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WO2016050817A1 - Procédé de production d'acrylamide à partir d'acrylonitrile dans une solution aqueuse - Google Patents

Procédé de production d'acrylamide à partir d'acrylonitrile dans une solution aqueuse Download PDF

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Publication number
WO2016050817A1
WO2016050817A1 PCT/EP2015/072507 EP2015072507W WO2016050817A1 WO 2016050817 A1 WO2016050817 A1 WO 2016050817A1 EP 2015072507 W EP2015072507 W EP 2015072507W WO 2016050817 A1 WO2016050817 A1 WO 2016050817A1
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WO
WIPO (PCT)
Prior art keywords
acrylamide
acrylonitrile
saccharide
aqueous solution
nitrile hydratase
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PCT/EP2015/072507
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English (en)
Inventor
Michael Braun
Juergen Daeuwel
Peter OEDMAN
Michael Budde
Kai-Uwe Baldenius
Matthias Kleiner
Stephan Freyer
Michael Kiefer
Hans-Juergen Lang
Original Assignee
Basf Se
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.)
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Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2016050817A1 publication Critical patent/WO2016050817A1/fr

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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00Preparation of nitrogen-containing organic compounds
    • C12P13/02Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y402/00Carbon-oxygen lyases (4.2)
    • C12Y402/01Hydro-lyases (4.2.1)
    • C12Y402/01084Nitrile hydratase (4.2.1.84)

Definitions

  • the present invention relates to methods for producing acrylamide from acrylonitrile in an aqueous solution with a Nitrile hydratase (NHase) producing microorganism in the presence of a saccharide.
  • the present invention further relates to methods for reducing the amount of acrylic acid which is generated while producing acrylamide from acrylonitrile in an aqueous solution with the help of microorganisms.
  • the methods of the present invention are further capable of reducing the reaction time necessary to convert acrylonitrile into acrylamide with a Nitrile hydratase (NHase) producing microorganism in an aqueous solution and of increasing the reaction rate of acrylonitrile into acrylamide mediated by a Nitrile hydratase (NHase) producing microorganism in an aqueous solution.
  • a Nitrile hydratase a Nitrile hydratase
  • NHase Nitrile hydratase
  • Polyacrylamide is widely used in industry, for example as flocculants, as thickener in the paper industry, as additive in tertiary oil recovery, and many other fields.
  • the raw material for polyacrylamide is typically its monomer acrylamide.
  • chemical synthesis and biological synthesis are more and more on the rise due to milder reaction conditions, the absence of copper catalyst, the quantitative conversion of the nitrile, and inherent process safety.
  • expensive downstream processing steps such as distillation or ion exchange can be avoided in the biological synthesis, which allows for the design of cheaper production facilities, inter alia due to the drastically reduced plant footprint.
  • the acrylamide producing industry seeks for an optimal utilization/work capacity of the respective facilities (e.g. the manufacturing plants including the fermenters etc.) which adds to a cost efficient production of the monomer acrylamide.
  • An optimized utilization requires inter alia an optimized reaction time that is needed to convert the starting material acrylonitrile into acrylamide. It goes without saying that the time period that is necessary to convert a given amount of acrylonitrile into acrylamide with the help of a microorganism (bioconversion) should be as short as possible in order to increase the output of the monomer acrylamide per time, i.e. there is always a need for methods which allow for reducing the reaction time necessary to convert acrylonitrile into acrylamide with a Nitrile hydratase (NHase) producing microorganism in an aqueous solution.
  • NHase Nitrile hydratase
  • the present inventors came across a so far undisclosed correlation. They detected inter alia that the presence of a saccharide in the course of the bioconversion process results in a decreased amount of the unwanted by product acrylic acid. The present inventors have further detected that, the presence of saccharide in the course of the bioconversion has also a so far undisclosed positive effect on the reaction rate (increase) which resulted in a significant reduction of the reaction time that is necessary to convert acrylonitrile into acrylamide.
  • the present invention thus relates in essence to a method for producing acrylamide from acrylonitrile in an aqueous solution, comprising contacting in a reaction vessel an aqueous solution comprising acrylonitrile with a Nitrile hydratase (NHase) producing microorganism in the presence of a saccharide, preferably in the presence of more than 0,01 w/w% of a saccharide.
  • a reaction vessel an aqueous solution comprising acrylonitrile with a Nitrile hydratase (NHase) producing microorganism in the presence of a saccharide, preferably in the presence of more than 0,01 w/w% of a saccharide.
  • contacting is not specifically limited and includes for example bringing into contact with, admixing, stirring, shaking, pouring into, flowing into, incorporating into etc. It is thus only decisive that the mentioned ingredients come into contact with each other (preferably within a reaction vessel) no matter how that contact is achieved.
  • contacting not further limited, i.e. it is for example envisaged that either the aqueous solution comprising acrylonitrile is added first, or the Nitrile hydratase (NHase) producing microorganism is added first, or both are added simultaneously etc. -generally speaking: it is merely necessary that the ingredients come into contact, preferably within the reaction vessel, but the sequential order is not relevant. It is for example even envisaged that also the ingredients of the aqueous solution comprising acrylonitrile are added separately (e.g. one could start to charge the reaction vessel with e.g. water and add acrylonitrile subsequently, or vice versa, or both are charged simultaneously etc.).
  • NHase Nirile hydratase producing microorganism
  • microorganism microorganism
  • biocatalysts are able to produce (i.e. they encode and express) the enzyme nitrile hydratase (also referred to as, e.g., NHase) either per se (naturally) or they have been genetically modified respectively.
  • nitrile hydratase also referred to as, e.g., NHase
  • Microorganisms which have been "genetically modified” means that these microorganisms have been manipulated such that they have acquired the capability to express the required enzyme NHase, e.g.
  • nitrile hydratase Nase
  • nitrile hydratase NHase
  • Processed products of the microorganisms that can be used in the context of the present invention are also contemplated, e.g. suspensions obtained by partial or complete cell disruption of the microorganisms.
