WO2011145687A1 - Procédé pour stabiliser un composé amide ayant une liaison insaturée - Google Patents

Procédé pour stabiliser un composé amide ayant une liaison insaturée Download PDF

Info

Publication number
WO2011145687A1
WO2011145687A1 PCT/JP2011/061546 JP2011061546W WO2011145687A1 WO 2011145687 A1 WO2011145687 A1 WO 2011145687A1 JP 2011061546 W JP2011061546 W JP 2011061546W WO 2011145687 A1 WO2011145687 A1 WO 2011145687A1
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
acrylamide
ppm
reaction
amide compound
Prior art date
Application number
PCT/JP2011/061546
Other languages
English (en)
Japanese (ja)
Inventor
努 石田
新 佐藤
重男 渡辺
輝夫 有井
Original Assignee
三井化学株式会社
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 三井化学株式会社 filed Critical 三井化学株式会社
Priority to JP2012515929A priority Critical patent/JPWO2011145687A1/ja
Publication of WO2011145687A1 publication Critical patent/WO2011145687A1/fr

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/88—Lyases (4.)
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y402/00—Carbon-oxygen lyases (4.2)
    • C12Y402/01—Hydro-lyases (4.2.1)
    • C12Y402/01084—Nitrile hydratase (4.2.1.84)

