Method for decomposing polyol or polyol ester

Abstract

The present invention provides a method for more easily decomposing a polyol or a polyol ester. A method for decomposing a polyol or a polyol ester according to the present invention is a decomposition method in which a substance to be decomposed containing at least one of a polyol and a polyol ester and a solid of a metal oxide or a metal hydroxide having a standard redox potential different from that of water are brought into contact with each other in specific reaction water, and in which the substance to be decomposed is heated to 100°C to 250°C inclusive in a state of being in contact with the solid in the specific reaction water.

Description

Method for decomposing polyols or polyol esters

[0001] The present invention relates to a method for decomposing polyols or polyol esters.

[0002] To reduce the consumption of natural resources and lessen the environmental burden, organic matter contained in waste is being reused as energy resources and chemical raw materials. For example, Patent Document 1 describes a method for producing terephthalic acid and ethylene glycol by hydrolyzing polyesters, polyamides, and polycarbonates contained in waste using water as a medium under conditions of 200°C to 300°C and 15 atmospheres or more.

[0003] Furthermore, biomass (renewable organic resources of biological origin excluding fossil resources), including leftover food, beer residue, sawdust, livestock manure, used clothing, and waste paper, is utilized as fuel, animal feed, and compost, and is also sometimes used in the production of sugars. For example, Patent Document 2 describes a method for producing polysaccharides by repeatedly performing a heat treatment in the presence of a dilute alkali and a cellulase on the extraction residue of coffee beans.

[0004] U.S. Patent No. 4,605,762; Japanese Patent Publication No. 2007-217466; Japanese Patent Publication No. 2015-157792

[0005] Duncan, SM; Alkasrawi, M.; Gurram, R.; Almomani, F.; Wiberley-Bradford, AE; Singsaas, E. Paper Mill Sludge as a Source of Sugars for Use in the Production of Bioethanol and Isoprene. Energies 2020, 13, 4662.Meadows S, Hosur M, Celikbag Y, Jeelani S. Comparative Analysis on the Epoxidation of Soybean Oil using Formic and Acetic Acids. Polymers and Polymer Composites. 2018;26(4):289-298.Ismail, Dandi N. and Nazlee Faisal Ghazali. “SEPARATION OF FATTY ACIDS FROM PALM OIL USING ORGANIC SOLVENT NANOFILTRATION.” Malaysian Journal of Analytical Science (2018): n. pag.MS Sinaga et al 2017 IOP Conf. Ser.: Mater. Sci. Eng. 180 012125Mohammad, S.; Baidurah, S.; Kobayashi, T.; Ismail, N.; Leh, CP Palm Oil Mill Effluent Treatment Processes - A Review. Processes 2021, 9, 739.

[0006] The method described in Patent Document 1 requires a powerful heat source to raise the water temperature to a high temperature of 200°C to 300°C. Patent Document 1 describes introducing high-pressure steam from an external source into the reactor as the main heat source, but attempting to secure such a powerful heat source may actually increase the environmental burden. The method in Patent Document 2 requires repeated dilute alkali treatment and enzyme treatment, and the process is unbearably cumbersome.

[0007] The organic matter contained in waste is diverse, but in many cases it is classified as polyol or polyol ester. Because polyols and polyol esters remaining in waste have a chemical structure that makes them difficult to biodegrade, their decomposition reactions by enzymes and microorganisms are unstable and slow.

[0008] The problem that this invention aims to solve is to provide a simpler method for decomposing polyols or polyol esters.

[0009] The present invention, developed to solve the above problems, is a method for decomposing polyols or polyol esters, comprising contacting a substance to be decomposed, which includes at least one of a polyol and a polyol ester, with a solid metal oxide or metal hydroxide having a different standard oxidation-reduction potential from water in a predetermined reaction water, wherein the substance to be decomposed is heated to a temperature of 100°C or higher and 250°C or lower while in contact with the solid in the predetermined reaction water.

[0010] In this specification, "polyol" means a compound having two or more hydroxyl groups in its molecule, and "polyol ester" means a compound obtained by esterifying a polyol.

[0011] Examples of metal oxides and metal hydroxides with a standard oxidation-reduction potential different from that of water include alumina (Al2O3), silica (SiO2), zeolite (Al2O3·SiO2), titania (TiO2), vanadium pentoxide (V2O5), manganese dioxide (MnO2), iron hydroxide (FeO(OH)), zinc oxide (ZnO), germanium oxide (GeO2), tin oxide (SnO2), lead oxide (PbO2), nickel oxide (NiO2, Ni3O4), nickel hydroxide (Ni(OH)3), and mixtures of two or more of these. Of course, other metal oxides and metal hydroxides with a standard oxidation-reduction potential different from that of water can also be used.

[0012] In the method for decomposing polyols or polyol esters according to the present invention, in order to increase the rate of the hydrolysis reaction described later, the substance to be decomposed is heated to 100°C or higher and 250°C or lower while in contact with a solid metal oxide or metal hydroxide in a predetermined reaction water.

[0013] The solid metal oxides and metal hydroxides can be in any shape as long as their surface can come into contact with the substance to be decomposed (polyol or polyol ester), but it is preferable that they be in granular or powder form to increase the contact area with the substance to be decomposed and thereby increase the rate of the hydrolysis reaction described later. Similarly, the substance to be decomposed can be in any shape, but it is preferable that it be in the form of small pieces (chips) to increase the contact area with the solid metal oxides and metal hydroxides and thereby increase the rate of the hydrolysis reaction described later.

[0014] The reaction water is typically pure water (1 MΩ·cm or higher) or ultrapure water (18.2 MΩ·cm or higher), but it can also be industrial purified water (typically 10 kΩ·cm or higher) or industrial wastewater (typically 10 kΩ·cm or lower). Furthermore, the reaction water is typically neutral (pH=6-8), but it may contain acids (sulfuric acid, phosphoric acid, carbonic acid, etc.), alkalis or salts (sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, sodium bicarbonate, etc.), or water-soluble oxides (calcium hypochlorite, sodium percarbonate, hydrogen peroxide, etc.) that have been conventionally used to hydrolyze polymer compounds.

