every two minutes.
In diesem Zeitfenster wird vorzugsweise 1 Spektrum mit 32 oder 64 Scans, besonders bevorzugt 64 Scans - wobei die Interferrogramme aufaddiert und dann durch die Anzahl der Meßungen dividiert werden - genommen und durch das Backgroundspektrum dividiert. Das so erhaltene Spektrum wird zur Bestimmung der jeweiligen Acrylnitril- bzw. Acrylamidkonzentration herangezogen.In this time window, preferably 1 spectrum with 32 or 64 scans, particularly preferably 64 scans - with the interferrograms added up and then divided by the number of measurements - is taken and divided by the background spectrum. The spectrum obtained in this way is used to determine the respective acrylonitrile or acrylamide concentration.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung werden die Meßwerte der On-Line-Messung zur Regelung der biokatalysierten Umsetzung von Acrylnitril zu Acrylamid eingesetzt. Vorzugsweise werden die Biokatalysatorkonzentration, die Temperatur und/oder die Acrylnitrilkonzentration geregelt. Außerdem kann mit der On-Line-Messung der Zeitpunkt bestimmt werden, zu dem die Umsetzung abgebrochen wird.In a preferred embodiment of the present invention, the measured values of the on-line measurement are used to regulate the biocatalyzed conversion of acrylonitrile to acrylamide. The biocatalyst concentration, the temperature and / or the acrylonitrile concentration are preferred regulated. In addition, the on-line measurement can be used to determine the point in time at which the implementation is terminated.
Nach Beendigung der Acrylnitrildosierung ist eine Nachreaktion von vorzugsweise 4 bis 20 Minuten, besonders bevorzugt 5 bis 10 Minuten, erforderlich, um das Acrylnitril möglichst vollständig umzusetzen. Während dieser Nachreaktionszeit ist es vorteilhaft, wenn die Kühlung mit dem Bypass sukzessive reduziert wird. Die Länge der Nachreaktionszeit kann ebenfalls durch die Ergebnisse der On-Line-Messung gesteuert werden.After the acrylonitrile metering has ended, a subsequent reaction of preferably 4 to 20 minutes, particularly preferably 5 to 10 minutes, is required in order to convert the acrylonitrile as completely as possible. During this post-reaction time, it is advantageous if the cooling is successively reduced with the bypass. The length of the post-reaction time can also be controlled by the results of the online measurement.
Die erfindungsgemäße Vorrichtung hat den Vorteil, daß die Aktivität des Biokatalysator während der Umsetzung des Acrylnitrils zu Acrylamid weitgehend erhalten bleibt, daß weniger Nebenprodukte anfallen, daß die Umsetzung des Acrylnitrils zumindest nahezu vollständig erfolgt und daß eine bis zu 50 Gew.-%ige Acrylamidlösung erzielbar ist. Die erfindungsgemäße Vorrichtung ist einfach und kostengünstig durchzuführen. Die Reaktionszeiten können mit dem erfindungsgemäßen Verfahren drastisch reduziert werden. Der Biokatalysator wird optimal ausgenutzt.The device according to the invention has the advantage that the activity of the biocatalyst is largely retained during the conversion of the acrylonitrile to acrylamide, that fewer by-products are obtained, that the conversion of the acrylonitrile takes place at least almost completely and that an up to 50% by weight acrylamide solution can be obtained is. The device according to the invention is simple and inexpensive to carry out. The reaction times can be drastically reduced with the method according to the invention. The biocatalyst is optimally used.
Im folgenden wird die Erfindung anhand Figur 1 erläutert. Diese Erläuterungen sind lediglich beispielhaft und schränken den allgemeinen Erfindungsgedanken nicht ein.The invention is explained below with reference to FIG. 1. These explanations are only examples and do not limit the general idea of the invention.