Definitions

  • the present invention relates to a method for stabilizing an amide compound having an unsaturated bond.
  • Amide compounds having unsaturated bonds are important industrial raw materials as raw material monomers for various materials, and in particular, (meth) acrylamide is a polymer flocculant, a secondary and tertiary recovery agent for crude oil, and a paper agent. It is an important industrial raw material widely used as a raw material monomer. However, since the amide compound is very easily polymerized, it is a big problem in storage and transportation.
  • Patent Documents 1 and 2 So far, stable storage methods by adding a polymerization inhibitor have been reported (Patent Documents 1 and 2). On the other hand, a physical response method such as continuous stirring has been devised. However, in the former, there is a problem that the quality is affected, for example, the purity of the amide compound having an unsaturated bond is lowered, and in the latter, a dedicated device is required and the equipment cost is increased.
  • Patent Document 3 discloses that when an acrylamide aqueous solution obtained by reacting acrylonitrile and water in a liquid phase in the presence of a copper-containing catalyst is purified, unreacted acrylonitrile in the reaction solution is substantially free of oxygen. Distilled in the presence, then contacted with oxygen or an oxygen-containing gas to maintain a dissolved oxygen concentration of at least 4 ppm and treated with oxygen, followed by a strongly acidic cation exchange resin and / or a strongly basic anion exchange resin A method for purifying an aqueous acrylamide solution to be treated is disclosed.
  • Patent Document 4 in a method for directly hydrating acrylamide from acrylonitrile using a microorganism having nitrile hydration ability, when the acrylamide concentration is increased, pigments and trace impurities are extracted from the microorganism into an aqueous solution. Therefore, when purifying an aqueous acrylamide solution using activated carbon, the dissolved oxygen concentration in the water after contact was increased to 0.5 ppm or more by bringing the activated carbon into contact with water in which oxygen was dissolved. Subsequently, a method for purifying an aqueous acrylamide solution in which the activated carbon is brought into contact with the activated carbon is disclosed.
  • Patent Document 4 there is no description or suggestion about the stage of reaction from acrylonitrile to acrylamide in the microbial method and the stage of storage of acrylamide obtained after purification, which may cause problems in practice.
  • An object of the present invention is to stably store an amide compound having an unsaturated bond without adding a chemical substance or adding a special device or design to an amide compound having an unsaturated bond that is extremely polymerized and difficult to handle. To provide a law.
  • the inventors of the present invention have an effect of preventing polymerization by containing 1 wt ppm or more of oxygen in an aqueous amide compound solution having a high concentration of unsaturated bonds that are more easily polymerized.
  • the present inventors have found that the quality of a polymer (polyamide compound) obtained from an amide compound having an unsaturated bond is good, and completed the present invention.
  • the present invention is as follows.
  • reaction the step of obtaining a reaction solution containing an amide compound having an unsaturated bond from an aqueous solution containing a nitrile compound by a hydration reaction using a catalyst containing an enzyme capable of generating an amide compound from a nitrile compound.
  • reaction the step of removing the enzyme and the like by purifying the resulting reaction solution of the amide compound having an unsaturated bond using activated carbon or the like as the “purification step”, and passing through these two steps, the nitrile Obtaining an amide compound having an unsaturated bond from a compound is referred to as “production”.
  • amide compound having an unsaturated bond is also simply referred to as “amide compound” or “unsaturated amide compound”.
  • a reaction solution containing an amide compound in the middle of a reaction for generating an amide compound from a nitrile compound; a reaction solution containing an amide compound after reaction; a reaction solution containing an amide compound after purification; and an amide compound during and after storage Since any of the reaction liquids contains at least an amide compound, it is also referred to as an “amide compound-containing liquid” or an “amide compound aqueous solution”.
  • Weight ppm which is a unit of oxygen concentration may be simply expressed as “ppm”, but unless otherwise specified, all means “ppm by weight”.
  • the terms “amide compound polymer” and “polyamide compound” are used interchangeably.
  • the amide compound having an unsaturated bond is always stable without substantially increasing the impurity content of the amide compound having an unsaturated bond and without adding an expensive facility. Can be manufactured and stored.
  • the quality of the polyamide compound obtained by polymerizing the amide compound using such a stabilization method is good.
  • a catalyst containing an enzyme capable of producing an amide compound from a nitrile compound is used to carry out the following steps.
  • Oxygen is made to be 1 ppm by weight or more and saturated oxygen concentration or less.
  • Reaction step a step in which the amide compound is produced from a nitrile compound by a catalytic reaction in an aqueous solution containing the nitrile compound and the catalyst; and a purification step: a catalyst (activated carbon is used from the reaction solution obtained in the reaction step).
  • a process of removing proteins, polypeptides, etc. derived from a purified enzyme / a crudely purified enzyme, a microorganism containing the enzyme or a culture solution of the microorganism) (the above is collectively referred to as a production process); and / or Storage step: A step of storing the reaction solution obtained in the manufacturing process.
  • the reaction solution during or after the reaction includes an unreacted or residual nitrile compound, the generated amide compound, and a catalyst.
  • the aqueous solution before the reaction contains a nitrile compound and a catalyst.
  • the amide compound having an unsaturated bond of the present invention is obtained through the stabilization method of the present invention, and the polyamide compound of the present invention polymerizes the amide compound having an unsaturated bond of the present invention. It is characterized by being obtained.
  • the nitrile compound applied to the present invention is a substrate of an enzyme (preferably nitrile hydratase) that can generate an amide compound from the nitrile compound, and any nitrile compound that can generate an amide compound having an unsaturated bond described later is used in the present invention.
  • an enzyme preferably nitrile hydratase
  • any nitrile compound that can generate an amide compound having an unsaturated bond described later is used in the present invention.
  • acrylonitrile and methacrylonitrile are preferable.
  • acrylonitrile and methacrylonitrile are collectively referred to as “(meth) acrylonitrile”.
  • the amide compound having an unsaturated bond applied to the present invention is not particularly limited as long as it is an amide compound having an unsaturated double bond in the molecule.
  • Examples of the amide compound having an unsaturated bond applied to the present invention include acrylamide, methacrylamide, crotonamide, tiglic amide, 2-pentenoic acid amide, 3-pentenoic acid amide, 4-pentenoic acid amide, 2- Monoamide compounds such as hexenoic acid amide, 3-hexenoic acid amide, 5-hexenoic acid amide, fumaric acid diamide, maleic acid diamide, citraconic acid diamide, mesaconic acid diamide, itaconic acid diamide, 2-pentenedioic acid diamide, 3-hexene And diamide compounds such as diacid diamide.
  • a monoamide compound is mentioned, More preferably, acrylamide or methacrylamide is mentioned.
  • acrylamide and methacrylamide are collectively referred to as “(meth) acrylamide”.