[0015] In this invention, a substance to be decomposed, which includes at least one of a polyol and a polyol ester, can be decomposed by bringing it into contact with a solid metal oxide or metal hydroxide having a different standard oxidation-reduction potential from water in a predetermined reaction water, and then heating it to a temperature of 100°C or higher and 250°C or lower.

[0016] The mechanism by which such reactions occur is not yet fully understood, and is thought to differ depending on the type of metal oxide and metal hydroxide, but it is presumed to be due to the difference in standard redox potential. Generally, reducers in systems with a lower standard redox potential tend to release electrons, while oxidizers in systems with a higher standard redox potential tend to accept electrons. Therefore, on the surface of a solid metal oxide or the aforementioned metal hydroxide, which has a higher standard redox potential than water, water molecules (H2O) are spontaneously oxidized to protons (H2O). + ) and electrons (e - It is presumed that hydroxyl (OH) and oxygen (O2) are generated, and the solid surface (solid-liquid interface) of the metal oxide or metal hydroxide becomes a strongly acidic environment. Furthermore, on the solid surface of the metal oxide or metal hydroxide, which has a lower standard oxidation-reduction potential than water, water molecules (H2O) are spontaneously reduced to hydrogen (H2) and hydroxide ions (OH). - It is presumed that this will occur, and the solid surface (solid-liquid interface) of the metal oxide or metal hydroxide will become a strongly alkaline environment.

[0017] However, since a strongly acidic or alkaline environment occurs only near the solid-liquid interface, and the entire water (bulk) is not considered to be in an acidic or alkaline environment, in this invention, a substance to be decomposed, containing at least one of a polyol and a polyol ester, is brought into contact with the surface of a solid metal oxide or metal hydroxide in a predetermined reaction water, and heated to 100°C or higher and 250°C or lower. This effectively hydrolyzes the substance to be decomposed.

[0018] As described above, according to the method for decomposing polyols or polyol esters of the present invention, a substance to be decomposed, which includes at least one of a polyol and a polyol ester, can be brought into contact with water and a solid metal oxide or metal hydroxide having a different standard oxidation-reduction potential in a predetermined reaction water, and heated to 100°C or higher and 250°C or lower, thereby more easily decomposing the polyol or polyol ester.

[0019] A diagram showing polyols and polyol esters. A schematic diagram showing the hydrolysis reaction according to the embodiment. Chromatogram of the components contained in the filtrate obtained in Experiment 21. Chromatogram of the components contained in the filtrate obtained in Experiment 22. Chromatogram of the components contained in the filtrate obtained in Experiment 26. Chromatogram of the components contained in the filtrate obtained in Comparative Experiment 1. Chromatogram of the components contained in the filtrate obtained in Experiment 33. Chromatogram of the components contained in the filtrate obtained in Experiment 34. Chromatogram of the components contained in the filtrate obtained in Experiment 35. Chromatogram of the components contained in the filtrate obtained in Experiment 41. Chromatogram of the components contained in water as the filtrate obtained in Experiment 42. Chromatogram of the components contained in the hexane extract obtained in Experiment 42. Chromatogram of the components contained in the filtrate obtained in Experiment 47. Chromatogram of the components contained in the filtrate obtained in Experiment 48. Chromatogram of the components contained in the filtrate obtained in Experiment 49. Chromatogram of the components contained in the filtrate obtained in Experiment 50. XRD spectrum of the substance adhering to the surface of lead oxide remaining on the filter. XRD spectrum of commercially available disodium terephthalate. XRD spectrum of lead oxide powder remaining on the filter. XRD spectrum of unused lead oxide powder. SEM image of unused lead oxide. Chromatogram of the components contained in the filtrate obtained in Experiment 51 when the reaction time was 1 hour. Chromatogram of the components contained in the filtrate obtained in Experiment 51 when the reaction time was 3 hours. Chromatogram of the components contained in the filtrate obtained in Experiment 51 when the reaction time was 6 hours. Chromatogram of the components contained in the filtrate obtained in Comparative Experiment 2. XRD spectrum of the substance adhering to the surface of lead oxide remaining on the filter. XRD spectrum of commercially available disodium terephthalate.

[0020] An exemplary embodiment of the decomposition method for polyols or polyol esters according to the present invention will be described. In this embodiment, a substance to be decomposed, which includes at least one of a polyol and a polyol ester, and a solid metal oxide or metal hydroxide having a different standard oxidation-reduction potential from water are placed in a reaction vessel containing water and brought into contact with each other, and heated to a temperature of 100°C or higher and 250°C or lower.

[0021] The substance to be decomposed in this embodiment is any polyol or polyol ester as shown in Figure 1, such as glucose, starch, cellulose, galactose, mannose, arabinose, fructose, sucrose, maltose, lactose, cellobiose, pectin, lignin, xylan, xylose, glycerol, triacetin, glycerides (glycerides, acylglycerols, vegetable oils, edible oils, lubricating oils for machinery, etc.), polyvinyl alcohol, polyester, ethylene glycol, and mixtures of two or more of these. The reaction water used in this embodiment is typically pure water (1 MΩ·cm or higher) to ultrapure water (18.2 MΩ·cm or higher), but industrial purified water (typically 10 kΩ·cm or higher) or industrial wastewater (typically 10 kΩ·cm or lower) can also be used. Furthermore, although the reaction water used in this embodiment is typically neutral (pH=6~8), it may also contain acids (sulfuric acid, phosphoric acid, carbonic acid, etc.), alkalis and salts (sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, sodium bicarbonate, etc.), and water-soluble oxides (calcium hypochlorite, sodium percarbonate, etc.) that have been conventionally used to hydrolyze polymer compounds. Examples of metal oxides and metal hydroxides used in this embodiment that have a different standard oxidation-reduction potential from water include alumina (Al2O3), silica (SiO2), zeolite (Al2O3・SiO2), titania (TiO2), vanadium pentoxide (V2O5), manganese dioxide (MnO2), iron hydroxide (FeO(OH)), zinc oxide (ZnO), germanium oxide (GeO2), tin oxide (SnO2), lead oxide (PbO2), nickel oxide (NiO2, Ni3O4), nickel hydroxide (Ni(OH)3), and mixtures of two or more of these. Of course, metal oxides and metal hydroxides other than those mentioned above, which have a different standard oxidation-reduction potential from water, can also be used. The decomposition method according to this embodiment can be carried out by arbitrarily combining the substances to be decomposed, reaction water, metal oxides, and metal hydroxides exemplified above.