Figur 1 zeigt ein Verfahrensschema des erfindungsgemäßen Verfahrens bzw. Teile der erfindungsgemäßen Vorrichtung. Vor dem Beginn der eigentlichen Umsetzung des Acrylnitrils zu Acrylamid wird in den Reaktor 3 vollentsalztes Wasser 1 und eine Suspension 2, die den Biokatalysator enthält, vorgelegt. Der Inhalt des Reaktors 3 wird mit einem motorgetriebenen Rührer 16 homogen durchmischt. An der Außenseite des Reaktors 3 sind Kühlschlangen 17, die mit dem Kaltwasservorlauf 5 und dem Kaltwasserrücklauf 4 verbunden sind. Der Fachmann erkennt, daß mit diesen Kühlschlangen auch der Reaktorinhalt vor dem Beginn der eigentlichen Reaktion auf eine bestimmte Temperatur vorgewärmt werden kann. Des weiteren weist der Reaktor 3 einen Umpumpkreislauf 18 auf, durch den ein Teil des Reaktorinhalts mittels der magnetisch gekuppelten Seitenkanalpumpe 7 im Kreis gefördert wird. In dem Umpumpkreislauf 18 sind drei parallel geschaltete Rohrbündelwärmetauscher 6 angeordnet, mit denen der Reaktorinhalt erwärmt bzw. gekühlt werden kann. Die Wärmetauscher 6 sind ebenfalls mit der Kaltwasservorlauf bzw. - rücklauf in Reihe verbunden. Weiterhin weist der Umpumpkreislauf den Bypass 15 auf, mit dem die Wärmetauscher 6 umfahren werden können. Die entsprechenden Ventile sind nicht dargestellt. In dem Umpumpkreislauf ist außerdem das Fourier- Transformations-Infrarot-Gerät (FT-IR Gerät) 9 zur Online-Messung der Acrylnitril- und der Acrylamidkonzentration in dem Umlaufstrom 18 und damit in dem Reaktor 3 gemessen. Der Probenstrom wird dem Umpumpkreislauf 18 entnommen und mit der Kolben-Membranpumpe 8 kontinuierlich in das FT-IR Gerät 9 gefördert und dort analysiert. Bei dem FT-IR-Gerät handelt es sich um ein Avatar System 360 der Firma Nicolet (Sitz der deutschen Niederlassung: Offenbach, Deutschland). Das Gerät ermittelt innerhalb von 1 ,5 Minuten ein Spektrum mit 64 Scans. Das so erhaltene Spektrum wird zur Bestimmung der jeweiligen Acrylnitril- bzw. Acrylamidkonzentration herangezogen. Die Auflösung beträgt 4 cm"1. Nach 2 Minuten wird das nächste Spektrum gemessen, so daß alle zwei Minuten jeweils ein Acrylamid- und ein Acrylnitril-Konzentrationsmeßwert vorliegt. Die Meßwerte werden zur Steuerung des Verfahrens herangezogen. Kurz bevor der Umpumpkreislauf 18 wieder in den Reaktor 3 eintritt, wird ihm das umzusetzende Acrylnitril mit der Membrandosierpumpe 11 aus der Acrylnitrilvorlage 10 zudosiert. Die Acrylnitrilvorlage 10 und der Reaktor 3 sind über eine Pendelleitung 19 gasseitig miteinander verbunden. Die Leitung 19 wird vor dem Dosierungsbeginn des Acrylnitrils geöffnet und nach Beendigung der Dosierung wieder geschlossen. Nach Abschluß der Reaktion wird das wässrige Acrylamid mit einer Ringspaltzentrifuge 12 von der Biomasse getrennt und das wässrige Acrylamid in der Vorlage 13 und die Biomasse in der Vorlage 14 aufgefangen. Applicant's or agent's International applicationNo. fϊle reference ST0030PCTFigure 1 shows a process diagram of the method according to the invention or parts of the device according to the invention. Before the actual conversion of the acrylonitrile to acrylamide begins, fully demineralized water 1 and a suspension 2, which contains the biocatalyst, are placed in the reactor 3. The contents of the reactor 3 are mixed homogeneously with a motor-driven stirrer 16. On the outside of the reactor 3 are cooling coils 17, which are connected to the cold water supply 5 and the cold water return 4. The person skilled in the art recognizes that the reactor contents can also be preheated to a specific temperature before the actual reaction begins with these cooling coils. Furthermore, the reactor 3 has a pumping circuit 18, through which part of the reactor content is conveyed in a circuit by means of the magnetically coupled side channel pump 7. In the pumping circuit 18, three tube bundle heat exchangers 6 connected in parallel are arranged, by means of which the reactor contents can be heated or cooled. The heat exchangers 6 are also connected to the cold water flow or return in series. Furthermore, the pumping circuit has the bypass 15 with which the heat exchangers 6 can be bypassed. The corresponding valves are not shown. The Fourier transformation infrared device (FT-IR device) 9 for online measurement of the acrylonitrile and acrylamide concentration in the circulating stream 18 and thus in the reactor 3 is also measured in the pumping circuit. The sample stream is taken from the pumping circuit 18 and continuously conveyed into the FT-IR device 9 with the piston diaphragm pump 8 and analyzed there. The FT-IR device is an Avatar System 360 from Nicolet (headquarters of the German branch: Offenbach, Germany). The device determines a spectrum with 64 scans within 1.5 minutes. The spectrum obtained in this way is used to determine the respective acrylonitrile or acrylamide concentration. The resolution is 4 cm "1. After 2 minutes, the next spectrum is measured so that an acrylamide