  • Nitrile hydratase (NHase) producing microorganism or “microorganism” or “biocatalysts” or the like, includes the cells and/or the processed products thereof as such, and/or suspensions containing such microorganisms and/or the processed products. It is also envisaged that the microorganisms and/or processed products thereof are further treated before they are employed in the embodiments of the present invention. “Further treated” thereby includes for example washing steps (for example with aqueous acrylic acid solutions as disclosed in US10472482A1 ) and/or steps to concentrate the microorganism etc. It is also envisaged that the microorganisms that are employed in the embodiments of the present invention have been pre-treated by a drying step. The term “pretreated by drying step” is explained herein elsewhere.
  • microorganisms or processed products thereof that are employed in the context of the present invention, are either in suspension, and/or (partly) immobilized by well-known standard methods, for example via entrapment such as wax or calcium-alginate entrapment, via cross linkage such as glutaraldehyde-polyethylenimine (GA-PEI) crosslinking, via cross linking to a matrix and/or via carrier binding etc., including variations and/or combinations of the aforementioned methods.
  • the microorganisms are whole cells pre-treated by a drying step.
  • aqueous suspension thereby includes all kinds of liquids, such as buffers or culture medium etc. that are suitable to keep microorganisms in suspension.
  • liquids are well-known to the skilled person and include for example storage buffers such as storage buffers which are used to deposit microorganisms, TRIS-based buffers, Saline based buffers etc.; water in all quality grades such as distilled water, pure water, tap water, or sea water etc.; culture medium, growing medium, nutrient solutions, fermentation broths etc., for example the fermentation broth that was used to culture the microorganisms etc.
  • saccharide that is used in the context of the present invention refers in essence to all kinds of saccharide(s) that can be detected and/or quantified by the phenol sulfuric acid method.
  • the Phenol - Sulphuric Acid Method is a well-established and very easy and reliable method amongst the quantitative assays for carbohydrate estimation. It is used in measuring saccharides as such as well as sugar content in oligosaccharides, proteoglycans, glycoproteins and glycolipids etc. Said method is based on the method discovered in the year 1956 by Michel DuBois who has published this method under the caption "Colorimetric Method for Determination of Sugars and Related Substances" in Anal.
  • saccharide examples include monosaccharides, oligosaccharides, polysaccharides, and mixtures thereof, which generate furfural or a furfural derivatives with the aid of sulfuric acid.
  • “Polysaccharides” contain more than ten monosaccharide units which are connected via glycosidic bonds and which are either linear or branched. “Polysaccharide” therefore includes but is not limited to e.g.
  • Oligosaccharides means up to ten (including ten) monosaccharides which are connected via glycosidic bonds and which are either linear or branched - oligosaccharides of the invention are preferably water soluble.
  • Preferred oligosaccharides are sucrose, lactose and maltose.
  • “Monosaccharides” refers to the well-known ketoses or aldoses that can be classified, based on the number of C-atoms, as dioses, trioses, teroses, pentoses, hexoses, heptoses, octoses and so on. Well-known variations of these monosaccharides are also contemplated (such as e.g. amino sugars of the monosaccharides such as galactosamine, glucosamine, sialic acid etc. or sulfosugars such as sulfoquinovose).
  • Glucose mannose, fructose, arabinose, furanose, pyranose, xylose, lyxose, ribose, allose, altrose, gulose, iodose, galactose, talose, etc. are preferred saccharides.
  • Glucose is a particularly preferred saccharide in the context of the present invention.
  • saccharide further includes glycoconjugates, such as glycoproteins and glycolipids etc.
  • the present inventors While optimizing the bioconversion of acrylonitrile into acrylamide, the present inventors came across a so far undisclosed correlation. They have detected inter alia that the presence of a saccharide in the course of the bioconversion process results in a decreased amount of the unwanted byproduct acrylic acid. The present inventors have further detected that, the presence of saccharide in the course of the bioconversion has also a so far undisclosed positive effect on the reaction rate (increase) which resulted in a significant reduction of the reaction time that is necessary to convert acrylonitrile into acrylamide. It is thus advantageous to conduct the bioconversion of acrylonitrile into acrylamide in the presence of a saccharide (which is the core of the present invention).
  • the source for the saccharide that is to be employed in the context of the present invention can be manifold and is not particularly limited.
  • the microorganism that is used in the context of the present invention already contains and/or consists of saccharide (e.g. within its cytoplasm, in form of storage forms or in form of glycoproteins, glycolipids, bacterial capsules and cell walls etc.) it is envisaged that the microorganism and/or a processed product thereof as such can already be used as a source for the saccharide to be used in the context of the methods and embodiments of the present invention.
  • the aforementioned "aqueous suspension” is a source for the saccharide (e.g.
  • a source for a saccharide into the bioconversion reaction. Said addition is preferably but not necessarily conducted before the start of the bioconversion reaction, wherein the "start” is the step of contacting the microorganism with the educt acrylonitrile which is contained in the aqueous solution.
  • start is the step of contacting the microorganism with the educt acrylonitrile which is contained in the aqueous solution.
  • the present invention thus particularly includes methods and further embodiments where all or part of the saccharide that is present in the aqueous solution wherein the bioconversion reaction takes place, might originate for example from the microorganism, where all or further parts of said saccharide might originate from the aqueous suspension (e.g. a C-source in the fermentation broth), and/or where all or further parts of said saccharide might originate from an active addition of a saccharide to the bioconversion reaction etc.
  • the aqueous suspension e.g. a C-source in the fermentation broth
  • “Active addition” thereby means in essence, that the corresponding saccharide is neither part of the aqueous suspension nor part of the microorganism but is additionally added and/or admixed into/with the aqueous solution comprising acrylonitrile wherein the bioconversion (conversion of acrylonitrile into acrylamide by a NHase producing microorganism) takes place (or vice versa, i.e. it is of course also envisaged to add/admix the aqueous solution comprising acrylonitrile into/with the saccharide).