[0022] In the decomposition method for polyols or polyol esters according to this embodiment, in order to increase the rate of the hydrolysis reaction, the substance to be decomposed is heated to 100°C or higher while in contact with a solid metal oxide or metal hydroxide in a predetermined reaction water. In particular, when monosaccharides, which are typical polyols, are heated to 100°C or higher, they can undergo exothermic decomposition on their own, and the rate of the decomposition reaction can increase dramatically.

[0023] The solid metal oxides and metal hydroxides can be in any shape as long as their surface can come into contact with the substance to be decomposed (polyol or polyol ester), but it is preferable that they be granular or powdered in order to increase the contact area with the substance to be decomposed and thereby increase the rate of the hydrolysis reaction. The substance to be decomposed can also be in any shape, but it is preferable that it be in the form of small pieces (chips) in order to increase the contact area with the solid metal oxides and metal hydroxides and thereby increase the rate of the hydrolysis reaction. In the decomposition method according to this embodiment, either the substance to be decomposed or the solid metal oxides and metal hydroxides may be in the above shapes, or both may be in the above shapes.

[0024] The reaction vessel used in this embodiment can be a known type, and it is preferable that it be a sealed vessel. The inside of the reaction vessel may be an air atmosphere or a gas atmosphere. In this embodiment, as a heating method, for example, an electric heater, a heat transfer medium such as steam or oil, or microwaves can be used.

[0025] In this embodiment, the reaction of water (H2O) in the reaction vessel and the standard oxidation-reduction potential (E o The details are as follows (1) and (2). Furthermore, as examples of the reactions and standard redox potentials of solid metal oxides or metal hydroxides used in this embodiment, the reactions and standard redox potentials of lead oxide, nickel oxide, and nickel hydroxide are shown in (3) to (6) below.

[0026] (1) 2H2O (liquid) ⇔ 4H + + 4e - + O2E o = 1.229V (2) 2H2O (liquid) + 2e - ⇔ H2 + 2OH- E o = -0.83V (3) PbO2 (solid) + 4H + + 2e - ⇔ Pb 2+ + 2H2O E o = 1.468V (4) NiO2 (solid) + 4H + + 2e - ⇔ Ni 2+ + 2H2O E o = 1.68V (5) Ni3O4 (solid) + 8H + + 2e - ⇔ 3Ni 2+ + 4H2O E o = 1.977V (6) Ni(OH)3 (solid) + 3H + + e - ⇔ Ni 2+ + 3H2O E o = 2.08V In the reaction formulas shown in the above (1) to (6), the bidirectional arrow symbol (⇔) represents equilibrium.

[0027] When two or more chemical equilibria consisting of the above (1) and any one or more of (3) to (6) exist simultaneously, the reductant in the system with a smaller standard oxidation-reduction potential is more likely to release electrons, and the oxidant in the system with a larger standard oxidation-reduction potential is more likely to accept electrons. Therefore, on the surface of solids of metal oxides and metal hydroxides, whose standard oxidation-reduction potential is higher than that of water, the reaction of the above (1) proceeds spontaneously to the right, and the solid surface (solid-liquid interface) of the metal oxide or the metal hydroxide is considered to become a strong acidic environment. In that state, as shown in Fig. 2, the substance to be decomposed containing at least one of polyol and polyol ester in contact with the surface of the solid of the metal oxide or metal hydroxide is hydrolyzed, and industrially useful chemical components such as combustible gas, alcohol, and organic acid can be easily obtained.

[0028] The same applies to metal oxides and metal hydroxides other than those shown in (3) to (6) above, which have a standard oxidation-reduction potential higher than that of water. Also, on the surface of solids of metal oxides and metal hydroxides having a standard oxidation-reduction potential lower than that of water, the reaction in (2) above spontaneously proceeds to the right, and it is considered that the solid surface (solid-liquid interface) of the metal oxide or the metal hydroxide becomes a strong alkaline environment.

[0029] The measured value of the standard oxidation-reduction potential may vary depending on the measurement method. In the present embodiment, the value of the standard oxidation-reduction potential may be measured by any known measurement method. Based on the values in (1) and (2) above, the embodiments of the present invention include cases where the standard oxidation-reduction potential of the metal oxide or metal hydroxide is less than -0.83 V and cases where it is greater than 1.229 V.

[0030] The upper limit of the heating temperature is 375°C, which is the critical point of water, but in the present embodiment, it is carried out at 100°C to 250°C. In the method described in Patent Document 1, by introducing high-pressure steam from the outside into the reactor, the temperature of water is raised to a high temperature of 200°C to 300°C. Therefore, a powerful heat source is required. However, the method for decomposing the polyol or polyol ester according to the present embodiment can be carried out at a lower temperature and with a simpler apparatus by utilizing the hydrothermal method, so the environmental load related to ensuring the heat source can be small.

[0031] Also, when decomposing polyols or polyol esters using water as a medium with metal oxides such as PbO2, etc., since the reaction becomes an exothermic mechanism, even if the temperature control is set to 200°C, the temperature of the reactor may naturally rise to 250°C or higher. It is desirable for safety to set the design specifications of the reactor to a temperature resistance of 300°C and a pressure resistance of 8.6 MPa (saturated water vapor pressure at 300°C).

