WO2023167314A1 - Procédé d'hydrolyse du nylon - Google Patents

Procédé d'hydrolyse du nylon Download PDF

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WO2023167314A1
WO2023167314A1 PCT/JP2023/008043 JP2023008043W WO2023167314A1 WO 2023167314 A1 WO2023167314 A1 WO 2023167314A1 JP 2023008043 W JP2023008043 W JP 2023008043W WO 2023167314 A1 WO2023167314 A1 WO 2023167314A1
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nylon
solution
acid
hydrolyzing
dispersion
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PCT/JP2023/008043
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Japanese (ja)
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太一郎 加藤
雄樹 白石
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国立大学法人 鹿児島大学
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Publication of WO2023167314A1 publication Critical patent/WO2023167314A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/26—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing carboxylic acid groups, their anhydrides or esters
    • 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
    • C12P1/00—Preparation of compounds or compositions, not provided for in groups C12P3/00 - C12P39/00, by using microorganisms or enzymes
    • 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
    • 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
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a method for hydrolyzing nylon.
  • Nylon a type of polyamide, is widely used as fibers and plastics due to its toughness, heat resistance, and chemical resistance. Nylon, on the other hand, is incinerated or landfilled after use because it hardly undergoes biodegradation.
  • Non-Patent Document 1 a method of hydrolyzing nylon using a nylon hydrolase to monomerize it has been reported.
  • Non-Patent Document 1 The method for hydrolyzing nylon in Non-Patent Document 1 cannot be said to have high enzymatic decomposition efficiency, and there is still room for improvement.
  • the present invention has been made in view of the above matters, and its object is to provide a method for hydrolyzing nylon that can improve the enzymatic decomposition efficiency of nylon.
  • the method for hydrolyzing nylon comprises: A method for hydrolyzing nylon by monomerizing nylon using a nylon hydrolase, comprising: a step of dissolving the nylon in an organic solvent capable of dissolving the nylon to prepare a nylon solution; a step of adding the nylon solution to a precipitation solvent for precipitating the nylon into particles to prepare a nylon precipitation solution; removing the organic solvent and the precipitation solvent from the nylon precipitation solution; adding an aqueous solution to the nylon obtained by removing the organic solvent and the precipitation solvent to prepare a nylon dispersion; adding the nylon hydrolase to the nylon dispersion to hydrolyze the nylon; It is characterized by
  • the nylon dispersion may be prepared by adding the aqueous solution to the nylon obtained by removing the oxidizing agent or the acid.
  • nylon 4 nylon 6, nylon 11, nylon 12, nylon 6,6, nylon 6,10, nylon 6,12, nylon 4,6, nylon 6T, nylon 6I, nylon M5T, nylon 6i, or , Nylon 6i-11 may be used.
  • a phosphate buffer solution containing glycerol as the aqueous solution.
  • the method for hydrolyzing nylon according to the second aspect of the present invention comprises: A method for hydrolyzing nylon by monomerizing nylon using a nylon hydrolase, comprising: a step of adding the nylon to a solution containing an oxidizing agent or an acid capable of decomposing the nylon and heating to reduce the molecular weight of the nylon; removing the oxidizing agent or the acid from the heated solution; adding an aqueous solution to the nylon obtained by removing the oxidizing agent or the acid to prepare a nylon dispersion; adding a nylon hydrolase to the nylon dispersion to hydrolyze the nylon; It is characterized by
  • the nylon obtained by removing the organic solvent and the precipitation solvent may be added to a solution containing the oxidizing agent or the acid and heated to reduce the molecular weight of the nylon.
  • a hydrogen peroxide solution as the oxidizing agent.
  • a phosphate buffer solution containing glycerol is preferably used as the aqueous solution.
  • FIG. 1 is a process chart showing a method for hydrolyzing nylon according to Embodiment 1.
  • FIG. It is process drawing which shows the hydrolysis method of nylon which concerns on another form.
  • FIG. 4 is a process chart showing a method for hydrolyzing nylon according to Embodiment 2.