  • the amide compound-containing liquid having an unsaturated bond applied to the present invention is not particularly limited, but preferably, the amide compound is applied to a product liquid obtained by a hydration reaction of a corresponding nitrile compound. . More preferably, it is particularly preferably applied to an acrylamide-containing liquid obtained by hydration reaction of acrylonitrile or a methacrylamide-containing liquid obtained by hydration reaction of methacrylonitrile.
  • the method for producing an amide compound having an unsaturated bond is not particularly limited, for example, a production method using a microorganism is preferably exemplified.
  • the microorganisms producing nitrile hydratase which are preferably used include Nocardia, Corynebacterium, Bacillus, thermophilic Bacillus, Pseudomonas, Micrococcus.
  • Rhodococcus genus represented by Rhodochrous species, Acinetobacter genus, Xanthobacter genus, Streptomyces genus, Rhizobium genus, Klebsiella (Rhizobium genus) Klebsiella, Enterobacter, Erwinia, Aeromonas, Citrobacter, Achromobacter, Agrobacterium or thermophila ) Pseudonocardia genus represented by species, Bacteridiu m) microorganisms belonging to the genus and Brevibacterium.
  • a transformant in which a nitrile hydratase gene cloned from these microorganisms is highly expressed in an arbitrary host, and one or more of the constituent amino acids of the nitrile hydratase using other DNA by using recombinant DNA technology
  • a transformant expressing a mutant nitrile hydratase with further improved amide compound resistance, nitrile compound resistance, and temperature resistance by substitution, deletion, deletion or insertion.
  • Escherichia coli Escherichia coli
  • Escherichia coli is mentioned as a representative example as described in the examples below, but is not particularly limited to Escherichia coli, and bacillus such as Bacillus subtilis.
  • Other microbial strains such as genera, yeasts and actinomycetes are also included.
  • MT-10822 this strain was established on February 7, 1996, 1-3-1 Higashi 1-chome, Tsukuba, Ibaraki Prefecture, Institute of Biotechnology, Institute of Industrial Technology, Ministry of International Trade and Industry (currently Tsukuba Ibaraki Prefecture). City East 1-1-1 Tsukuba Center Chuo No. 6 (National Institute of Advanced Industrial Science and Technology, Patent Biological Deposit Center) under the accession number FERM BP-5785, based on the Budapest Treaty on the international approval of the deposit of microorganisms under patent procedures Is deposited).
  • a microorganism belonging to the genus Pseudonocardia and a nitrile hydratase gene cloned from the microorganism can be highly expressed in any host.
  • a transformant in which a mutant nitrile hydratase is expressed is preferable.
  • the said transformant is preferable at the point which raises the stability of nitrile hydratase more and the activity per microbial cell is higher.
  • Rhodococcus rhodochrous J-1 which can highly express nitrile hydratase in microorganisms, and transformants in which the nitrile hydratase gene cloned from the microorganism is highly expressed in any host.
  • the microbial cell producing the nitrile hydratase can be prepared by a general method known in the fields of molecular biology, biotechnology, and genetic engineering.
  • the recombinant vector according to the present invention contains a gene encoding nitrile hydratase and can be obtained by linking a gene encoding nitrile hydratase to the vector.
  • the vector is not particularly limited.
  • the expression plasmid of nitrile hydratase can be constructed.
  • the host organism to be used for transformation is not limited as long as the recombinant vector is stable and capable of self-propagation and can express foreign DNA traits.
  • E. coli is a good example.
  • the transformant having the ability to produce nitrile hydratase can be obtained by introducing it into Bacillus subtilis, yeast or the like.
  • a microorganism producing nitrile hydratase as described above may be appropriately cultured and grown by a known method to produce nitrile hydratase.
  • a medium used in this case either a synthetic medium or a natural medium can be used as long as it contains a suitable amount of carbon source, nitrogen source, inorganic salts and other nutrients.
  • an appropriate culture temperature generally 20 ° C. to 50 ° C., but in the case of thermophilic bacteria, it may be 50 ° C. or higher). It can be prepared by culturing in the above.
  • Culturing can be performed using a conventional culture method such as shaking culture, aeration and agitation culture, continuous culture, or fed-batch culture in a liquid medium containing the culture components.
  • the culture temperature of the transformant is preferably 15 to 37 ° C.
  • the culture conditions may be appropriately selected depending on the type of culture and the culture method, and are not particularly limited as long as the strain can grow and produce nitrile hydratase.
  • nitrile hydratase in order to react the microbial cell producing the above-mentioned nitrile hydratase with the nitrile compound, various treatments such as collection of cells by centrifugation or crushing to produce a crushed cell product are performed.
  • the microbial cells that have been subjected to any of these treatments are collectively referred to as processed microbial cells.
  • microorganisms to be crushed there are no particular limitations on the form of microorganisms to be crushed as long as they contain microorganisms that produce nitrile hydratase.
  • the culture itself containing the microorganisms Examples of the collected and collected bacterial bodies, and those obtained by washing the collected bacterial bodies with physiological saline and the like.
  • the device for crushing the cells is not particularly limited as long as the cells can be crushed. Examples thereof include grinding devices such as an ultrasonic crusher, a French press, a bead shocker, a homogenizer, a dyno mill, and a cool mill. It is done. Among these, a homogenizer is preferable because it can be scaled up at low cost.
  • a homogenizer is a device that adjusts the clearance of a homovalve provided at the outlet of a plunger-type high-pressure pump that feeds liquid with a piston with screws or hydraulic pressure, and has a synergistic effect on the introduced fluid such as shearing, collision, and cavitation. It is a device that generates instantaneously. This homogenizer is commercially available from Sanwa Machinery Co., Ltd. and Izumi Food Machinery Co., Ltd.
  • the temperature at which the cells are crushed is not particularly limited, but is preferably 0 ° C. or higher and 50 ° C. or lower, more preferably 0 ° C. or higher and 25 ° C. or lower.
  • the pH at which the cells are disrupted is not particularly limited, but is preferably 4 to 10 and more preferably 6 to 8.
  • the pressure when crushing the cells using a homogenizer is not particularly limited as long as the cells are crushed, but is preferably 10 MPa or more and 300 MPa or less, more preferably 30 MPa or more and 100 MPa or less.
  • nitrile hydratase has a polymerization promoting effect on unsaturated amide compounds.
  • the oxygen concentration of the unsaturated amide compound-containing liquid is not particularly limited as long as it is between 1 ppm by weight and saturated solubility, but more preferably from 1.2 ppm by weight to saturated solubility, and even more preferably from 2 ppm by weight to saturated solubility. From the viewpoint of preventing polymerization.
  • the oxygen concentration of the unsaturated amide compound-containing liquid is preferably within the above range.
  • the pH of the unsaturated amide compound-containing liquid is less than 7, particularly when the pH is 3 or more and less than 7, the polymerization of the unsaturated amide compound is promoted. It is preferably between saturated solubilities, more preferably between 2 ppm by weight and saturated solubilities.
  • the method for supplying oxygen to the unsaturated amide compound-containing solution is not particularly limited as long as the oxygen concentration of the unsaturated amide compound-containing solution is maintained from 1 ppm by weight to saturated solubility, and may be a known method.
  • a supply method by stirring the unsaturated amide compound-containing liquid in the presence of a gas containing oxygen a supply method by blowing a gas containing oxygen into the unsaturated amide compound-containing liquid, and the like can be exemplified.
  • a supply method by stirring is preferable from the viewpoint of supplying oxygen uniformly.
  • the gas used for supplying oxygen is not particularly limited as long as it contains oxygen, and oxygen, air, and the like are preferably used.