[0032] Hereinafter, as examples of the method for decomposing a polyol or a polyol ester according to the present embodiment, the results of experiments for confirming the effects of the method for decomposing a polyol or a polyol ester according to the present embodiment will be described in plurality. The types and amounts of substances generated in each experiment were measured using various devices. That is, the concentration of hydrogen (H2) gas was measured with XP-3340(2) manufactured by Shin Cosmos Electric Co., Ltd. (the number in parentheses is a Roman numeral), the Kitagawa type gas detector tube manufactured by GASTEC, etc., and the concentration of carbon monoxide (CO) gas was measured with the Kitagawa type gas detector tube manufactured by GASTEC, etc., and the concentration of methane (CH4) gas was measured with GX-6000 manufactured by Riken Keiki Co., Ltd., etc. Regarding the concentrations of water-soluble components such as lower alcohols, acetones, aldehydes, and organic acids, the components contained in the filtrate obtained by removing metal oxides or metal hydroxides by suction filtration using a filter manufactured by Merck Millipore (pore size 0.025 μm, diameter 47 mm) were measured simultaneously with a standard substance using a gas chromatograph mass spectrometer (GC-MS) GCMS-QP2010Ultra manufactured by Shimadzu Corporation for quantification. Regarding water-insoluble components such as higher alcohols and light oil attached to the metal oxides or metal hydroxides, the metal oxides or metal hydroxides after the above suction filtration were dried at 80 ° C and then extracted with hexane, and the hexane solution in which the water-insoluble components were dissolved was measured simultaneously with a standard substance using the above GC-MS for quantification.

[0033] In all measurements, the measurement conditions for the gas chromatograph (GC) section and the mass spectrometry (MS) section in GC-MS were as follows. (1) GC section Carrier gas: Helium (He) (linear velocity is 40 cm / sec, split ratio is 50) Column: DB-WAX UI manufactured by Agilent Technologies, Inc. (30 m, diameter 0.25 mm, film thickness 0.25 μm) Injection temperature: 220 ° C Column temperature: 50 ° C - 200 ° C (10 ° C / min) (2) MS section Interface temperature: 220 ° C Ion source temperature: 200 ° C Measurement mode: Scan mode (mass-to-charge ratio is 25 - 300)

[0034] [Experiment 1] In Experiment 1, 1.0348 g (0.0057 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 9.07 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, the glucose concentration was 0.115 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour while stirring at a rotation speed of 200 rpm. As a result, from the gas phase, 0.00233 mol (40.5 mol%) of hydrogen and 0.00004 mol (0.7 mol%) of carbon monoxide were obtained. From the liquid phase, aqueous solutions of acetic acid were obtained as follows: 0.15 mol / L (130 mol%) (where mol% is the ratio of the amount of product (acetic acid) to the amount of starting material (glucose). The same applies hereafter in this specification.), 0.012 mol / L (10.1 mol%) of formic acid, 0.0041 mol / L (3.6 mol%) of ethylene glycol, 0.0025 mol / L (2.16 mol%) of diethylene glycol, and trace amounts of acetone, methanol, and ethanol were obtained.

[0035] [Experiment 2] In Experiment 2, 2.08 g (0.012 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 4 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, the glucose concentration was 0.23 mol / L. In this state, the decomposition reaction was carried out at 250 °C for 1 hour while stirring at a rotation speed of 400 rpm. As a result, from the gas phase, 0.0058 mol (50.4 mol%) of hydrogen and 0.0005 mol (0.4 mol%) of carbon monoxide were obtained. From the liquid phase, aqueous solutions of acetone (0.0083 mol / L, 3.6 mol%), methanol (0.0019 mol / L, 0.87 mol%), ethanol (0.0026 mol / L, 1.1 mol%), acetic acid (0.016 mol / L, 6.7 mol%), formic acid (0.0020 mol / L, 0.88 mol%), ethylene glycol (0.0018 mol / L, 0.77 mol%), and diethylene glycol (0.00033 mol / L, 0.14 mol%) were obtained.

[0036] [Experiment 3] In Experiment 3, 1.0364 g (0.0058 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 9.13 g of tin oxide (SnO2, manufactured by Fujifilm Wako Pure Chemical Industries Ltd.), and 50 mL of industrial purified water were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure Glass Industry Co., Ltd., with a capacity of 128 mL) and sealed. At this point, the glucose concentration was 0.115 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour while stirring at a rotational speed of 200 rpm. As a result, from the gas phase, 0.000404 mol (7.02 mol%) of hydrogen and 0.00000505 mol (0.088 mol%) of carbon monoxide were detected. From the liquid phase, as aqueous solutions, 0.039 mol / L (33.7 mol%) of acetic acid, 0.00183 mol / L (1.59 mol%) of formic acid, 0.00147 mol / L (1.27 mol%) of ethylene glycol, 0.013 mol / L (1.1 mol%) of acetone, and 0.00023 m³ of 1-propanol were detected. The following concentrations were obtained: 0.0087 mol / L (0.2 mol%) of 2-propanol, 0.001 mol / L (0.9 mol%) of acetoin, 0.009 mol / L (7.8 mol%) of hydroxyacetone, 0.0001 mol / L (0.09 mol%) of levulinic acid, 0.00029 mol / L (0.025 mol%) of furfural, and 0.00081 mol / L (0.07 mol%) of 5-hydroxymethylfurfural.

[0037] [Experiment 4] In Experiment 4, 1.0603 g (0.0059 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 9.07 g of germanium oxide (GeO2, manufactured by Nacalai Tesque Co., Ltd.), and 50 mL of industrial purified water were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure Glass Industry Co., Ltd., with a capacity of 128 mL) and sealed. At this point, the glucose concentration was 0.118 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour while stirring at a rotational speed of 200 rpm. As a result, from the gas phase, 0.0000504 mol (0.856 mol%) of hydrogen and 0.00000403 mol (0.068 mol%) of carbon monoxide were found. From the liquid phase, as aqueous solutions, 0.0014 mol / L (1.2 mol%) of methanol, 0.0025 mol / L (2.1 mol%) of ethanol, 0.012 mol / L (10.3 mol%) of acetic acid, 0.00713 mol / L (6.03 mol%) of formic acid, and 0.0014 mol of ethylene glycol were found. The following concentrations were obtained: 1.2 mol / L of acetone, 0.0021 mol / L (1.8 mol%) of 1-propanol, 0.00022 mol / L (0.18 mol%) of 2-propanol, 0.0035 mol / L (3 mol%) of hydroxyacetone, 0.00057 mol / L (0.49 mol%) of furfural, 0.00082 mol / L (0.7 mol%) of furfural, and 0.0002 mol / L (0.17 mol%) of 5-hydroxymethylfurfural.