  • FIG. It is process drawing which shows the hydrolysis method of nylon which concerns on another form. 4 is a photograph showing the TLC analysis results of Experiment 1.
  • FIG. 1 is a graph showing measurement results of free amino concentration by TNBS method in Experiment 1.
  • FIG. 2 is a photograph showing the TLC analysis results when nylon 6 was hydrolyzed as it was in Experiment 2.
  • FIG. 2 is a graph showing the measurement results of free amino concentration by TNBS method when nylon 6 is hydrolyzed as it is in Experiment 2.
  • FIG. 10 is a photograph showing the results of TLC analysis when the nylon dispersion was hydrolyzed in Experiment 2.
  • FIG. 10 is a graph showing the measurement results of the free amino concentration by the TNBS method when the nylon dispersion was hydrolyzed in Experiment 2.
  • FIG. 4 is a graph showing the measurement results of free amino concentration by the TNBS method in Experiment 3.
  • FIG. 10 is a graph showing the measurement results of the free amino concentration by the TNBS method in the case of hydrolyzing a nylon dispersion prepared by treating with nylon 6 and formic acid at 120° C. in Experiment 4.
  • 10 is a graph showing the measurement results of the free amino concentration by the TNBS method when a nylon dispersion prepared by treating nylon 6,6 and formic acid at 100° C. in Experiment 4 is hydrolyzed.
  • 10 is a graph showing the measurement results of the free amino concentration by the TNBS method when a nylon dispersion prepared by treating nylon 6 and hydrogen peroxide water at 100° C. in Experiment 4 is hydrolyzed.
  • 10 is a graph showing measurement results of free amino concentration by TNBS method when nylon 6i-11 (50%) and nylon dispersion prepared by treatment with formic acid at 100° C. in Experiment 4 were hydrolyzed.
  • the method for hydrolyzing nylon according to Embodiment 1 is a method for hydrolyzing nylon in which nylon is monomerized using a nylon hydrolase, and as shown in FIG. It comprises a preparation step, a solvent removal step, a nylon dispersion preparation step, and a hydrolysis step.
  • nylon solution preparation process In the nylon solution preparing step, a nylon solution is prepared by dissolving nylon in an organic solvent capable of dissolving nylon. By allowing nylon to intervene in an organic solvent, the hydrogen bonds of nylon are cut and each molecule becomes dispersed in the organic solvent. In addition, dissolution of nylon can be performed at room temperature.
  • the nylon used for preparing the solution may be pulverized into pellets.
  • Nylons used include nylon 4, nylon 6, nylon 11, nylon 12, nylon 6,6, nylon 6,10, nylon 6,12, nylon 4,6, nylon 6T, nylon 6I, nylon M5T nylon 6i, nylon 6i- 11 are mentioned.
  • Nylon is preferably finely crushed before use so that it can be easily dissolved in a short time.
  • organic solvent to be used should be capable of dissolving nylon, and examples thereof include trifluoroethanol and hexafluoroisopropanol.
  • nylon precipitate preparation process In the nylon deposit preparation step, a nylon deposit is obtained by adding a nylon solution to a solvent for depositing dissolved nylon.
  • nylon solution is dropped little by little into the precipitation solvent. Since nylon is basically insoluble in solvents other than the organic solvents mentioned above, when it is added dropwise to the precipitation solvent, the dissolved nylon aggregates and precipitates in the form of fine particles. As a result, a nylon precipitate liquid in which the nylon precipitated in the form of fine particles is dispersed is obtained.
  • the precipitation solvent is not limited as long as it can precipitate nylon in the form of particles, and examples include methanol, ethanol, and ethylene glycol, with ethanol and ethylene glycol being preferred.
  • solvent removal step In the solvent removal step, the organic solvent and the precipitation solvent are removed from the nylon precipitation solution. Any method can be used as long as the organic solvent and the precipitation solvent can be separated and removed. For example, the nylon precipitation solution is centrifuged and the supernatant is removed to remove the organic solvent and the precipitation solvent. In this case, the precipitated nylon is recovered as a precipitate.