  • a saccharide is actively added/admixed to/with the aqueous solution comprising acrylonitrile
  • the saccharide is a polysaccharide (e.g. starch, cellulose fibres etc.) which is preferably water soluble, and/or an oligosaccharides (preferably water soluble).
  • Mono- or disaccharides are also envisaged and preferred.
  • Glucose is a particularly preferred saccharide to be added to or admixed with the aqueous solution comprising acrylonitrile.
  • the biocatalyst may have been dried before being added to the reactor.
  • the term "before” does not necessarily mean that the biocatalyst has been dried and is then directly added to the reactor. It is rather sufficient that the biocatalyst has undergone a drying step at any time before it is added to the reactor, independently of whether further steps between the drying and the addition are performed or not. As non-limiting examples, such further steps between the drying step and the addition to the reactor may be storage or reconstitution. However, it is also possible to add the biocatalyst to the reactor directly after drying.
  • a biocatalyst which has undergone a drying step
  • the concentration of acrylic acid in an aqueous acrylamide solution obtained by any one of the methods described herein is further reduced in comparison to the case that a biocatalyst is used which has not undergone drying before being employed in the bioconversion.
  • a biocatalyst may be used which has been dried using freeze-drying, spray drying, heat drying, vacuum drying, fluidized bed drying and/or spray granulation.
  • a dried biocatalyst may be added to the reactor.
  • the biocatalyst is added to the reactor in a dried form.
  • the biocatalyst may have the form of a powder or a granule.
  • the dried biocatalyst may be reconstituted before being added to the reactor.
  • the biocatalyst may be reconstituted by suspending in an aqueous composition.
  • the aqueous composition may be water or a buffer.
  • the term "dried biocatalyst" as used herein refers to a biocatalyst that has been subjected to a drying step.
  • a dried biocatalyst typically has a moisture content of less than about 20 w/w %, more preferably less than about 15 w/w %, even more preferably less than about 14 w/w %, most preferably from about 5 to about 10 w/w % based on the total weight of the biocatalyst sample. Methods of determining the moisture content are familiar to the skilled person.
  • the moisture content of a sample of the dried biocatalyst may be determined via thermogravimetric analysis.
  • the initial weight of the sample is determined.
  • the sample is then heated and the moisture vaporizes. Heating is continued until the sample weight remains constant.
  • the difference between the constant weight at the end of the analysis and the initial weight represents the amount of water vaporized during the analysis, which allows for calculation of the moisture content of the sample.
  • the biocatalyst sample may be, for example, analyzed on a 'Mettler Toledo HB43-S Halogen moisture analyzer', operated at 130 °C until the sample weight remains constant for at least 30 seconds.
  • aqueous solution or “aqueous solution comprising acrylonitrile” that is mentioned and used in the context of the methods and embodiments of the present invention, comprises acrylonitrile, or another nitrile that is amenable to the hydration reaction catalyzed by nitrile hydratase and characterized by the hydration of nitriles to their corresponding amides, in water.
  • Said water can be water in all quality grades as long as this quality grade allows for the bioconversion of the invention namely of acrylonitrile into acrylamide. It is envisaged to use pure water, ultra-pure water, filtered water, distilled water, double distilled water, tap water, river water and/or sea water etc., to name some.
  • Said water may also contain further ingredients, such as buffers, salts, etc. that are typically used to adjust for example the pH of the aqueous solution, the ionic strength of the aqueous solution or the like.
  • the saccharide may be added to said aqueous solution with the microorganism and/or with the aqueous suspension and/or it is actively added (active addition) as explained herein elsewhere. It is also contemplated that the aqueous solution comprising acrylonitrile already comprises some (or all) of the required saccharide.
  • saccharide that is used in the context of the present invention refers in essence to all kinds of saccharide(s) that is(are) present in the bioconversion reaction (in particular in the aqueous solution wherein acrylonitrile is converted into acrylamide by a Nitrile hydratase (NHase) producing microorganism in the reaction vessel) and that can be detected by the phenol sulfuric acid method.
  • NHase Nitrile hydratase
  • the amount of saccharide that can be detected by the phenol sulphuric acid method can also be expressed in "glucose equivalents", namely when the total amount of saccharide that is detected via the Phenol-Sulphuric Acid Method is compared to a standard curve obtained with ascending concentrations of glucose in an aqueous medium (such as water or buffer).
  • the amount of saccharide that is present in the methods and further embodiments of the invention is thus, in a preferred embodiment, represented in terms of mg glucose / ml distilled water as determined by the phenol sulphuric acid method mentioned herein and specified for example in DuBois et al., "Colorimetric Method for Determination of Sugars and Related Substances" in Anal. Chem., 1956, 28 (3), pp 350-356).
  • the present invention relates in essence to a method for producing acrylamide from acrylonitrile in an aqueous solution containing acrylonitrile, comprising contacting acrylonitrile with a Nitrile hydratase (NHase) producing microorganism "in the presence of a saccharide” which means in the presence of equal to or more than 0,01 w/w% saccharide.
  • a Nitrile hydratase N-se
  • Said 0,01 w/w% of saccharide are in a preferred embodiment of the present invention referred to the total weight of components that represent the aqueous solution before the start of the bioconversion reaction, wherein the "start” is the step of contacting the microorganism with the educt acrylonitrile in the aqueous solution.
  • the microorganisms are therefore not yet part of the aqueous solution.
  • the saccharide content thereby reflects the amount of saccharide that is already contained in the aqueous solution and/or which is actively added thereto, but it does not reflect the saccharide that will be introduced by the microorganism and/or the aqueous suspension and/or by a further active addition of saccharide into the reaction vessel.
  • the aqueous solution containing acrylonitrile contains as such no saccharide (e.g.
  • the 0,01 w/w% Saccharide are referred to the total weight of components that represent the aqueous solution at the start of the bioconversion reaction in the reaction vessel, wherein the "start” is the step of contacting the microorganism with the educt acrylonitrile in the aqueous solution in the reaction vessel, i.e. said contacting is included.