[0038] [Experiment 5] In Experiment 5, 1.0800 g (0.006 mol) of glucose (180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 9.04 g of silicon oxide (SiO2, manufactured by Fujifilm Wako Pure Chemical Industries Ltd.), and 50 mL of industrial purified water were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure Glass Industry Co., Ltd., with a capacity of 128 mL) and sealed. At this point, the glucose concentration was 0.12 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour while stirring at a rotation speed of 200 rpm. As a result, 0.000032 mol (0.54 mol%) of carbon monoxide was obtained from the gas phase, and from the liquid phase, 0.0014 mol / L (1.2 mol%) of methanol, 0.0014 mol / L (1.2 mol%), 0.0014 mol / L (1.2 mol%) of ethanol, 0.011 mol / L (9.5 mol%) of acetic acid, 0.011 mol / L (9.5 mol%) of formic acid, 0.00068 mol / L (0.56 mol%) of ethylene glycol, 0.0016 mol / L (1.3 mol%) of acetone, 0.00027 mol / L (0.23 mol%) of acetoin, 0.0015 mol / L (1.2 mol%) of hydroxyacetone, 0.0017 mol / L (1.4 mol%) of furfural, and 0.0005 mol / L (0.4 mol%) of 5-hydroxymethylfurfural were obtained as aqueous solutions.

[0039] [Experiment 6] In Experiment 6, 1.0127 g (0.006 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 9.03 g of alumina (Al2O3, manufactured by Mizusawa Chemical Industries, Ltd.), and 50 mL of industrial purified water were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure Glass Industry Co., Ltd., with a capacity of 128 mL) and sealed. At this point, the glucose concentration was 0.11 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour while stirring at a rotational speed of 200 rpm. As a result, 0.000015 mol (0.26 mol%) of carbon monoxide was obtained from the gas phase, and from the liquid phase, aqueous solutions of acetic acid (0.0076 mol / L, 6.6 mol%), formic acid (0.0026 mol / L, 2.4 mol%), ethylene glycol (0.0000895 mol / L, 0.0785 mol%), acetoin (0.00096 mol / L, 0.85 mol%), hydroxyacetone (0.0097 mol / L, 8.5 mol%), furfural (0.00025 mol / L, 0.2 mol%), and 5-hydroxymethylfurfural (0.0005 mol / L, 0.4 mol%) were obtained. Additionally, dihydroxyacetone, 2-hydroxy-γ-butyrolactone, and levulinic acid were obtained as components of GCMS chromatographic peaks, although their concentrations were not yet determined.

[0040] [Experiment 7] In Experiment 7, 1.0442 g (0.0058 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 9.04 g of anatase-type titanium dioxide (TiO2, manufactured by Tokyo Chemical Industry Co., Ltd.), and 50 mL of industrially purified water were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure Glass Industry Co., Ltd., with a capacity of 128 mL) and sealed. At this point, the glucose concentration was 0.12 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour while stirring at a rotational speed of 200 rpm. As a result, from the gas phase, 0.00040 mol (7 mol%) of hydrogen and 0.000013 mol (0.22 mol%) of carbon monoxide were obtained, and from the liquid phase, as aqueous solutions, 0.0011 mol / L (0.97 mol%) of methanol, 0.00094 mol / L (0.81 mol%) of acetic acid, 0.011 mol / L (9.4 mol%) of formic acid, 0.000036 mol / L (0.031 mol%) of acetoin, 0.00032 mol / L (0.28 mol%) of hydroxyacetone, 0.00043 mol / L (0.37 mol%) of furfural, and 0.00023 mol / L (0.2 mol%) of 5-hydroxymethylfurfural were obtained.

[0041] [Experiment 8] In Experiment 8, 1.0065 g (0.0056 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 9.02 g of rutile titanium dioxide (TiO2, manufactured by Fujifilm Wako Pure Chemical Industries Ltd.), and 50 mL of industrial purified water were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure Glass Industry Co., Ltd., with a capacity of 128 mL) and sealed. At this point, the glucose concentration was 0.11 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour while stirring at a rotational speed of 200 rpm. As a result, 0.00005 mol (0.9 mol%) of carbon monoxide was obtained from the gas phase, and from the liquid phase, aqueous solutions of methanol 0.0011 mol / L (0.98 mol%), acetic acid 0.0042 mol / L (3.8 mol%), formic acid 0.00043 mol / L (0.39 mol%), ethylene glycol 0.000031 mol / L (0.028 mol%), acetoin 0.00017 mol / L (0.15 mol%), hydroxyacetone 0.0020 mol / L (1.8 mol%), levulinic acid 0.001 mol / L (0.9 mol%), furfural 0.001 mol / L (0.9 mol%), and 5-hydroxymethylfurfural 0.000058 mol / L (0.052 mol%) were obtained.

[0042] [Experiment 9] In Experiment 9, 1 g (0.0056 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 8 g of vanadium pentoxide (V2O5, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (NR0218, manufactured by Flon Chemical Co., Ltd., capacity 100 mL) and sealed. At this point, the glucose concentration was 0.11 mol / L. In this state, the decomposition reaction was carried out at 200°C for 2 hours while stirring at a rotation speed of 200 rpm. As a result, 0.00082 mol (14.8 mol%) of hydrogen and 0.0003 mol (5 mol%) of carbon monoxide were obtained from the gas phase, and 0.03 mol / L (26.6 mol%) of acetic acid, 0.011 mol / L (10 mol%) of formic acid, 0.00037 mol / L (0.34 mol%) of ethylene glycol, and 0.00076 mol / L (0.69 mol%) of diethylene glycol were obtained from the liquid phase as aqueous solutions.