  • the solvent removal step it is preferable to add an aqueous solution to this, perform centrifugation, and remove the supernatant several times for washing. By performing this washing operation multiple times, the organic solvent and the precipitation solvent can be sufficiently separated and removed.
  • nylon dispersion liquid preparation process By separating the organic solvent and the precipitation solvent and adding an aqueous solution to the removed nylon, a nylon dispersion liquid in which nylon is dispersed can be obtained.
  • a phosphate buffer to which glycerol has been added.
  • the pH of the phosphate buffer to which glycerol is added is 7.2-7.4, preferably 7.3, and the content of glycerol is 5-15% by weight, preferably 9-11% by weight.
  • Hydrolysis step In the hydrolysis step, a nylon hydrolase is added to the nylon dispersion to hydrolyze the nylon. Nylon hydrolase cleaves the polymer chain of nylon, decomposing it into oligomers, dimers, and monomers.
  • nylon hydrolase As a nylon hydrolase, a combination of both an endo-type nylonase that cleaves the polymer chain from the intermediate site of the repeating unit of the nylon molecule and an exo-type nylonase that cleaves the polymer chain from the end of the repeating unit. Good to use. Efficient nylon monomerization can be achieved by using both.
  • the compounding ratio may be arbitrary, for example, 1:9 to 9:1. Hydrolysis should be carried out for 2 hours or more, preferably 24 hours or more.
  • the efficiency of the enzymatic hydrolysis reaction of nylon is increased by preparing a nylon dispersion liquid in which nylon is dissolved and precipitated in fine particles, and then allowing the nylon hydrolase to act.
  • the improved enzymatic degradation efficiency of nylon enables the recycling of nylon as a monomer.
  • nylon solution preparation step after the above-described nylon solution preparation step, nylon precipitation solution preparation step, and solvent removal step are performed, the below-described low-molecular-weighting step and oxidizing agent or acid removing step are performed, and the oxidizing agent Alternatively, it is preferable to perform the above-described nylon dispersion preparation step and hydrolysis step using nylon after the acid removal step.
  • the nylon after solvent removal from the above-described nylon precipitation solution is added to a solution containing an oxidizing agent or an acid capable of decomposing nylon, followed by heating.
  • an oxidizing agent When an oxidizing agent is used, the oxidizing agent becomes a nucleophilic agent, hydrolyzing nylon, and reducing the molecular weight.
  • the oxidizing agent is not limited as long as it can promote the decomposition of nylon, and examples thereof include hydrogen peroxide water and hypohalites such as sodium hypochlorite.
  • the acid acts as a catalyst to hydrolyze the nylon and reduce the molecular weight.
  • acids include organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid and citric acid, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid.
  • the heating temperature is preferably 75 to 120.degree.
  • the heating time is sufficient as long as the nylon is sufficiently decomposed, and is 96 hours or longer, preferably 168 hours or longer, more preferably 336 hours or longer, depending on the type of nylon and the oxidizing agent.
  • Step of removing oxidizing agent or acid the oxidizing agent or acid used in the molecular weight reduction step is removed.
  • the method for removing the oxidizing agent or acid is not limited as long as the oxidizing agent or acid can be removed, and examples thereof include a removal method using a freeze-drying method.
  • nylon dispersion preparation step and hydrolysis step are performed. After dissolving nylon and precipitating it in the form of fine particles, further improvement in enzymatic decomposition efficiency can be achieved by allowing a nylon hydrolase to act on nylon that has been further reduced in molecular weight.
  • the method for hydrolyzing nylon according to Embodiment 2 is a method for hydrolyzing nylon in which nylon is monomerized using a nylon hydrolase, and as shown in FIG. , a nylon dispersion preparation step, and a hydrolysis step.
  • the nylon to be hydrolyzed those mentioned in the first embodiment are used.
  • nylon is added to a solution containing an oxidizing agent or acid capable of decomposing nylon and heated.
  • an oxidizing agent When an oxidizing agent is used, the oxidizing agent becomes a nucleophilic agent, hydrolyzing nylon, and reducing the molecular weight.