  • the saccharide content in the reaction vessel reflects in this case the saccharide that is introduced by the microorganism and/or the aqueous suspension and/or by active addition and/or which is already contained in the aqueous solution as such.
  • the 0,01 w/w% Saccharide are referred to the total weight of components that represent the weight of the aqueous solution at the end of the bioconversion reaction in the reaction vessel, wherein the "end of the bioconversion reaction" means that point of time when the amount of acrylamide reaches for the first time 40-60 w/w%, 50w/w% being preferred and 52 w/w% being particularly preferred (w/w% acrylamide being thereby referred to the total weight of components that represent the aqueous solution at the end of the bioconversion reaction).
  • the content of acrylamide in an aqueous solution can be easily determined by methods well known in the art, e.g.
  • FTIR Fourier transform infrared spectroscopy
  • the content of w/w% Saccharide that is present in the methods and further embodiments of the present invention during the step of contacting the aqueous solution comprising acrylonitrile with a Nitrile hydratase (NHase) producing microorganism in a reaction vessel, does not fall or does not significantly fall below the limit of 0,01 w/w%.
  • a Nitrile hydratase Nase
  • the amount of saccharide (represented by glucose equivalents as explained herein elsewhere) in the reaction vessel is frequently determined and, if necessary, adjusted such that it is thereafter above (or equal to) 0,01 w/w% saccharide, preferably throughout the bioconversion up to the "end of the bioconversion reaction".
  • the w/w% is thereby referred to the total weight of the aqueous solution contained in the reaction vessel at the respective point of time (i.e. at the point of time when the saccharide content is determined).
  • the saccharide content falls (or is) below 0,01 w/w%, then it is envisaged to add further saccharide to the reaction vessel such that the 0,01 w/w% are met or exceeded.
  • the content of saccharide is equal to or above 0,01 w/% throughout the bioconversion, in particular up to the "end of the bioconversion reaction”.
  • the amount of saccharide that is contained in the context of the methods and further embodiments of the present invention does not exceed 0,2 w/w% (referred to the respective total amount of the aqueous solution contained in the reaction vessel).
  • the content of saccharide that is present in the methods and further embodiments of the present invention during the step of contacting the aqueous solution comprising acrylonitrile with a Nitrile hydratase (NHase) producing microorganism in a reaction vessel, is alternatively expressed as mg glucose/ml (or liter) distilled water.
  • the saccharide concentration expressed as w/w% saccharide referred to the respective total weight of the aqueous solution contained in the reaction vessel at the respective point of time
  • said concentration is equal to or above 100, 1 10 or 120mg glucose per 1000ml distilled water (120 being preferred). As already discussed hereinbefore, it is envisaged that the concentration of the saccharide can be adjusted provided that the concentration falls (or is) below said value (in analogy to the embodiments discussed hereinbefore). In a more preferred embodiment, said concentration is equal to or above 100mg/l, 1 10mg/l, or 120mg/l, 120mg/l being particularly preferred. In a preferred embodiment said concentration is equal to or above the mentioned value of mg/l up to the "end of the bioconversion reaction".
  • the present invention thus also relates to a method for producing acrylamide from acrylonitrile in an aqueous solution, comprising contacting in a reaction vessel an aqueous solution comprising acrylonitrile with a Nitrile hydratase (NHase) producing microorganism in the presence of a saccharide whose concentration is equal to or more than 100, 1 10, or 120mg glucose/l distilled water (120 being preferred) as measured with the Phenol - Sulphuric Acid Method.
  • NHase Nitrile hydratase
  • the methods and further embodiments of the present invention are carried out in a batch, semi-batch or continuous process, semi-batch being preferred.
  • further acrylonitrile may be added to the reaction vessel as needed (e.g. in the course of the bioconversion).
  • the acrylonitrile may be added continuously or intermittently, continuously being preferred. Addition of acrylonitrile may be at constant or variable feed rate or batch-wise.
  • the acrylonitrile may be added in pure form or in solution. For example, an aqueous solution of acrylonitrile may be used.
  • saccharide may be added continuously or intermittently. Addition of saccharide may be at constant or variable feed rate or batch-wise.
  • the present inventors While optimizing the bioconversion of acrylonitrile into acrylamide, the present inventors detected that the presence of a saccharide in the course of the bioconversion process results in a decreased amount of the unwanted by product acrylic acid.
  • the present invention thus also relates to a method for reducing the amount of acrylic acid which is generated while producing acrylamide from acrylonitrile in an aqueous solution in a reaction vessel, comprising contacting an aqueous solution comprising acrylonitrile with a Nitrile hydratase (NHase) producing microorganism in the presence of a saccharide.
  • a method for reducing the amount of acrylic acid which is generated while producing acrylamide from acrylonitrile in an aqueous solution in a reaction vessel comprising contacting an aqueous solution comprising acrylonitrile with a Nitrile hydratase (NHase) producing microorganism in the presence of a saccharide.
  • NHase Nitrile hydratase
  • Reducing means in its broadest sense a reduction of the content of acrylic acid in the reaction solution, preferably at the "end of the bioconversion reaction” which means that point of time when the amount of acrylamide reaches for the first time 40-60 w/w%, 50w/w% being preferred and 52 w/w% being particularly preferred (w/w% acrylamide being referred to the total weight of components that represent the aqueous solution at the end of the bioconversion reaction).
  • the reference method which will indicate said reduction at the end of the bioconversion reaction is an method that is conducted in analogy to the respective method of the invention, with the only difference that the amount (or concentration) of the saccharide is below the amount (or concentration) of saccharide which is used in the methods of the present invention.
  • the acrylic acid concentration that is contained in the aqueous solution in the reaction vessel may be reduced by at least 10 %, preferably by at least 15 %, more preferably by at least 20 %, even more preferably by at least 30 %, and most preferably by at least 40 % when compared to an identical method that was conducted without saccharide or with a reduced amount of saccharide (reduced thereby means below the amount of saccharide indicated in the context of the embodiments of the present invention).