[0043] [Experiment 10] In Experiment 10, 1 g (0.0056 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 8 g of vanadium pentoxide (V2O5, manufactured by Kanto Chemical Co., Ltd.), 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation), and 100 μL of 1 mol / L sulfuric acid were placed in a pressure-resistant container (NR0218, manufactured by Flon Chemical Co., Ltd., capacity 100 mL) and sealed. At this point, the glucose concentration was 0.11 mol / L and the pH was approximately 2. Under these conditions, the decomposition reaction was carried out at 200°C for 2 hours while stirring at a rotational speed of 200 rpm. As a result, 0.00082 mol (14.8 mol%) of hydrogen and 0.00041 mol (7.4 mol%) of carbon monoxide were obtained from the gas phase, and 0.0024 mol / L (2.1 mol%) of methanol, 0.0027 mol / L (2.4 mol%) of acetic acid, 0.0031 mol / L (2.8 mol%) of formic acid, and 0.0014 mol / L (1.3 mol%) of ethylene glycol were obtained as aqueous solutions from the liquid phase.

[0044] [Experiment 11] In Experiment 11, 1 g (0.0056 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 8 g of vanadium pentoxide (V2O5, manufactured by Kanto Chemical Co., Ltd.), 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation), and 100 μL of 1 mol / L sodium hydroxide were placed in a pressure-resistant container (NR0218, manufactured by Flon Chemical Co., Ltd., capacity 100 mL) and sealed. At this point, the glucose concentration was 0.11 mol / L and the pH was approximately 12. Under these conditions, the decomposition reaction was carried out at 200°C for 2 hours while stirring at a rotation speed of 200 rpm. As a result, 0.00029 mol (5.2 mol%) of hydrogen and 0.00017 mol (3.1 mol%) of carbon monoxide were obtained from the gas phase, and 0.0016 mol / L (1.4 mol%) of methanol, 0.053 mol / L (48 mol%) of acetic acid, and 0.13 mol / L (119 mol%) of formic acid were obtained as aqueous solutions from the liquid phase.

[0045] [Experiment 12] 1 g (0.0056 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 8 g of manganese dioxide (MnO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (NR0218, manufactured by Flon Chemical Co., Ltd., capacity 100 mL) and sealed. At this point, the glucose concentration was 0.11 mol / L. In this state, the decomposition reaction was carried out at 200°C for 2 hours while stirring at a rotation speed of 200 rpm. As a result, 0.00040 mol (7.2 mol%) of hydrogen and 0.00013 mol (2.4 mol%) of carbon monoxide were obtained from the gas phase, and 0.0012 mol / L (1.1 mol%) of acetone, 0.0013 mol / L (1.2 mol%) of methanol, 0.020 mol / L (18.4 mol%) of ethanol, and 0.022 mol / L (20.2 mol%) of acetic acid were obtained as aqueous solutions from the liquid phase.

[0046] [Experiment 13] In Experiment 13, 1 g (0.0056 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 8 g of manganese dioxide (MnO2, manufactured by Kanto Chemical Co., Ltd.), 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation), and 100 μL of 1 mol / L sulfuric acid were placed in a pressure-resistant container (NR0218, manufactured by Flon Chemical Co., Ltd., capacity 100 mL) and sealed. At this point, the glucose concentration was 0.11 mol / L and the pH was approximately 2. Under these conditions, the decomposition reaction was carried out at 200°C for 2 hours while stirring at a rotation speed of 200 rpm. As a result, 0.00082 mol (14.8 mol%) of hydrogen and 0.00033 mol (6 mol%) of carbon monoxide were obtained from the gas phase, and 0.0058 mol / L (5.3 mol%) of methanol, 0.011 mol / L (10.1 mol%) of acetic acid, and 0.0035 mol / L (3.1 mol%) of formic acid were obtained as aqueous solutions from the liquid phase.

[0047] [Experiment 14] In Experiment 14, 1 g (0.0056 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 8 g of manganese dioxide (MnO2, manufactured by Kanto Chemical Co., Ltd.), 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation), and 100 μL of 1 mol / L sodium hydroxide were placed in a pressure-resistant container (NR0218, manufactured by Flon Chemical Co., Ltd., capacity 100 mL) and sealed. At this point, the glucose concentration was 0.11 mol / L and the pH was approximately 12. Under these conditions, the decomposition reaction was carried out at 200°C for 2 hours while stirring at a rotation speed of 200 rpm. As a result, 0.00029 mol (5.2 mol%) of hydrogen and 0.00017 mol (3.1 mol%) of carbon monoxide were obtained from the gas phase, and 0.0044 mol / L (3.9 mol%) of methanol, 0.011 mol / L (10.1 mol%) of acetic acid, and 0.0065 mol / L (5.9 mol%) of formic acid were obtained as aqueous solutions from the liquid phase.

[0048] [Experiment 15] In Experiment 15, 1.0318 g (0.0057 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 9.0212 g of α-iron hydroxide (FeO(OH)), manufactured by Kojun Chemical Laboratory Co., Ltd., and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., capacity 100 mL) and sealed. At this point, the glucose concentration was 0.11 mol / L. In this state, the decomposition reaction was carried out at 200°C for 4 hours while stirring at a rotation speed of 200 rpm. As a result, 0.000025 mol (0.44 mol%) of hydrogen, 0.0000051 mol (0.089 mol%) of carbon monoxide, and 0.0000051 mol (0.089 mol%) of methane were obtained from the gas phase. From the liquid phase, aqueous solutions of acetone (0.0033 mol / L, 2.9 mol%), methanol (0.0035 mol / L, 3.0 mol%), ethanol (0.0026 mol / L, 2.3 mol%), acetic acid (0.0078 mol / L, 6.8 mol%), formic acid (0.0069 mol / L, 6.0 mol%), and ethylene glycol (0.00052 mol / L, 0.46 mol%) were obtained. Simultaneously, hydroxyacetone, 2-methyl-2-cyclopentene, and propionic acid were also prominently detected as chromatographic peaks by GC-MS.