  • the storage temperature of the unsaturated amide compound is not particularly limited, but is preferably ⁇ 10 ° C. to 50 ° C., more preferably 10 ° C. to 30 ° C. from the viewpoint of stability.
  • the polypeptide concentration contained in the unsaturated amide compound-containing solution before the purification step is usually about 10 ppm to 500 ppm, preferably about 10 ppm to 100 ppm.
  • the residual polypeptide concentration contained in the unsaturated amide compound-containing liquid purified by using activated carbon after removing the microorganism with filter paper or the like is preferably about 0.00. It is about 1 ppm to 3 ppm, usually about 0.5 ppm to 1.5 ppm.
  • Example (1-1) ⁇ Preparation of microbial catalyst containing nitrile hydratase>
  • Example 1 of Japanese Patent Laid-Open No. 2001-340091 no.
  • Three clonal cells were obtained and similarly cultured by the method of Example 1, that is, the following method, to obtain wet cells containing nitrile hydratase.
  • a medium having the following composition 100 mL of a medium having the following composition was prepared in a 500 mL Erlenmeyer flask with a baffle and sterilized by autoclaving at 121 ° C. for 20 minutes. After adding ampicillin to this medium so that the final concentration is 50 ⁇ g / mL, Three clones were inoculated with ears of white and cultured at 37 ° C./130 rpm for 20 hours. Centrifugation (15000G ⁇ 15 minutes) separated only the cells from the culture solution, and then resuspended the cells in 50 mL of physiological saline, and then centrifuged again to obtain wet cells. .
  • the wet cells obtained by the above culture method were suspended in pure water.
  • the suspension was continuously fed at a rate of 11 g / h while stirring in the first reactor.
  • Acrylonitrile was continuously fed at a rate of 32 g / h, and pure water was continuously fed at a rate of 37 g / h. Further, a 0.1 M NaOH aqueous solution was fed so that the reaction pH was 7.5 to 8.5. These feeds were fed from each storage tank in a single line and did not come into contact with other feeds until fed into the reactor.
  • reaction solution is continuously withdrawn from the first reactor at a rate of 80 g / h, and continuously fed to the second reactor. The reaction was allowed to proceed further in the reactor.
  • the amount of wet cells added was adjusted so that the acrylonitrile conversion rate in the first reactor was 97%.
  • Teflon (registered trademark) tube 20 m having an inner diameter of 5 mm was used as the second reactor.
  • the reaction liquid continuously extracted from the first reactor is continuously fed to the second reactor, and the reaction is further advanced.
  • the first reactor and the second reactor were both immersed in a water bath having a temperature of 10 to 20 ° C., and the temperature was controlled so that the liquid temperature inside each reactor was 15 ° C.
  • the methanol test is a test in which 90 mL of methanol is added to 10 mL of a reaction solution and the like, and the transmittance at 360 nm is measured. As a result, when the transmittance is 99.9% or more, the presence of an acrylamide polymer is not recognized. .
  • the reaction liquid extracted from the first reactor was filtered with filter paper to remove the cells.
  • acrylamide was dissolved in pure water to prepare an aqueous acrylamide solution having a known concentration, and a calibration curve for acrylamide concentration analysis in HPLC was prepared. Using this, the area value at the time of HPLC analysis of the test solution was converted to acrylamide concentration (absolute calibration curve method). The amount of the reaction solution used for HPLC measurement was 5 ⁇ L. In addition, since there was almost no influence of the density of each reaction liquid, the acrylamide density
  • the activated carbon was washed with 300 g of pure water, mixed with the previous activated carbon treatment solution, neutralized with a 1M NaOH aqueous solution, and a pH of 7 was obtained to obtain about 7900 g of product. .
  • the final acrylamide concentration in the product after the activated carbon treatment was 50.5% by weight.
  • polypeptide is a term including a protein, one or more polypeptides constituting the protein, and a fragment of the polypeptide.
  • Spectrophotometer U-2000 (Hitachi) Dialysis membrane: Spectra / Por CE (Nippon Genetics) Coloring reagent: DYE reagent (Bio-Rad) (Methanol test) A methanol test was performed on the resulting product. That is, 90 mL of methanol was added to 10 mL of the obtained product, and the transmittance at 360 nm was measured. The transmittance was 99.9% or more, and the presence of a polymer was not recognized.
  • the reagent When the reagent was injected, the supply of nitrogen gas was stopped because it was observed that the temperature inside the polyethylene container increased after an induction period of several minutes.
  • the temperature inside the polyethylene container reached about 70 ° C. Therefore, the polyethylene container was taken out of the heat insulation block and immersed in 97 ° C. water for 2 hours to further proceed the polymerization reaction. Thereafter, it was immersed in cold water and cooled to stop the polymerization reaction.
  • the water-containing acrylamide polymer gel thus obtained was taken out of the polyethylene container, divided into small blocks, and ground with a meat grinder. This ground acrylamide polymer hydrogel was dried with hot air at 100 ° C. for 2 hours, and further pulverized with a high-speed rotary blade pulverizer to obtain a dry powdery acrylamide polymer.
  • the water solubility test means that 600 mL of water is put into a 1 L beaker, and 0.6 g of acrylamide polymer is added while stirring at 25 ° C. using a stirring blade of a predetermined shape, and the insoluble matter is filtered off and dried. The content of insoluble matter is determined from the weight.
  • the obtained dry powdery acrylamide polymer was passed through a sieve to fractionate a 32-42 mesh polymer.
  • this fractionated acrylamide polymer was evaluated by a water solubility test, the content of the insoluble matter was 0.3%, indicating a good water solubility.
  • ⁇ Acrylamide preservation process Aeration treatment is performed continuously for 10 days at a flow rate of 1 m 3 / h in a constant temperature bath at 20 ° C. for 500 g of the activated carbon treated product (acrylamide concentration 50.6%) obtained in the purification process. And a storage solution was obtained.
  • the aeration was stopped and the dissolved oxygen concentration was measured and found to be 8 ppm.
  • 90 mL of methanol was added to 10 mL of the obtained storage treatment solution, and the transmittance at 360 nm was measured (methanol test). In either case, the transmittance was 99.9% or more, and the presence of a polymer was not recognized.
  • Example (1-1) the dissolved oxygen concentration in the first reaction step is 8 ppm to 4 ppm (Example (1-2)), 2 ppm (Example (1-3)) or 1.2 ppm (Example (1) -4)), except that acrylamide was produced in the same manner as in Example (1-1) and subjected to various tests. The obtained results are shown in Table 1.
  • Example (1-1) the same operation as in Example (1-1) was performed except that the gas vented to the first reactor was a mixture of nitrogen and air instead of air. went. The proportion of air in the mixture was 50%, 25%, and 15%, respectively.
  • the dissolved oxygen concentration in the reaction solution at the outlet of the first reactor is 4 ppm, 2 ppm, and 1.2 ppm, respectively, and the dissolved oxygen concentration in the reaction solution at the outlet of the second reactor is 3.5 ppm, 1.8 ppm, and 1 ppm, respectively. 0.0 ppm.
  • the reaction liquid in the first reactor was filtered with filter paper to remove the cells. 90 mL of methanol was added to 10 mL of the obtained filtrate, and the transmittance at 360 nm was measured (methanol test). The transmittance was 99.9% or more in any case, and the presence of a polymer was not recognized.
  • activated carbon treatment was performed in the same manner as in Example (1-1) to obtain about 7900 g of product.
  • 90 mL of methanol was added to 10 mL of the obtained product, and the transmittance at 360 nm was measured (methanol test). In either case, the transmittance was 99.9% or more, and the presence of a polymer was not recognized.
  • Example (1-1) the dissolved oxygen concentration in the purification step is 8 ppm to 4 ppm (Example (2-1)), 2 ppm (Example (2-2)), or 1 ppm (Example (2-3)).