  • the solution containing the oxidizing agent is not limited as long as it can accelerate the decomposition of nylon, and examples thereof include hydrogen peroxide water and hypohalites such as sodium hypochlorite.
  • the acid acts as a catalyst to hydrolyze the nylon and reduce the molecular weight.
  • acids include organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid and citric acid, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid.
  • the heating temperature is preferably 75 to 120.degree.
  • the heating time is sufficient as long as the nylon is sufficiently decomposed, and is 96 hours or longer, preferably 168 hours or longer, more preferably 336 hours or longer, depending on the type of nylon and the oxidizing agent.
  • Step of removing oxidizing agent or acid the oxidizing agent or acid used in the molecular weight reduction step is removed.
  • the method for removing the oxidizing agent or acid is not limited as long as the oxidizing agent or acid can be removed, and examples thereof include a removal method using a freeze-drying method.
  • nylon dispersion liquid preparation process In the nylon dispersion preparation step, an aqueous solution is added to nylon after removal of the oxidizing agent or acid to prepare a nylon dispersion.
  • the amount of water to be added should be such that the nylon is sufficiently dispersed.
  • As the aqueous solution to be added it is preferable to use the phosphate buffer added with glycerol described in Embodiment 1.
  • Hydrolysis step In the hydrolysis step, a nylon hydrolase is added to the nylon dispersion to hydrolyze the nylon. Others are the same as those of the first embodiment described above, so the description is omitted.
  • the efficiency of the enzymatic hydrolysis reaction of nylon is increased by decomposing nylon with an oxidizing agent or acid to reduce the molecular weight and then allowing nylon hydrolase to act.
  • the improved enzymatic degradation efficiency of nylon enables the recycling of nylon as a monomer.
  • the nylon solution preparation step, the nylon precipitate preparation step, and the solvent removal step are performed, and the nylon after the solvent removal step may be used to perform the nylon dispersion preparation step and the hydrolysis step.
  • the description of the nylon solution preparation process, the nylon precipitation liquid preparation process, and the solvent removal process is the same as that of the first embodiment, so the description is omitted. Further improvement of enzymatic decomposition efficiency can be achieved by further dissolving the low-molecular-weight nylon and allowing a nylon hydrolase to act on the nylon precipitated in the form of fine particles.
  • Acetone, ethyl acetate, ethanol, methanol, water, and ethylene glycol were used as the nylon deposition liquid.
  • the enzyme solution was prepared so that the final concentrations of endo-type nylon hydrolase (hereinafter referred to as GYAQ) and hexo-type nylon hydrolase (hereinafter referred to as DNY) were each 1.0 mg/mL. .
  • GYAQ endo-type nylon hydrolase
  • DNY hexo-type nylon hydrolase
  • GYAQ an enzyme with a His-tag added to the N-terminus of EC number 3.5.1.117
  • DNY an enzyme with a His-tag added to the N-terminus of EC number 3.5.1.46
  • FIG. 6 shows the measurement results of free amino group concentration by the TNBS method. It can be seen that nylon 6 is decomposed and monomerized over time in all the cases where a nylon deposition solution other than water is used. Among them, the decomposition efficiency was high when ethylene glycol and ethanol were used. When the free amino group concentration was measured 2 hours after the hydrolysis was started, it was almost the same as the amino group concentration after 24 hours.
  • nylon 6 pellets (5 mg) were directly added to the above three types of enzyme solutions (400 ⁇ L). Then, TLC analysis and quantification of free amino groups by the TNBS method were performed in the same manner as described above.
  • Figures 7 and 8 show the results of TLC analysis when the nylon 6 dispersion was hydrolyzed and the measurement results of the concentration of free amino groups by the TNBS method.
  • Figures 9 and 10 show the results of TLC analysis when nylon 6 is hydrolyzed as it is and the measurement results of the free amino group concentration by the TNBS method, respectively.
  • nylon 6 dispersion When the nylon 6 dispersion was hydrolyzed, detection by TLC analysis was possible, whereas when nylon 6 was hydrolyzed as it was, it did not reach a level at which detection by TLC analysis was possible.