[0049] [Experiment 16] In Experiment 16, 1.0040 g (0.0056 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 9.0212 g of zinc oxide (ZnO, manufactured by Kojun Chemical Laboratory Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., capacity 100 mL) and sealed. At this point, the glucose concentration was 0.11 mol / L. In this state, the decomposition reaction was carried out at 200°C for 2 hours while stirring at a rotation speed of 200 rpm. As a result, 0.00075 mol (13.5 mol%) of hydrogen and 0.000015 mol (0.27 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0026 mol / L, 2.4 mol%), methanol (0.0018 mol / L, 1.6 mol%), acetic acid (0.011 mol / L, 10.0 mol%), formic acid (0.0059 mol / L, 5.3 mol%), and ethylene glycol (0.002 mol / L, 1.8 mol%) were obtained. Simultaneously, hydroxyacetone and acetoin were also prominently detected as chromatographic peaks by GCMS.

[0050] [Experiment 17] In Experiment 17, 1.07 g (0.0059 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 5 g of zeolite (TOSOH HZSM-5, manufactured by Tosoh Corporation, Si / Al2 = 21.6), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, the glucose concentration was 0.12 mol / L. In this state, the decomposition reaction was carried out at 200°C for 2 hours while stirring at a rotation speed of 200 rpm. As a result, 0.0010 mol (16.9 mol%) of hydrogen and 0.00040 mol (6.8 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0016 mol / L, 1.3 mol%), methanol (0.0016 mol / L, 1.4 mol%), ethanol (0.0017 mol / L, 1.4 mol%), acetic acid (0.076 mol / L, 6.4 mol%), formic acid (0.043 mol / L, 36.4 mol%), ethylene glycol (0.0025 mol / L, 2.1 mol%), and diethylene glycol (0.0016 mol / L, 1.3 mol%) were obtained.

[0051] [Experiment 18] In Experiment 18, 2.01 g (0.011 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 4.03 g of low silicon oxide zeolite (TOSOH HZSM-5, manufactured by Tosoh Corporation, Si / Al2 = 21.6), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, the glucose concentration was 0.22 mol / L. In this state, the decomposition reaction was carried out at 250 °C for 1 hour while stirring at a rotation speed of 400 rpm. As a result, 0.0010 mol (9 mol%) of hydrogen and 0.0030 mol (27 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0031 mol / L, 1.4 mol%), methanol (0.0019 mol / L, 0.86 mol%), ethanol (0.0019 mol / L, 0.86 mol%), acetic acid (0.013 mol / L, 5.9 mol%), formic acid (0.0061 mol / L, 2.7 mol%), ethylene glycol (0.0016 mol / L, 0.72 mol%), and diethylene glycol (0.00032 mol / L, 0.15 mol%) were obtained.

[0052] [Experiment 19] In Experiment 19, 2 g (0.011 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 4.07 g of high silicon oxide zeolite (HighSiZSM-5, Si / Al2 = 148.2, provided by Nishiyama Laboratory, Department of Chemical Engineering, Graduate School of Engineering Science, Osaka University), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, the glucose concentration was 0.22 mol / L. In this state, the decomposition reaction was carried out at 250°C for 1 hour while stirring at a rotation speed of 400 rpm. As a result, 0.0017 mol (15.4 mol%) of hydrogen and 0.00040 mol (3.6 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0030 mol / L, 1.4 mol%), methanol (0.0018 mol / L, 0.81 mol%), ethanol (0.0020 mol / L, 0.91 mol%), acetic acid (0.013 mol / L, 5.9 mol%), formic acid (0.0032 mol / L, 1.4 mol%), ethylene glycol (0.0017 mol / L, 0.75 mol%), and diethylene glycol (0.00032 mol / L, 0.15 mol%) were obtained.

[0053] [Experiment 20] In Experiment 20, 2.01 g (0.011 mol) of glucose (approximately 180 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 1.04 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), 4.06 g of zeolite (HighSiZSM-5, Si / Al2 = 148.2, provided by Nishiyama Laboratory, Department of Chemical Engineering, Graduate School of Engineering Science, Osaka University), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, the glucose concentration was 0.22 mol / L. In this state, the decomposition reaction was carried out at 250 °C for 1 hour while stirring at a rotation speed of 400 rpm. As a result, 0.0030 mol (27 mol%) of hydrogen and 0.000075 mol (0.67 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0027 mol / L, 1.2 mol%), methanol (0.0019 mol / L, 0.85 mol%), ethanol (0.0028 mol / L, 1.3 mol%), acetic acid (0.018 mol / L, 8.1 mol%), formic acid (0.0016 mol / L, 0.71 mol%), ethylene glycol (0.0018 mol / L, 0.79 mol%), and diethylene glycol (0.00033 mol / L, 0.15 mol%) were obtained.

[0054] The Si / Al2 ratio, which characterizes the zeolites used in experiments 17-20, represents the ratio of silicon to aluminum in terms of molar mass, and was calculated from data measured by X-ray fluorescence analysis (XRF).

[0055] Experiments 1-20 demonstrate that glucose can be decomposed using various metal oxides, easily yielding industrially useful chemical components such as flammable gases, alcohols, organic acids, ketones, aldehydes, lactones, and alkenes. Glucose is one of the most common organic compounds on Earth, and large quantities of waste and sludge containing glucose exist. Applying Experiments 1-20 could potentially lead to the construction of social infrastructure that efficiently converts and recycles this waste and sludge into energy resources and chemical raw materials.

[0056] Tables 1 to 4 summarize the substances to be decomposed, metal oxides or metal hydroxides, solvents, the presence or absence of acids or bases, and the types of products involved in experiments 1 to 20.

[0057] [Experiment 21] In Experiment 21, 3.1376 g (0.019 mol) of wheat-derived starch (approximately 162 g / mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 27.5035 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, the starch concentration was 0.387 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1.5 hours while stirring at a rotation speed of 300 rpm. As a result, 0.0086 mol (44.1 mol%) of hydrogen and 0.00020 mol (1.0 mol%) of carbon monoxide were obtained from the gas phase. Figure 3 is a chromatogram of the components contained in the filtrate obtained in Experiment 21. As shown in Figure 3, the following aqueous solutions were obtained from the liquid phase: acetone at 0.0086 mol / L (2.2 mol%), methanol at 0.015 mol / L (3.9 mol%), ethanol at 0.0050 mol / L (1.3 mol%), acetic acid at 0.07 mol / L (18.0 mol%), and formic acid at 0.089 mol / L (23.0 mol%).