  • Acrylamide was produced in the same manner as in Example (1-1) except for changing to, and subjected to various tests. The obtained results are shown in Table 1.
  • Example (1-1) the air flow during the activated carbon treatment at pH 5 was the same as in Example (1-1) except that air and nitrogen were mixed instead of air. The operation was performed. The proportion of air in the mixture was 50%, 25%, and 12%, respectively. As a result, the dissolved oxygen concentration of the treatment liquid after stirring for 24 hours was 4 ppm, 2 ppm, and 1.0 ppm, respectively. 90 mL of methanol was added to 10 mL of the obtained product, and the transmittance at 360 nm was measured (methanol test). In either case, the transmittance was 99.9% or more, and the presence of a polymer was not recognized.
  • the acrylamide polymer produced from the obtained aqueous acrylamide solution was evaluated by a water solubility test. In all cases, the content of insoluble matter was 0.3%, indicating good water solubility. .
  • Example (3-1) In Example (1-1), the point at which oxygen was dissolved when the acrylonitrile concentration in the first reaction step reached 0.4% by weight and the amount of wet cells added were the acrylonitrile conversion rate of the first reactor.
  • Acrylamide was produced in the same manner as in Example (1-1) except that the adjustment was made to 99% and subjected to various tests. The obtained results are shown in Table 1.
  • a 1 L glass flask equipped with a stirrer was prepared as the first reactor, and a Teflon (registered trademark) tube 20 m having an inner diameter of 5 mm was prepared as the second reactor.
  • the first reactor was charged with 400 g of water in advance. Air was bubbled through the gas phase portion of the first reactor at a flow rate of 1 L / min.
  • the wet cells obtained by the same method as described in Example (1-1) were suspended in pure water.
  • the suspension was continuously fed at a rate of 16 g / h while stirring in the first reactor.
  • Acrylonitrile was continuously fed at a rate of 32 g / h, and pure water was continuously fed at a rate of 32 g / h.
  • a 0.1 M NaOH aqueous solution was fed so that the reaction pH was 7.5 to 8.5.
  • These feeds were fed from each storage tank in a single line and did not come into contact with other feeds until fed into the reactor.
  • the reaction solution is continuously withdrawn from the first reactor at a rate of 80 g / h, and continuously fed to the second reactor. The reaction was allowed to proceed further in the reactor.
  • the amount of wet cells added was adjusted so that the conversion rate of acrylonitrile in the first reactor was 99%.
  • Both the first reactor and the second reactor were immersed in a water bath at a temperature of 10 to 20 ° C., and the temperature was controlled so that the liquid temperature inside each reactor was 15 ° C.
  • the reaction solution in each reactor was sampled and subjected to HPLC analysis.
  • the conversion rate to acrylamide at the first reactor outlet was 99%, and the reaction at the first reactor outlet was The acrylonitrile concentration was 0.4% by weight, the acrylonitrile concentration at the outlet of the second reactor was below the detection limit (100 ppm by weight or less), and the acrylamide concentration was 53.3% by weight.
  • the dissolved oxygen concentration in the reaction liquid at the outlet of the first reactor was 8 ppm, and the dissolved oxygen concentration in the reaction liquid at the outlet of the second reactor was 7 ppm.
  • the reaction liquid in the first reactor was filtered with filter paper to remove the cells. 90 mL of methanol was added to 10 mL of the obtained filtrate, and the transmittance at 360 nm was measured. The transmittance was 99.9% or more, and the presence of a polymer was not recognized.
  • the activated carbon is washed with 300 g of pure water, mixed with the previous activated carbon treatment solution, neutralized with 1M NaOH aqueous solution, and about 7900 g of product is prepared with a pH of 7. Obtained.
  • the final acrylamide concentration in the product after the activated carbon treatment was 50.4% by weight.
  • 90 mL of methanol was added to 10 mL of the obtained product, and the transmittance at 360 nm was measured. The transmittance was 99.9% or more, and the presence of a polymer was not recognized.
  • a dry powdery acrylamide polymer was produced from the obtained aqueous acrylamide solution using the same production method as described above.
  • the acrylamide polymer was passed through a sieve to fractionate a 32-42 mesh polymer.
  • this fractionated acrylamide polymer was evaluated by a water solubility test, the content of the insoluble matter was 0.5%, indicating good water solubility.
  • Examples (3-2) to (3-4) In each of Examples (1-2) to (1-4), the point at which oxygen was dissolved when the acrylonitrile concentration in the first reaction step reached 0.4% by weight and the amount of wet cells added were Acrylamide was produced in the same manner as in Examples (1-2) to (1-4) except that the acrylonitrile conversion rate in the reactor was adjusted to 99% and subjected to various tests. Examples (3-2) to (3-4)). The obtained results are shown in Table 1.
  • Example (3-1) the same operation as in Example (3-1) was performed except that the gas vented to the first reactor in Example (3-1) was a mixed gas of nitrogen and air instead of air. .
  • the proportion of air in the mixture was 50%, 25%, and 15%.
  • the dissolved oxygen concentration in the reaction liquid at the first reactor outlet is 4 ppm, 2 ppm, and 1.2 ppm, respectively, and the dissolved oxygen concentration in the reaction liquid at the second reactor outlet is 3.5 ppm, 1.8 ppm, and 1.0 ppm. Met.
  • the reaction liquid in the first reactor was filtered with filter paper to remove the cells. 90 mL of methanol was added to 10 mL of the obtained filtrate, and the transmittance at 360 nm was measured. The transmittance was 99.9% or more in any case, and the presence of a polymer was not recognized.
  • the activated carbon treatment was performed by the same operation as in Example (3-1) including the aeration conditions to obtain about 7900 g of product. 90 mL of methanol was added to 10 mL of the obtained product, and the transmittance at 360 nm was measured. In either case, the transmittance was 99.9% or more, and the presence of a polymer was not recognized.
  • Example (3-1) the dissolved oxygen concentration in the purification step is 8 ppm to 4 ppm (Example (4-1)), 2 ppm (Example (4-2)), or 1 ppm (Example (4-3)).
  • Acrylamide was produced in the same manner as in Example (3-1) except that it was changed to. The obtained results are shown in Table 1.
  • Example (3-1) the same operation as in Example (3-1) was performed except that the air during the activated carbon treatment at pH 5 was a mixed gas of nitrogen and air instead of air. It can be said that it went.
  • the ratio of air in the air-fuel mixture was 50%, 25%, and 12%.
  • the dissolved oxygen concentration of the treatment liquid after stirring for 24 hours was 4 ppm, 2 ppm, and 1.0 ppm, respectively.
  • the dissolved oxygen concentrations of the treatment liquid after stirring for 24 hours were 4 ppm, 2 ppm, and 1 ppm, respectively.
  • 90 mL of methanol was added to 10 mL of the obtained product, and the transmittance at 360 nm was measured. In either case, the transmittance was 99.9% or more, and the presence of a polymer was not recognized.
  • Example (1-1) acrylamide was produced in the same manner as in Example (1-1) except that the dissolved oxygen concentration in the first reaction step was changed from 8 ppm to less than 1 ppm, and subjected to various tests. The obtained results are shown in Table 1.
  • Example (1-1) the same operation as in Example (1-1) was performed except that the gas vented to the first reactor was a mixture of nitrogen and air instead of air. went. The ratio of nitrogen and air was adjusted so that the dissolved oxygen concentration in the reaction liquid at the outlet of the first reactor was less than 1.0 ppm and the dissolved oxygen concentration in the reaction liquid at the outlet of the second reactor was less than 1.0 ppm. This operation was repeated several times.
  • the reaction liquid in the first reactor and the second reactor was filtered with filter paper to remove the cells.
  • 90 mL of methanol was added to 10 mL of the obtained filtrate, and the transmittance at 360 nm was measured (methanol test).