and an acrylonitrile concentration measurement value is available every two minutes. The measurement values are used to control the process. Just before the pumping circuit 18 returns to the When reactor 3 enters, the acrylonitrile to be converted is metered into it from the acrylonitrile receiver 10 with the diaphragm metering pump 11. The acrylonitrile receiver 10 and the reactor 3 are connected to one another on the gas side via a pendulum line 19. The line 19 is opened before the start of metering of the acrylonitrile and after the metering has ended After the reaction has ended, the aqueous acrylamide is separated from the biomass using an annular gap centrifuge 12 and the aqueous acrylamide is collected in the receiver 13 and the biomass in the receiver 14. Applicant's or agent's International applicationNo. fall reference ST0030PCT
INDICATIONS RELATEVG TO DEPOSITED MICROORGA ISIV1 OR OTHER BIOLOGICAL MATERIALINDICATIONS RELATEVG TO DEPOSITED MICROORGA ISIV1 OR OTHER BIOLOGICAL MATERIAL
(PCT Rule l3iw)(PCT Rule l3iw)
A. The indications made below relate to the deposited microorganism or other biological material referred to in the description on page , line 31,32A. The indications made below relate to the deposited microorganism or other biological material referred to in the description on page, line 31,32
B. IDENTIFICATION OF DEPOSIT Further deposits are identified on an additional sheet | |B. IDENTIFICATION OF DEPOSIT Further deposits are identified on an additional sheet | |
Name of depositary institutionName of depositary institution
DSMZ Deutsche Sammlung von Mikrooranismen und Zellkulturen GmbHDSMZ German Collection of Microoranisms and Cell Cultures GmbH
Address of depositary institution (including postal code and country) Mascheroder Weg 1b, DE-38124 Braunschweig, DEUTSCHLANDAddress of depositary institution (including postal code and country) Mascheroder Weg 1b, DE-38124 Braunschweig, GERMANY
Date of deposit Accession NumberDate of deposit accession number
11.04.2001 DSM 1423004/11/2001 DSM 14230
C. ADDITIONAL INDICATIONS (leave blank ifnot applicable) This information is continued on an additional sheet I JC. ADDITIONAL INDICATIONS (leave blank ifnot applicable) This information is continued on an additional sheet I J
D. DESIGNATED STATES FOR WHICH INDICATIONS ARE MADE (ifthe indications are notfor all designated States)D. DESIGNATED STATES FOR WHICH INDICATIONS ARE MADE (if the indications are not for all designated states)
E. SEPARATE FURNISHING OF INDICATIONS (leave blank ifnot applicable)E. SEPARATE FURNISHING OF INDICATIONS (leave blank ifnot applicable)
The indications listed below will be submitted to the International Bureau later (specijy the general nature ofthe indications e.g.. "Accession Number of Deposit")The indications listed below will be submitted to the International Bureau later (specijy the general nature ofthe indications e.g. .. "Accession Number of Deposit")

Claims

Patentansprüche: claims:
1. Verfahren zur Herstellung einer wassrigen Acrylamidlösung durch Hydratisierung von Acrylnitril in einer wassrigen Lösung in Gegenwart eines Biokatalysators, dadurch gekennzeichnet, daß der Reaktionsverlauf durch eine On-Line-Messung überwacht wird.1. A process for the preparation of an aqueous acrylamide solution by hydrating acrylonitrile in an aqueous solution in the presence of a biocatalyst, characterized in that the course of the reaction is monitored by an online measurement.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die On-Line- Messung durch eine Fourier-Transformations-Infrarot-Messung erfolgt.2. The method according to claim 1, characterized in that the on-line measurement is carried out by a Fourier transform infrared measurement.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Hydratisierung in einem Reaktor erfolgt, der einen Umpumpkreislauf aufweist, in dem ein Teil des Reaktionsgemisches mit einer Pumpe im Kreis gefördert wird und daß die On-Line-Messung in dem Umpumpkreislauf angeordnet ist.3. The method according to claim 1 or 2, characterized in that the hydration takes place in a reactor which has a pumping circuit, in which part of the reaction mixture is pumped in a circuit and that the on-line measurement is arranged in the pumping circuit is.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß in dem Umpumpkreislauf vor der On-Line-Messung mindestens ein Wärmetauscher angeordnet ist.4. The method according to claim 3, characterized in that at least one heat exchanger is arranged in the pump circuit before the online measurement.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß der Wärmetauscher ein Rohrbündelwärmetauscher ist, in dem das Reaktionsgemisch gekühlt wird und dabei vorzugsweise nicht umgelenkt wird.5. The method according to claim 4, characterized in that the heat exchanger is a shell-and-tube heat exchanger in which the reaction mixture is cooled and is preferably not deflected.
6. Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß die Pumpe und die Wärmetauscherflächen so ausgelegt werden, daß starke Temperaturschwankungen bei der On-Line-Messung und ein zu starker Energieeintrag durch die Pumpe vermieden werden.6. The method according to claim 4 or 5, characterized in that the pump and the heat exchanger surfaces are designed so that strong temperature fluctuations in the on-line measurement and excessive energy input by the pump are avoided.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß mit der On-Line-Messung die Acrylnitril- und/oder die Acrylamidkonzentration bestimmt werden. 7. The method according to any one of claims 1 to 6, characterized in that the acrylonitrile and / or the acrylamide concentration can be determined with the online measurement.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß mindestens alle 4 Minuten, vorzugsweise alle zwei Minuten, die Acrylnitril- und/oder die Acrylamidkonzentration bestimmt werden.8. The method according to claim 7, characterized in that the acrylonitrile and / or the acrylamide concentration are determined at least every 4 minutes, preferably every two minutes.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß mit den Ergebnissen der On-Line-Messung das Verfahren, vorzugsweise die Acrylnitrilkonzentration, die Biokatalysatorkonzentration und/oder die Temperatur geregelt werden.9. The method according to any one of claims 1 to 8, characterized in that the method, preferably the acrylonitrile concentration, the biocatalyst concentration and / or the temperature are regulated with the results of the online measurement.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß der Biokatalysator Rhodococcus rhodochrous ist, der unter der Hinterlegungsbezeichnung 14230 bei der DSMZ, Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Deutschland, hinterlegt ist.10. The method according to any one of claims 1 to 9, characterized in that the biocatalyst Rhodococcus is rhodochrous, which is deposited under the depository name 14230 with the DSMZ, German Collection of Microorganisms and Cell Cultures GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Germany is.
11. Vorrichtung zur Herstellung einer wassrigen Acrylamidlösung durch Hydratisierung von Acrylnitril in einer wassrigen Lösung in Gegenwart eines Biokatalysators, dadurch gekennzeichnet, daß sie eine On-Line-Messung aufweist.11. Device for producing an aqueous acrylamide solution by hydrating acrylonitrile in an aqueous solution in the presence of a biocatalyst, characterized in that it has an on-line measurement.
12. Vorrichtung nach Anspruch 11 , dadurch gekennzeichnet, daß die On-Line- Messung eine Fourier-Transformations-Infrarot-Messung ist.12. The apparatus according to claim 11, characterized in that the on-line measurement is a Fourier transform infrared measurement.
13. Vorrichtung nach Anspruch 11 oder 12, dadurch gekennzeichnet, daß sie einen Reaktor mit einem Umpumpkreislauf aufweist, in dem ein Teil des Reaktorgemisches von einer Pumpe im Kreis gefördert wird und in dem die On-Line-Messung angeordnet ist.13. The apparatus according to claim 11 or 12, characterized in that it has a reactor with a pumping circuit, in which part of the reactor mixture is conveyed in a circuit by a pump and in which the on-line measurement is arranged.
14. Vorrichtung nach Anspruch 13, dadurch gekennzeichnet, daß in dem Umpumpkreislauf vor der On-Line-Messung mindestens ein Wärmetauscher angeordnet ist. 14. The apparatus according to claim 13, characterized in that at least one heat exchanger is arranged in the pump circuit before the online measurement.
15. Vorrichtung nach Anspruch 14, dadurch gekennzeichnet, daß der Wärmetauscher ein Rohrbündelwärmetauscher ist.15. The apparatus according to claim 14, characterized in that the heat exchanger is a shell-and-tube heat exchanger.
16. Vorrichtung nach einem der Ansprüche 13 bis 15, dadurch gekennzeichnet, daß die Pumpe eine Seitenkanalpumpe ist.16. The device according to one of claims 13 to 15, characterized in that the pump is a side channel pump.
17. Vorrichtung nach einem der Ansprüche 11 bis 16, dadurch gekennzeichnet, daß mit der On-Line-Messung die Acrylnitril- und/oder die Acrylamidkonzentration bestimmbar ist.17. The device according to one of claims 11 to 16, characterized in that the acrylonitrile and / or the acrylamide concentration can be determined with the online measurement.
18. Vorrichtung nach Anspruch 16, dadurch gekennzeichnet, daß die Konzentrationen mindestens alle 4 Minuten, vorzugsweise alle zwei Minuten, bestimmt wird. 18. The apparatus according to claim 16, characterized in that the concentrations are determined at least every 4 minutes, preferably every two minutes.
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