  • the acrylic acid concentration at the end of the bioconversion may be determined using HPLC.
  • the acrylic acid concentration of the aqueous solution in the reaction vessel preferably at the end of the bioconversion, is 1500 ppm or less, preferably 1200 ppm or less, more preferably 1000 ppm or less, further preferably 750 ppm or less, even more preferably 500 ppm or less, still more preferably 300 ppm or less, still more preferably 200 ppm or less and most preferably 100 ppm or less, wherein indications of ppm each relate to weight parts and are each referred to the total weight of the composition at the respective point of time and in particular at the end of the bioconversion reaction.
  • the acrylic acid concentration of the composition at the end of the bioconversion may be determined using HPLC.
  • the present inventors have detected that the presence of a saccharide in the course of the bioconversion process has a so far undisclosed positive effect on the reaction rate (increase) which resulted in a significant reduction of the reaction time that is necessary to convert acrylonitrile into acrylamide.
  • the present invention thus also relates to a method for reducing the reaction time necessary to convert acrylonitrile into acrylamide with a Nitrile hydratase (NHase) producing microorganism in an aqueous solution in a reaction vessel, comprising contacting an aqueous solution comprising acrylonitrile with a Nitrile hydratase (NHase) producing microorganism in the presence a saccharide.
  • NHase Nitrile hydratase
  • the presence of a saccharide in a concentration that is equal to or more than 100, 1 10, or 120mg glucose/l distilled water (120 being preferred) as measured with the "Phenol - Sulphuric Acid Method" is thereby preferred (as explained hereinbefore).
  • the reference method which will indicate said reduction of the reaction time is an identical method that is conducted in analogy to the respective method of the invention, with the only difference that the amount of the saccharide is below the amount of saccharide which is used in the methods of the present invention. Thus, once both methods have e.g. reached the end of the bioconversion reaction, one can determine the reduction of the reaction time as a function of the reduced amount of saccharide.
  • the reaction time may be reduced by at least 10 %, preferably by at least 12,5 %, more preferably by at least 15 %, even more preferably by at least 25 %.
  • the present invention also relates to a method for increasing the reaction rate of acrylonitrile into acrylamide mediated by a Nitrile hydratase (NHase) producing microorganism in an aqueous solution in a reaction vessel, comprising contacting acrylonitrile with a Nitrile hydratase (NHase) producing microorganism in the presence of a saccharide.
  • a Nitrile hydratase Nitrile hydratase
  • NHase Nitrile hydratase
  • the presence of a saccharide in a concentration that is equal to or more than 100, 1 10 or 120mg glucose/l distilled water (120 being preferred) as measured with the "Phenol - Sulphuric Acid Method" is thereby preferred (as explained hereinbefore).
  • the reference method which will indicate said increase of the reaction rate is an identical method that is conducted in analogy to the respective method of the invention, with the only difference that the amount of the saccharide is below the amount of saccharide which is used in the methods of the present invention. Thus, once both methods have e.g. reached the end of the bioconversion reaction, one can determine the decrease of the reaction rate as a function of the reduced amount of saccharide.
  • the reaction rate may be increased by at least 10 %, preferably by at least 12,5 %, more preferably by at least 15 %, even more preferably by at least 25 %.
  • the present invention further relates to the use of a saccharide, preferably in a concentration that is equal to or more than 100, 1 10, or 120mg glucose/l distilled water (120 being preferred) as measured with the "Phenol - Sulphuric Acid Method", for:
  • the chemical synthesis method uses copper catalysts (e.g., US4048226, US3597481 )
  • the biological synthesis method also known as bio-based method or bioconversion
  • biocatalysts which hydrate (i.e. convert) acrylonitrile into acrylamide.
  • biocatalysts are microorganisms which are able to produce (i.e. which encode) the enzyme nitrile hydratase (IUBMB nomenclature as of April 1 , 2014 EC 4.2.1.84; CAS-No.
  • NHase per se
  • microorganisms which have been genetically modified such that they have acquired the capability to express the required enzyme NHase (e.g by way of incorporation of a naturally and/or modified nitrile hydratase gene).
  • Nitrile hydratase producing microorganisms i.e.
  • microorgansims that have the capability to express NHase naturally are largely distributed in the environment and comprise, inter alia, representatives of the species Rhodococcus rhodochrous, Rhodococcus erythropolis, Rhodococcus equi, Rhodococcus ruber, Rhodococcus opacus, Aspergillus niger, Acidovorax avenae, Acidovorax facilis, Agrobacterium tumefaciens, Agrobacterium radiobacter, Bacillus subtilis, Bacillus pallidus, Bacillus smithii, Bacillus sp BR449, Bradyrhizobium oligotrophicum, Bradyrhizobium diazoefficiens, Bradyrhizobium japonicum, Burkholderia cenocepacia, Burkholderia gladioli, Escherichia coli, Geobacillus sp.
  • RAPc8 Klebsiella oxytoca, Klebsiella pneumonia, Klebsiella variicola, Mesorhizobium ciceri, Mesorhizobium opportunistum, Mesorhizobium sp F28, Moraxella, Pantoea endophytica, Pantoea agglomerans, Pseudomonas chlororaphis, Pseudomonas putida, Rhizobium, Rhodopseudomonas palustris, Serratia liquefaciens, Serratia marcescens, Amycolatopsis, Arthrobacter, Brevibacterium sp CH1 , Brevibacterium sp CH2, Brevibacterium sp R312, Brevibacterium imperiale, Corynebacterium nitrilophilus, Corynebacterium pseudodiphteriticum, Corynebacterium glutamicum, Corynebacterium hoffmanii, Microbacter
  • nitrile hydratase is either iron- or cobalt- dependent (i.e. it possesses either an iron or a cobalt atom coordinated in its activity center) which is particularly characterized by its ability to catalyze conversion of acrylonitrile to obtain acrylamide by hydrating acrylonitrile (Kobayashi, Nature Biotechnology (1998), 16: 733 - 736).