  • the transmittance of the reaction solution from the first reactor was 99.9% or more, and the presence of a polymer was not recognized.
  • the transmittance of the reaction solution from the second reactor was usually 99.9% or more, but it became 98.5% at a rate of about once every 10 times, and the presence of a polymer was observed. there were.
  • the activated carbon treatment was performed in the same manner as in Example (1-1) to obtain about 7900 g of product.
  • 90 mL of methanol was added to 10 mL of the obtained product, and the transmittance at 360 nm was measured (methanol test).
  • the transmittance was 99.9%, and no polymer was observed, but the acrylamide solution in which the polymer was found in the second reactor was activated carbon.
  • the transmittance was 98.0%, and the presence of a polymer was recognized.
  • the acrylamide polymer produced from the obtained acrylamide aqueous solution was evaluated by a water solubility test.
  • the content of insoluble matter was 0.3%.
  • the content of the insoluble matter was 5%.
  • the transmittance was 99.9%, and no polymer was observed.
  • the transmittance of the acrylamide from the aqueous acrylamide solution when the presence of the polymer was recognized in the second reactor was 98%, and the presence of the polymer was recognized.
  • the acrylamide polymer produced from the acrylamide aqueous solution at this time was evaluated by a water solubility test, the content of the insoluble matter was 4%, which caused a problem in quality.
  • Example (3-1) the dissolved oxygen concentration in the first reaction step was changed from 8 ppm to less than 1 ppm, and the amount of wet cells added was adjusted so that the acrylonitrile conversion rate in the first reactor was 99%.
  • the acrylamide was purified in the same manner as in Example (3-1) except that the above was performed. This operation was repeated several times. The obtained results are shown in Table 1.
  • a 1 L glass flask equipped with a stirrer as a first reactor and a Teflon (registered trademark) tube 20 m with an inner diameter of 5 mm were prepared as a second reactor.
  • the first reactor was charged with 400 g of water in advance. Nitrogen was bubbled through the first reactor at a flow rate of 1 L / min.
  • the wet cells obtained by the same method as described in Example (1-1) were suspended in pure water.
  • the suspension was continuously fed at a rate of 16 g / h while stirring in the first reactor.
  • Acrylonitrile was continuously fed at a rate of 32 g / h, and pure water was continuously fed at a rate of 32 g / h.
  • a 0.1 M NaOH aqueous solution was fed so that the reaction pH was 7.5 to 8.5.
  • the reaction solution is continuously withdrawn from the first reactor at a rate of 80 g / h, and continuously fed to the second reactor.
  • the reaction was allowed to proceed further in the reactor.
  • the amount of wet cells added was adjusted so that the conversion rate of acrylonitrile in the first reactor was 99%.
  • Both the first reactor and the second reactor were immersed in a water bath at a temperature of 10 to 20 ° C., and the temperature was controlled so that the liquid temperature inside each reactor was 15 ° C.
  • the reaction solution in each reactor was sampled and subjected to HPLC analysis.
  • the conversion rate to acrylamide at the first reactor outlet was 99%, and the reaction at the first reactor outlet was
  • the acrylonitrile concentration was 0.4% by weight
  • the acrylonitrile concentration at the outlet of the second reactor was below the detection limit (100 ppm by weight or less)
  • the acrylamide concentration was 53.3% by weight.
  • the dissolved oxygen concentration in the reaction liquid at the first reactor outlet and the second reactor outlet was both less than 1 ppm.
  • the reaction solution in the first reactor was filtered with filter paper to remove the cells.
  • 90 mL of methanol was added to 10 mL of the obtained filtrate, and the transmittance at 360 nm was measured. Usually, it was 99.9% or more, but it became 98.5% at a rate of about once every 10 times, and the presence of a polymer was sometimes observed.
  • the activated carbon is washed with 300 g of pure water, mixed with the previous activated carbon treatment solution, neutralized with 1M NaOH aqueous solution, and about 7900 g of product is prepared with a pH of 7. Obtained.
  • the final acrylamide concentration in the product after the activated carbon treatment was 50.5% by weight. 90 mL of methanol was added to 10 mL of the obtained product, and the transmittance at 360 nm was measured.
  • the acrylamide from the acrylamide aqueous solution when the presence of the polymer was not recognized in the first reactor had a transmittance of 99.9% or more, but the acrylamide when the presence of the polymer was recognized in the first reactor. In the case of acrylamide from an aqueous solution, the transmittance was 98%, and the presence of a polymer was recognized.
  • the acrylamide polymer produced from the obtained acrylamide aqueous solution was evaluated by a water solubility test, the acrylamide polymer from the acrylamide aqueous solution when the presence of the polymer was not recognized in the first reactor, The content rate was 0.3%, but in the acrylamide polymer from the acrylamide aqueous solution when the presence of the polymer was recognized in the first reactor, the content rate of the insoluble content was 5%.
  • Example (3-1) the concentration of dissolved oxygen in the purification step was changed from 8 ppm to less than 1 ppm, and the amount of wet cells added was adjusted so that the acrylonitrile conversion rate in the first reactor was 99%. Except for the above points, acrylamide was purified in the same manner as in Example (3-1). The obtained results are shown in Table 1.
  • a 1 L glass flask equipped with a stirrer as a first reactor and a Teflon (registered trademark) tube 20 m with an inner diameter of 5 mm were prepared as a second reactor.
  • the first reactor was charged with 400 g of water in advance. Air was bubbled through the first reactor at a flow rate of 1 L / min.
  • the wet cells obtained by the same method as described in Example (1-1) were suspended in pure water.
  • the suspension was continuously fed at a rate of 16 g / h while stirring in the first reactor.
  • Acrylonitrile was continuously fed at a rate of 32 g / h, and pure water was continuously fed at a rate of 32 g / h.
  • a 0.1 M NaOH aqueous solution was fed so that the reaction pH was 7.5 to 8.5.
  • These feeds were fed from each storage tank in a single line and did not come into contact with other feeds until fed into the reactor.
  • the reaction solution is continuously withdrawn from the first reactor at a rate of 80 g / h, and continuously fed to the second reactor. The reaction was allowed to proceed further in the reactor.
  • the amount of wet cells added was adjusted so that the conversion rate of acrylonitrile in the first reactor was 99%.
  • Both the first reactor and the second reactor were immersed in a water bath at a temperature of 10 to 20 ° C., and the temperature was controlled so that the liquid temperature inside each reactor was 15 ° C.
  • the reaction solution in each reactor was sampled and analyzed under the above HPLC conditions.
  • the conversion rate to acrylamide at the outlet of the first reactor was 99%.
  • the acrylonitrile concentration at the reactor outlet was 0.4% by weight
  • the acrylonitrile concentration at the outlet of the second reactor was below the detection limit (100 ppm by weight or less)
  • the acrylamide concentration was 53.3% by weight.
  • the dissolved oxygen concentration in the reaction liquid at the outlet of the first reactor was 8 ppm
  • the dissolved oxygen concentration in the reaction liquid at the outlet of the second reactor was 7 ppm.
  • the reaction liquid in the first reactor was filtered with filter paper to remove the cells. 90 mL of methanol was added to 10 mL of the obtained filtrate, and the transmittance at 360 nm was measured. The transmittance was 99.9% or more, and the presence of a polymer was not recognized.
  • Example (3-1) acrylamide was produced in the same manner as in Example (3-1) except that the dissolved oxygen concentration in the storage step was changed from 8 ppm to less than 1 ppm. The obtained results are shown in Table 1.