  • the estimated free amino group concentration when the used nylon 6 is completely decomposed is 44.2 mM in the case of the nylon 6 dispersion, and 110.5 mM in the case of hydrolyzing the nylon 6 as it is, according to the TNBS method.
  • Table 1 summarizes the decomposition rate of nylon 6 after the reaction for 72 hours calculated based on the analysis. Compared to the hydrolysis of nylon 6 as it is, hydrolysis efficiency of nylon 6 dispersion was about 4 to 7 times higher.
  • Table 2 summarizes the decomposition rate of each nylon after 72 hours of reaction based on analysis by the TNBS method. All nylons were hydrolyzed, and nylon 6,6 and nylon 6 had higher decomposition efficiency.
  • nylon 6i-11 is a nylon obtained from 1-aminohexyl-2-pyrrolidone-4-carboxylic acid (hereinafter referred to as 6i monomer unit) and 11 aminoundecanoic acid (hereinafter referred to as 11 monomer unit), nylon 6i -11 (50%) was obtained at a compounding ratio of 6i monomer units and 11 monomer units of 50:50. This nylon 6i-11 (50%) was provided by Mr.
  • Yoshiro Kaneko of National University Corporation Kagoshima University The mixture was heated at the set temperature for 96 hours while stirring with a stirrer. After heating, distilled water (25 mL) was added and freeze-dried to remove formic acid. After removing formic acid, 20 mM phosphate buffer (pH 7.3) containing 10% glycerol was added and resuspended to prepare a nylon dispersion. The final concentration of each nylon was adjusted to 10 mg/mL. The set temperatures were set to 75° C., 100° C., and 120° C., and the test was performed at each set temperature.
  • nylon dispersion was prepared in the same manner as above, except that 30% hydrogen peroxide water (6.8 mL) was used instead of formic acid.
  • Table 3 shows the decomposition rate of nylon when a nylon dispersion prepared using formic acid is hydrolyzed for 72 hours, and the decomposition rate of nylon when a nylon dispersion prepared using hydrogen peroxide water is hydrolyzed for 72 hours. are summarized in Table 4.
  • a nylon dispersion prepared by treating nylon 6 with formic acid at 120 ° C. nylon 6,6, a nylon dispersion prepared by treating with formic acid at 100 ° C., nylon 6, and hydrogen peroxide solution and nylon 6i-11 (50%), prepared by treatment with formic acid at 100°C.
  • the measurement results of amino group concentrations are shown in FIGS. 12, 13, 14 and 15, respectively. Both nylons are hydrolyzed.
  • the enzymatic decomposition efficiency was high when treated at 100°C, and when hydrogen peroxide was used, the enzymatic decomposition efficiency was high when treated at 75°C.
  • the free amino group concentration was measured 2 hours after the hydrolysis was started, it was almost the same as the amino group concentration after 24 hours.
  • nylon dispersion was prepared in the same manner as in Experiment 4, except that nylon 6,6 (1 g) and formic acid (6.8 mL) were used, and the heating time was set at 100°C for 168 hours.
  • nylon 6i-11 (50%) (1 g) and formic acid (6.8 mL) were used, and a nylon dispersion was prepared in the same manner as in Experiment 4 except that the heating time was 168 hours at 100°C.
  • a nylon dispersion was also prepared in the same manner as in Experiment 4, except that nylon 6 (50 mg) and 30% hydrogen peroxide solution (5 mL) were used, and the heating time was set at 75°C for 192 hours.
  • nylon 6i-11 (50%) (1 g) and formic acid (6.8 mL) were used, and a nylon dispersion was prepared in the same manner as in Experiment 4 except that the heating time was 336 hours at 100°C.
  • nylon 6i-11 (75%) (1 g) and formic acid (6.8 mL) were used, and a nylon dispersion was prepared in the same manner as in Experiment 4 except that the heating time was 168 hours at 100°C.
  • nylon 6i-11 (75%) was obtained at a compounding ratio of 6i monomer units and 11 monomer units of 25:75. This nylon 6i-11 (75%) was provided by Mr. Yoshiro Kaneko of Kagoshima University.