  • the biocatalyst capable of converting acrylonitrile to acrylamide may be a microorganism which encodes the enzyme nitrile hydratase.
  • the microorganism is naturally encoding nitrile hydratase, or whether it has been genetically modified to encode said enzyme, or whether a microorganism naturally encoding nitrile hydratase has been modified such as to be able to produce more and/or enhanced nitrile hydratase.
  • biocatalyst e.g., microorganism
  • encoding the enzyme
  • nitrile hydratase or the like generally means that such a microorganism is generally also able to produce and stably maintain nitrile hydratase. That is, as used herein and as readily understood by the skilled person, a biocatalyst (e.g., a microorganism) to be employed in accordance with the present invention which (naturally or non-naturally) encodes nitrile hydratase is generally also capable of producing and stably maintaining nitrile hydratase.
  • microorganisms only produced nitrile hydratase during cultivation (or fermentation) of the microorganism - thus then containing nitrile hydratase - before being added to a reactor according to step (a) of any one of the methods described and provided herein.
  • the microorganisms do not produce nitrile hydratase during the methods described and provided herein any more, but they act only via the nitrile hydratase units which they have produced before and which they still contain.
  • biocatalyst encompasses the enzyme nitrile hydratase per se, as long as it is able to convert acrylonitrile to acrylamide as described and exemplified herein.
  • biocatalyst it is also possible to directly employ nitrile hydratase as biocatalyst.
  • microorganisms naturally encoding nitrile hydratase comprise species belonging to a genus selected from the group consisting of Rhodococcus, Aspergillus, Acidovorax, Agrobacterium, Bacillus, Bradyrhizobium, Burkholderia, Escherichia, Geobacillus, Klebsiella, Mesorhizobium, Moraxella, Pantoea, Pseudomonas, Rhizobium, Rhodopseudomonas, Serratia, Amycolatopsis, Arthrobacter, Brevibacterium, Corynebacterium, Microbacterium, Micrococcus, Nocardia, Pseudonocardia, Trichoderma, Myrothecium, Aureobasidium, Candida, Cryptococcus, Debaryomyces, Geotrichum, Hanseniaspora, Kluyveromyces,
  • biocatalysts to be employed in context with any one of the methods of the present invention comprise representatives of the genus Rhodococcus.
  • Species suitable as biocatalyst to be employed in context with any one of the methods of the present invention may comprise, e.g., Rhodococcus rhodochrous (e.g., NCIMB 41 164 or J1/FERM-BP 1478), Rhodococcus pyridinovorans, Rhodococcus erythropolis, Rhodococcus equi, Rhodococcus ruber, Rhodococcus opacus, Aspergillus niger, Acidovorax avenae, Acidovorax facilis, Agrobacterium tumefaciens, Agrobacterium radiobacter, Bacillus subtilis, Bacillus pallidus, Bacillus smithii, Bacillus sp BR449, Bradyrhizobium oligotrophicum, Bradyrhizob
  • RAPc8 Klebsiella oxytoca, Klebsiella pneumonia, Klebsiella variicola, Mesorhizobium ciceri, Mesorhizobium opportunistum, Mesorhizobium sp F28, Moraxella, Pantoea endophytica, Pantoea agglomerans, Pseudomonas chlororaphis, Pseudomonas putida, Rhizobium, Rhodopseudomonas palustris, Serratia liquefaciens, Serratia marcescens, Amycolatopsis, Arthrobacter, Brevibacterium sp CH1 , Brevibacterium sp CH2, Brevibacterium sp R312, Brevibacterium imperiale, Brevibacterium casei, Corynebacterium nitrilophilus, Corynebacterium pseudodiphteriticum, Corynebacterium glutamicum, Corynebacterium
  • the biocatalyst to be employed belongs to the species Rhodococcus rhodochrous.
  • Preferred examples for strains belonging to Rhodococcus rhodochrous which may be employed in context with any one of the methods and further embodiments described herein comprise NCIMB 41 164 and J1 (FERM-BP 1478).
  • nitrile hydratase encoding microorganisms which are not naturally encoding nitrile hydratase may be genetically engineered microorganisms which naturally do not contain a gene encoding a nitrile hydratase but which have been manipulated such as to contain a polynucleotide encoding a nitrile hydratase (e.g., via transformation, transduction, transfection, conjugation, or other methods suitable to transfer or insert a polynucleotide into a cell as known in the art; cf.
  • additional polynucleotides which may be necessary to allow transcription and translation of the nitrile hydratase gene or mRNA, respectively.
  • additional polynucleotides may comprise, inter alia, promoter sequences, polyT- or polyU-tails, or replication origins or other plasmid-control sequences.
  • such genetically engineered microorganisms which naturally do not contain a gene encoding a nitrile hydratase but which have been manipulated such as to contain a polynucleotides encoding a nitrile hydratase may be prokaryotic or eukaryotic microorganisms.
  • prokaryotic microorganisms include, e.g., representatives of the species Escherichia coli.
  • examples for such eukaryotic microorganisms include, e.g., yeast (e.g., Saccharomyces cerevisiae).
  • the present invention further relates to an aqueous acrylamide solution obtained or obtainable by the method of the invention.
  • the aqueous acrylamide solution may be obtained along with the biocatalyst.
  • the biocatalyst may be separated from the obtained aqueous acrylamide solution.
  • Such a separation of the biocatalyst may be performed with regard to the desired applications, which may, for example, include the homopolymerization or copolymerization of the acrylamide.
  • Suitable methods for separation of the biocatalyst are known in the art and include, for example, centrifugation and filtration.