  • Example 3-1 10 g of nitrogen at a flow rate of 1 m 3 / h in a constant temperature bath at 20 ° C. was applied to 500 g of the activated carbon-treated product (acrylamide concentration 50.6%) obtained in Example (3-1). Aeration treatment was performed continuously for days to obtain a preservation solution. After 10 days, the aeration was stopped and the dissolved oxygen concentration was measured and found to be less than 1 ppm. 90 mL of methanol was added to 10 mL of the obtained storage treatment solution, and the transmittance at 360 nm was measured. The transmittance was 95%, and the presence of a polymer was recognized.
  • Example 5 In the first reaction step of Example (1-1), instead of adjusting the amount of wet cells added so that the acrylonitrile conversion rate in the first reactor was 97%, the conversion rate was 90%.
  • Acrylamide was produced in the same manner as in Example (1-1) except that adjustment was performed so as to be, and subjected to various tests. The obtained results are shown in Table 1.
  • Example 5 As a reaction step of Example 5, a 1 L glass flask equipped with a stirrer as a first reactor and a Teflon (registered trademark) tube 20 m with an inner diameter of 5 mm were prepared as a second reactor.
  • the first reactor was charged with 400 g of water in advance. In the first reactor, air was passed through the gas phase portion at a flow rate of 1 L / min.
  • the wet cells obtained by the same method as described in Example (1-1) were suspended in pure water.
  • the suspension was continuously fed at a rate of 11 g / h while stirring in the first reactor.
  • Acrylonitrile was continuously fed at a rate of 32 g / h, and pure water was continuously fed at a rate of 37 g / h.
  • a 0.1 M NaOH aqueous solution was fed so that the reaction pH was 7.5 to 8.5.
  • These feeds were fed from each storage tank in a single line and did not come into contact with other feeds until fed into the reactor.
  • the reaction solution is continuously withdrawn from the first reactor at a rate of 80 g / h, and continuously fed to the second reactor. The reaction was allowed to proceed further in the reactor.
  • the amount of wet cells added was adjusted so that the acrylonitrile conversion rate in the first reactor was 90%.
  • Both the first reactor and the second reactor were immersed in a water bath at a temperature of 10 to 20 ° C., and the temperature was controlled so that the liquid temperature inside each reactor was 15 ° C.
  • the reaction solution in each reactor was sampled and analyzed under the above HPLC conditions.
  • the conversion rate to acrylamide at the outlet of the first reactor was 90%
  • the second The acrylonitrile concentration at the outlet of the reactor was below the detection limit (100 ppm by weight or less), and the acrylamide concentration was 53.5% by weight.
  • the dissolved oxygen concentration in the reaction liquid at the outlet of the first reactor was 8 ppm
  • the dissolved oxygen concentration in the reaction liquid at the outlet of the second reactor was 7 ppm.
  • this reaction was analyzed on the second day and continued for about 4 days. In about 4 days, about 7500 g of reaction liquid was obtained.
  • 30 g of activated carbon (Kuraray Chemical Co., Ltd., powdered activated carbon PM-SX) was added, and after adding 0.5 wt% -acrylic acid aqueous solution 160 g, the pH was adjusted to 5 with 1 M NaOH aqueous solution. . This was stirred for 5 hours at 25 ° C. in an environment in which air was aerated at a flow rate of 1 L / min, and then filtered through filter paper to remove activated carbon. The dissolved oxygen concentration of the treatment liquid after stirring for 5 hours was 8 ppm.
  • the activated carbon is washed with 300 g of pure water, mixed with the previous activated carbon treatment solution, neutralized with 1M NaOH aqueous solution, and about 7900 g of product is prepared with a pH of 7. Obtained.
  • the final acrylamide concentration in the product after the activated carbon treatment was 50.6% by weight.
  • Example 5 In the storage step of Example 5, the same treatment as in Example 5 was performed except that nitrogen having a purity of 99.9% was used instead of using air to obtain a treatment liquid. The dissolved oxygen concentration of this treatment liquid was 0.08 ppm. When 90 mL of methanol was added to 10 mL of the obtained treatment solution, it became cloudy and the presence of a polymer was observed.
  • Example 6 In Example (1-1), it was carried out except that the oxygen was dissolved when the acrylonitrile concentration in the first reaction step reached 0.8% by weight and the dissolved oxygen concentration was changed from 8 ppm to 1.2 ppm. Acrylamide was produced in the same manner as in Example (1-1). At this time, the dissolved oxygen concentration in the second reaction step was 1.0 ppm. Furthermore, Example 6 was implemented several times.
  • Example (1-1) In Example (1-1), except that the oxygen was dissolved when the acrylonitrile concentration in the first reaction step reached 0.8% by weight, and the dissolved oxygen concentration was changed from 8 ppm to less than 1 ppm. Acrylamide was produced in the same manner as (1-1). At this time, the dissolved oxygen concentration in the second reaction step was less than 1.0 ppm. Further, Comparative Example 6 was performed a plurality of times.
  • Example 6 and Comparative Example 6 that is, in the first reaction step of Example (1-1), the conversion rate to acrylamide at the outlet of the first reactor was 98%, and at the outlet of the first reactor.
  • the same procedure as in Example (1-1) was performed except that the acrylonitrile concentration in the first reactor was 0.8% by weight and that the gas vented to the first reactor was a mixed gas of nitrogen and air instead of air. went. The proportion of air in the mixture was 15% and 5%, respectively.
  • the dissolved oxygen concentrations in the reaction solution at the outlet of the first reactor were 1.2 ppm and less than 1.0 ppm, respectively.
  • the reaction solution in the first reactor was filtered with filter paper to remove the cells.
  • 90 mL of methanol was added to 10 mL of the obtained filtrate, and the transmittance at 360 nm was measured (methanol test).
  • the transmittance was 99.9% or more when the dissolved oxygen concentration was 1.2 ppm (Example 6), and the presence of a polymer was not observed, but the dissolved oxygen concentration was less than 1.0 ppm (comparison). In Example 6), it was usually 99.9% or more, but it became 98.5% at a rate of about once in 10 times, and the presence of a polymer was sometimes observed.
  • Example 6 when the acrylamide polymer produced from the acrylamide aqueous solution obtained by operating the second reaction step and the purification step in the same manner as in Example (1-1) was evaluated by a water solubility test, the transmittance was determined by the first reaction.
  • the dissolved oxygen concentration was 1.2 ppm in the process (Example 6)
  • the content of insoluble matter was 0.3%, indicating good water solubility.
  • the dissolved oxygen concentration was less than 1.0 ppm in the first reaction step (Comparative Example 6)
  • the content of insoluble matter was 4% at a rate of about once every 10 times, resulting in quality problems. .
  • Table 1 The obtained results are shown in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Genetics & Genomics (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Microbiology (AREA)
  • Biotechnology (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un procédé pour préserver, dans un état stable, un composé amide ayant une liaison insaturée, qui est industriellement très important mais subit très aisément une polymérisation et, par conséquent, est très difficile à manipuler, sans ajouter une substance chimique ou en utilisant nouvellement un dispositif ou une conception spéciaux. La présente invention concerne un procédé pour stabiliser un composé amide ayant une liaison insaturée, qui est industriellement très important mais subit très aisément une polymérisation et, par conséquent, est très difficile à manipuler, comprenant le contrôle de la concentration d'oxygène d'une solution contenant ledit composé amide ayant une liaison insaturée.
PCT/JP2011/061546 2010-05-21 2011-05-19 Procédé pour stabiliser un composé amide ayant une liaison insaturée WO2011145687A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012515929A JPWO2011145687A1 (ja) 2010-05-21 2011-05-19 不飽和結合を有するアミド化合物の安定化方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-117551 2010-05-21
JP2010117551 2010-05-21