  • the decomposition rate of nylon is summarized in Tables 5 and 6. Enzymatic decomposition efficiency tended to increase with longer heating time.
  • the enzyme solution (200 ⁇ L) was added to the nylon dispersion (200 ⁇ L) and allowed to stand at 37°C. Then, in the same manner as in Experiment 1, free amino groups were quantified by the TNBS method to determine the decomposition rate of nylon 6.
  • As the enzyme solution three types (final concentration: 1.0 mg/mL) of GYAQ alone, DNY alone, and GYAQ and DNY in combination (weight ratio 1:1) were prepared and used.
  • Table 7 summarizes the decomposition rate of nylon 6 72 hours after adding the enzyme solution. It was demonstrated that the degradation rate of nylon can be increased by allowing a nylon hydrolase to act on a nylon dispersion prepared by further reducing the molecular weight of nylon precipitated in the form of fine particles. In particular, a high decomposition rate (88 to 97%) was exhibited when ethanol was used as the nylon depositing solution and heating was performed using formic acid for 168 hours.
  • the enzyme solution (200 ⁇ L) was added to the nylon dispersion (200 ⁇ L) and allowed to stand at 37°C. Then, in the same manner as in Experiment 1, free amino groups were quantified by the TNBS method to determine the decomposition rate of nylon 6,6.
  • As the enzyme solution three types (final concentration: 1.0 mg/mL) of GYAQ alone, DNY alone, and GYAQ and DNY in combination (weight ratio 1:1) were prepared and used.
  • Table 8 shows the decomposition rate of nylon 6,6 72 hours after adding the enzyme solution. The combination of GYAQ and DNY achieved 100% decomposition rate.

Abstract

Procédé d'hydrolyse du nylon consistant à monomériser le nylon par utilisation de nylon hydrolase et comprenant : une étape de dissolution du nylon dans un solvant organique dans lequel le nylon est soluble de façon à préparer une solution de nylon ; une étape de préparation d'un liquide de précipitation du nylon par addition de la solution de nylon à un solvant de précipitation pour provoquer la précipitation du nylon sous forme de particules ; une étape d'élimination du solvant organique et du solvant de précipitation du liquide de précipitation du nylon ; une étape d'addition d'une solution aqueuse de façon à préparer un liquide de dispersion de nylon ; et une étape d'addition de nylon hydrolase au liquide de dispersion de nylon dans le but d'hydrolyser le nylon.
PCT/JP2023/008043 2022-03-03 2023-03-03 Procédé d'hydrolyse du nylon WO2023167314A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06296949A (ja) * 1993-04-14 1994-10-25 Kobe Steel Ltd 酵素による合成高分子化合物の分解方法
JP2009139107A (ja) * 2007-12-03 2009-06-25 Nec Corp ペプチドの酵素による加水分解方法
JP2016505650A (ja) * 2012-11-20 2016-02-25 キャルビオスＣａｒｂｉｏｓ プラスチック製品をリサイクルする方法
US20190233610A1 (en) * 2018-02-01 2019-08-01 The Hong Kong Research Institute Of Textiles And Apparel Limited Textile Waste Processing

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06296949A (ja) * 1993-04-14 1994-10-25 Kobe Steel Ltd 酵素による合成高分子化合物の分解方法
JP2009139107A (ja) * 2007-12-03 2009-06-25 Nec Corp ペプチドの酵素による加水分解方法
JP2016505650A (ja) * 2012-11-20 2016-02-25 キャルビオスＣａｒｂｉｏｓ プラスチック製品をリサイクルする方法
US20190233610A1 (en) * 2018-02-01 2019-08-01 The Hong Kong Research Institute Of Textiles And Apparel Limited Textile Waste Processing

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SEIJI NEGORO ET AL., : "Chapter Seventeen - Structural and functional characterization of nylon hydrolases", ENZYMATIC PLASTIC DEGRADATION, ELSEVIER, 1 January 2021 (2021-01-01), pages 357 - 389, XP009548369, ISBN: 978-0-12-822012-2 *

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