  • An aqueous acrylamide solution in particular an aqueous acrylamide solution obtainable or being obtained by any one of the methods described herein, may contain 35 to 65 w/w % of acrylamide and may have an acrylic acid concentration of not more than 1500 ppm, preferably of not more than 1000 ppm, more preferably of not more than 750 ppm, further preferably of not more than 500 ppm, even more preferably of not more than 300 ppm, still more preferably of not more than 200 ppm and most preferably of not more than 100 ppm, wherein indications of w/w % and ppm are each referred to the total weight of the solution, and ppm each relates to weight parts.
  • the aqueous acrylamide solution contains 40 to 60 w/w % of acrylamide and has an acrylic acid concentration of not more than 1500 ppm, preferably of not more than 1000 ppm, more preferably of not more than 750 ppm, further preferably of not more than 500 ppm, even more preferably of not more than 300 ppm, still more preferably of not more than 200 ppm and most preferably of not more than 100 ppm, wherein indications of w/w % and ppm are each referred to the total weight of the solution, and ppm each relates to weight parts.
  • the aqueous acrylamide contains 45 to 55 w/w % of acrylamide and has an acrylic acid concentration of not more than 1500 ppm, preferably of not more than 1000 ppm, more preferably of not more than 750 ppm, further preferably of not more than 500 ppm, even more preferably of not more than 300 ppm, still more preferably of not more than 200 ppm and most preferably of not more than 100 ppm, wherein indications of w/w % and ppm are each referred to the total weight of the solution and ppm each relates to weight parts.
  • the aqueous acrylamide solution contains 50 to 54 w/w % of acrylamide and has an acrylic acid concentration of not more than 1500 ppm, preferably of not more than 1000 ppm, more preferably of not more than 750 ppm, further preferably of not more than 500 ppm, even more preferably of not more than 300 ppm, still more preferably of not more than 200 ppm and most preferably of not more than 100 ppm, wherein indications of w/w % and ppm are each referred to the total weight of the solution and ppm each relates to weight parts.
  • the aqueous acrylamide solutions disclosed herein, and in particular those disclosed hereinbefore comprises a saccharide, preferably in a concentration that is equal to or more than 120mg glucose/l distilled water as measured with the "Phenol - Sulphuric Acid Method.
  • the acrylamide content and/or the acrylic acid concentration may be determined using HPLC.
  • the present invention further relates to a polyacrylamide obtained by polymerizing the acrylamide solution of the invention. Since the present invention allows for preparation of aqueous acrylamide solutions having a reduced concentration of acrylic acid, in case that such aqueous acrylamide solutions are used for homopolymerization or copolymerization reactions, also the obtained acrylamide homopolymers or copolymers exhibit a reduced content of acrylic acid. Such acrylamide homopolymers or copolymers exhibit improved physical properties, such as solubility, and performance. The present invention therefore also encompasses a method for increasing the solubility of acrylamide homopolymers or copolymers.
  • the present invention relates to an acrylamide homopolymer or copolymer obtainable or being obtained by polymerizing the acrylamide of the aqueous solution as described herein.
  • a homopolymer the term “polymerizing” refers to a homopolymerization reaction
  • a copolymer the term “polymerizing” refers to a copolymerization reaction.
  • the homopolymerization or copolymerization may be performed using an aqueous acrylamide solution obtainable or being obtained by any one of the methods described herein.
  • an aqueous acrylamide solution may be used, from which the biocatalyst has been separated prior to the polymerization.
  • the acrylamide may have been isolated from the aqueous acrylamide solution before being subjected to homopolymerization or copolymerization.
  • An acrylamide homopolymer or copolymer in particular an acrylamide homopolymer or copolymer obtainable by polymerizing the acrylamide of the aqueous solution as described herein, may have an acrylic acid content of 1500 ppm or less, preferably of 1000 ppm or less, more preferably of 750 ppm or less, further preferably of 500 ppm or less, even more preferably of 300 ppm or less, still more preferably of 200 ppm or less, and most preferably of 100 ppm or less, wherein the indications of ppm each relate to weight parts and are each referred to the total weight of the solid acrylamide homopolymer or copolymer.
  • the acrylamide homopolymer or copolymer described and provided herein is an acrylamide copolymer, and more preferably it is a cationic polyacrylamide.
  • cationic polyacrylamide denotes a copolymer which in addition to acrylamide monomers contains cationic co-monomers, such as, e.g., co- monomers which comprise quaternary ammonium groups. It has been found that reduced performance of an acrylic acid polymer due to the presence of acrylic acid occurs in particular in case of cationic polyacrylamide products. This effect is even more evident for cationic polyacrylamide having low contents of cationic co-monomers.
  • anionic acrylic acid forms a complex with positively charged cationic co-monomers of the copolymer chain, which can significantly impair the physical properties of the polyacrylamide material, reduce solubility and performance in applications such as water treatment, paper making, oil recovery or mining.
  • a reduced acrylic acid content is in particular advantageous with regard to cationic polyacrylamide.
  • the acrylamide homopolymers and/or copolymers of the present invention comprise in a preferred embodiment a saccharide, preferably in a concentration that is equal to or more than 120mg glucose/l distilled water as measured with the "Phenol - Sulphuric Acid Method.
  • Acrylamide homopolymers and/or copolymers are, for example, used in oilfield applications.
  • use of acrylamide homopolymers and/or copolymers is made in tertiary oil recovery, which is also denoted as enhanced oil recovery.
  • an aqueous solution of the polymer may be injected into the rock in order to promote oil displacement and thus increase the yield of crude oil.
  • the present invention is therefore also related to an aqueous solution of any acrylamide homopolymer and/or copolymer described herein. As the water for the aqueous solution seawater may be used.
  • the biocatalyst and acrylonitrile may be added in any one of the methods described herein in a weight ratio of 0.001 to 0.5 w/w % of the biocatalyst and 22 to 45 w/w % of acrylonitrile; preferably of 0.005 to 0.2 w/w % of the biocatalyst and 26 to 42 w/w % of acrylonitrile; more preferably of 0.01 to 0.1 w/w % of the biocatalyst and 30 to 40 w/w % of acrylonitrile; most preferably of 0.02 to 0.065 w/w % of the biocatalyst and 35 to 39 w/w % of acrylonitrile, wherein in each case indications of w/w % are referred to the total weight (100 w/w %) of the total aqueous solution that is contained in the reaction vessel.