Publications (1)

Publication Number Publication Date
WO2011145687A1 true WO2011145687A1 (fr) 2011-11-24

Family

ID=44991778

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/061546 WO2011145687A1 (fr) 2010-05-21 2011-05-19 Procédé pour stabiliser un composé amide ayant une liaison insaturée

Country Status (3)

Country Link
JP (2) JPWO2011145687A1 (fr)
TW (1) TW201141817A (fr)
WO (1) WO2011145687A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11098299B2 (en) * 2016-12-28 2021-08-24 Mitsui Chemicals, Inc. Mutant nitrile hydratase, nucleic acid coding said mutant nitrile hydratase, expression vector and transformant including said nucleic acid, production method for said mutant nitrile hydratase, and production method for amide compound

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61122253A (ja) * 1984-11-16 1986-06-10 Nitto Chem Ind Co Ltd アクリルアミド水溶液の精製方法
JPH04312562A (ja) * 1991-04-11 1992-11-04 Showa Denko Kk アクリルアミド水溶液の精製方法
JPH07118216A (ja) * 1993-10-26 1995-05-09 Asahi Chem Ind Co Ltd メタクリルアミドの製造方法
JP2002281994A (ja) * 2001-03-27 2002-10-02 Mitsubishi Rayon Co Ltd アクリル酸水溶液で洗浄した微生物触媒によるアクリルアミドの製造方法。

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003277416A (ja) * 2002-03-22 2003-10-02 Daiyanitorikkusu Kk 糖類を含むアクリルアミド水溶液

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61122253A (ja) * 1984-11-16 1986-06-10 Nitto Chem Ind Co Ltd アクリルアミド水溶液の精製方法
JPH04312562A (ja) * 1991-04-11 1992-11-04 Showa Denko Kk アクリルアミド水溶液の精製方法
JPH07118216A (ja) * 1993-10-26 1995-05-09 Asahi Chem Ind Co Ltd メタクリルアミドの製造方法
JP2002281994A (ja) * 2001-03-27 2002-10-02 Mitsubishi Rayon Co Ltd アクリル酸水溶液で洗浄した微生物触媒によるアクリルアミドの製造方法。

Also Published As

Publication number Publication date
TW201141817A (en) 2011-12-01
JP2015164425A (ja) 2015-09-17
JP5925355B2 (ja) 2016-05-25
JPWO2011145687A1 (ja) 2013-07-22

Similar Documents

Publication Publication Date Title
JP4970276B2 (ja) アミド化合物の製造方法
JP2014176344A (ja) 反応経過を監視することを特徴とするアミド化合物の製造方法およびアミド化合物の製造装置
JP2015057968A (ja) アミド化合物の製造方法およびアミド化合物の製造装置
WO2007132601A1 (fr) Procédé de production du (méth)acrylamide
KR101598643B1 (ko) 아크릴아마이드 수용액의 안정화 방법
EP2540700B1 (fr) Solution aqueuse stable d'acrylamide
EP1167345B1 (fr) Procede de purification d'un compose amide
JP5925355B2 (ja) 不飽和結合を有するアミド化合物の安定化方法
JP2019176835A (ja) アミド化合物の製造方法
JP5430659B2 (ja) 菌体処理物の製造方法
WO2011148867A1 (fr) Procédé de fabrication d'un composé amide
EP2711429A1 (fr) Procédé pour la production de solution aqueuse d'acrylamide
JP2011241201A (ja) 不飽和結合を有するアミド化合物の精製方法
JP4959059B2 (ja) アミド化合物の精製方法
CN105247063B (zh) 丙烯酰胺的制造方法
JP2012062268A (ja) アミド化合物の精製方法
EP2711355B1 (fr) Procédé de fabrication de solution aqueuse d'acrylamide
RU2539033C1 (ru) РЕКОМБИНАНТНЫЙ ШТАММ БАКТЕРИЙ Rhodococcus rhodochrous, ОБЛАДАЮЩИЙ КОНСТИТУТИВНОЙ АЦИЛИРУЮЩЕЙ АКТИВНОСТЬЮ, И СПОСОБ СИНТЕЗА N-ЗАМЕЩЕННЫХ АКРИЛАМИДОВ С ИСПОЛЬЗОВАНИЕМ ЭТОГО ШТАММА В КАЧЕСТВЕ БИОКАТАЛИЗАТОРА
JP5849428B2 (ja) 微生物触媒を用いた化合物の製造方法
JP2012031126A (ja) アミド化合物の精製方法
JP2014113092A (ja) ポンプを用いるアミド化合物の製造方法およびアミド化合物の製造装置
JP2020115838A (ja) ニトリルヒドラターゼの保存方法
JP2019089727A (ja) アミド化合物の精製方法
JP2014079199A (ja) 原料混合供給によるアミド化合物の製造方法およびアミド化合物の製造装置
JP2019196317A (ja) アミド化合物の精製方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11783621

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012515929

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11783621

Country of ref document: EP

Kind code of ref document: A1