  • the bioconversion may be performed at 5 °C to 40 °C for 30 minutes to 48 hours, preferably at 5 °C to 35 °C for 10 hours to 30 hours, more preferably at 15 °C to 30 °C for 10 hours to 30 hours and most preferably at 20 °C to 28 °C for 10 hours to 30 hours.
  • reaction temperatures are preferred from the viewpoint of high activity of the biocatalyst and reasonable reaction times.
  • the actual time period also depends on the desired acrylamide content of the aqueous acrylamide solution to be produced.
  • the content of acrylonitrile may be maintained at 0.3 w/w % or more for 10 minutes to 48 hours, preferably for 15 minutes to 24 hours, more preferably for 30 minutes to 18 hours and most preferably for 1 hour to 12 hours.
  • the content of acrylonitrile may be maintained at 0.3 w/w % or more for 2 hours to 12 hours, for 4 hours to 12 hours, for 6 hours to 12 hours, for 8 hours to 12 hours or for 10 hours to 12 hours during step (b).
  • the content of acrylonitrile may be maintained at 0.3 w/w or more until an acrylamide content of at least 20 w/w %, preferably of at least 25 w/w %, more preferably of at least 30 w/w %, even more preferably of at least 35 w/w %, still more preferably of at least 40 w/w %, still more preferably of at least 42.5 w/w %, still more preferably of at least 45 w/w %, still more preferably of at least 47.5 w/w % and most preferably of at least 50 w/w % is reached, wherein the indications of w/w % are each referred to the total weight of the composition in the reactor. After such a concentration of acrylamide is reached, the addition of acrylonitrile may be stopped.
  • the acrylamide content of the composition in the reactor may be measured using Fourier Transform Infrared Spectros
  • the present invention also relates to a method for producing an aqueous acrylamide solution which comprises 40-60 w/w% acrylamide, 50w/w% being preferred and 52 w/w% being particularly preferred (w/w% acrylamide being referred to the total weight of components that represent the aqueous solution at the end of the bioconversion reaction) and less or equal than 0,03% w/w acrylic acid (w/w% acrylic acid being referred to the total weight of components that represent the aqueous solution at the end of the bioconversion reaction), comprising contacting acrylonitrile, preferably in a semi— batch reaction, with a Nitrile hydratase (NHase) producing microorganism in the presence of a saccharide as described herein; and obtaining said acrylamide.
  • a method for producing an aqueous acrylamide solution which comprises 40-60 w/w% acrylamide, 50w/w% being preferred and 52 w/w% being particularly preferred (w/w% acrylamide being
  • the present invention relates to all the embodiments described herein as well as to all permutations and combinations thereof. Any particular aspects or embodiments described herein must not be construed as limiting the scope of the present invention on such aspects or embodiments.
  • the conjunctive term "and/or" between multiple recited elements is understood as encompassing both individual and combined options. For instance, where two elements are conjoined by "and/or", a first option refers to the applicability of the first element without the second. A second option refers to the applicability of the second element without the first. A third option refers to the applicability of the first and second elements together. Any one of these options is understood to fall within the meaning, and therefore satisfy the requirement of the term "and/or” as used herein. Concurrent applicability of more than one of the options is also understood to fall within the meaning, and therefore satisfy the requirement of the term "and/or” as used herein.
  • “preferred embodiment” or “preferred aspect” means “preferred embodiment of the present invention” or “preferred aspect of the present invention”.
  • “an embodiments”, “another embodiment”, “an aspect”, “another aspect” means “an embodiments of the present invention”, “another embodiment of the present invention”, “an aspect of the present invention” and “another aspect of the present invention”, respectively.
  • the dried biomass was employed in semi-batch reaction mixtures.
  • 2416 g of water and 20 g of acrylonitrile (ACN) were initially introduced into a glass reactor; the reaction was started by the addition of biomass (1 g, slurred in 30 g water).
  • the concentration of ACN and acrylamide (ACM) were measured online by means of FTIR spectroscopy, and more ACN was added at a controlled rate so that the ACN concentration in the solution was kept constant at 0.8%.
  • 1553 g of ACN was converted (sum of initial batch and added ACN), so that a final concentration of 52% ACM was achieved in the aqueous solution.
  • the temperature was kept constant at 23 °C.
  • the total mass at the end of the reaction was 4 kg. It has been observed that the reaction proceeded with a higher reaction rate when glucose was added, and also that the concentration of the formed by-product acrylic acid was lower at the end.

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Abstract

La présente invention concerne des procédés de production d'acrylamide à partir d'acrylonitrile dans une solution aqueuse au moyen d'un micro-organisme producteur de nitrile hydratase (NHase) en présence d'un saccharide. La présente invention concerne en outre des procédés permettant de réduire la quantité d'acide acrylique, qui est généré lors de la production d'acrylamide à partir d'acrylonitrile dans une solution aqueuse, à l'aide de micro-organismes. Les procédés selon la présente invention sont en outre aptes à réduire le temps de réaction nécessaire pour convertir l'acrylonitrile en acrylamide au moyen d'un micro-organisme producteur de nitrile hydratase (NHase) dans une solution aqueuse et à augmenter la vitesse de réaction de l'acrylonitrile en acrylamide médiée par un micro-organisme producteur de nitrile hydratase (NHase) dans une solution aqueuse.
PCT/EP2015/072507 2014-09-30 2015-09-30 Procédé de production d'acrylamide à partir d'acrylonitrile dans une solution aqueuse WO2016050817A1 (fr)

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US11634516B2 (en) 2017-10-25 2023-04-25 Basf Se Process for producing aqueous polyacrylamide solutions
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