[0058] [Experiment 22] In Experiment 22, 3.0419 g (0.019 mol) of insoluble dietary fiber cellulose (approximately 162 g / mol, manufactured by Healthy Company Co., Ltd.), 27.2588 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, the cellulose concentration was 0.376 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1.5 hours while stirring at a rotation speed of 400 rpm. As a result, 0.0016 mol (6.2 mol%) of hydrogen was obtained from the gas phase. Figure 4 is a chromatogram of the components contained in the filtrate obtained in Experiment 22. As shown in Figure 4, aqueous solutions of acetone (0.0028 mol / L, 0.75 mol%), methanol (0.027 mol / L, 7.2 mol%), ethanol (0.0035 mol / L, 0.94 mol%), acetic acid (0.046 mol / L, 12.1 mol%), and formic acid (0.069 mol / L, 18.5 mol%) were obtained from the liquid phase.

[0059] Experiments 21 and 22 show that lead oxide can decompose starch (α-1,4 linked glucose polymer) and cellulose (β-1,4 linked glucose polymer), easily obtaining industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones. The results of Experiments 21 and 22 indicate that because the standard redox potential of lead oxide is higher than that of water, water on its surface is spontaneously oxidized, producing protons (H). + ) and electrons (e - This is thought to be caused by the generation of nitrate and oxygen (O2), creating a strongly acidic environment. Therefore, the same results as in experiments 21 and 22 can be obtained when using metal oxides and metal hydroxides other than lead oxide that have a higher standard oxidation-reduction potential than water (the same applies to other examples).

[0060] It is well known that coffee beans are the second most traded commodity after petroleum, and coffee bean extraction residue is a globally generated waste. The main components of coffee bean extraction residue are galactomannan, a copolymer (= polysaccharide) of galactose (hexanosaccharide) and mannose (hexanosaccharide), and arabinogalactan, a polysaccharide composed of arabinose (pentanosaccharide) and galactose (hexanosaccharide). Cellulose (β1,4 linked glucose polymer) is also present (see Patent Document 2). In the following experiments 23 to 26, galactose, mannose, and arabinose, which are monosaccharides similar to glucose, and the coffee bean extraction residue were each decomposed with lead oxide.

[0061] [Experiment 23] In Experiment 23, 3.0268 g (0.017 mol) of galactose (approximately 180 g / mol, manufactured by Kishida Chemical Co., Ltd.), 27.2608 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, the concentration of galactose was 0.3360 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1.5 hours while stirring at a rotational speed of 200 rpm. As a result, 0.002 mol (11.7 mol%) of hydrogen was obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0083 mol / L, 2.5 mol%), methanol (0.0019 mol / L, 0.57 mol%), ethanol (0.0008 mol / L, 0.24 mol%), acetic acid (0.026 mol / L, 7.7 mol%), formic acid (0.019 mol / L, 5.5 mol%), ethylene glycol (0.0037 mol / L, 1.1 mol%), and diethylene glycol (0.066 mol / L, 1.9 mol%) were obtained. A clear peak of acetoin was observed in the GC-MS.

[0062] [Experiment 24] In Experiment 24, 1.0779 g (0.006 mol) of mannose (approximately 180 g / mol, manufactured by Kishida Chemical Co., Ltd.), 9.0896 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, the concentration of mannose was 0.12 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour while stirring at a rotational speed of 200 rpm. As a result, 0.0028 mol (48.3 mol%) of hydrogen and 0.00045 mol (0.76 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0044 mol / L, 3.7 mol%), methanol (0.0018 mol / L, 1.5 mol%), ethanol (0.002 mol / L, 1.6 mol%), acetic acid (0.0017 mol / L, 1.5 mol%), formic acid (0.002 mol / L, 1.7 mol%), and ethylene glycol (0.0016 mol / L, 1.4 mol%) were obtained.

[0063] [Experiment 25] In Experiment 25, 1.0160 g (0.0068 mol) of arabinose (approximately 150 g / mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 9.0788 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of industrial purified water were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., 128 mL capacity) and sealed. At this point, the concentration of arabinose was 0.14 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour while stirring at a rotation speed of 200 rpm. As a result, 0.002 mol (29 mol%) of hydrogen and 0.00003 mol (0.4 mol%) of carbon monoxide were obtained from the gas phase, and 0.0011 mol / L (0.82 mol%) of acetone, 0.00026 mol / L (2.3 mol%) of methanol, 0.017 mol / L (12.6 mol%) of acetic acid, and 0.017 mol / L (12.6 mol%) of formic acid were obtained from the liquid phase as aqueous solutions.

[0064] [Experiment 26] In Experiment 26, 10 g (0.056 mol) of coffee bean extraction residue (medium roast, finely ground, assumed to be 162 g / mol), a commercially available paper coffee filter (cellulose, 1 g dry weight), 90.8464 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 300 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D1000M, manufactured by Pressure Glass Industry Co., Ltd., capacity 1550 mL) and sealed. At this point, the concentration of the coffee bean extraction residue was 0.2 mol / L, assuming that it was completely dissolved. In this state, the decomposition reaction was carried out at 200°C for 2.5 hours while stirring at a rotational speed of 200 rpm. As a result, 0.030 mol (48.9 mol%) of hydrogen and 0.0018 mol (2.9 mol%) of carbon monoxide were obtained from the gas phase. Figure 5 is a chromatogram of the components contained in the filtrate obtained in Experiment 26. As shown in Figure 5, the following aqueous solutions were obtained from the liquid phase: acetone at 0.0013 mol / L (0.64 mol%), methanol at 0.0046 mol / L (2.3 mol%), ethanol at 0.0012 mol / L (0.59 mol%), acetic acid at 0.028 mol / L (13.5 mol%), and formic acid at 0.023 mol / L (11.4 mol%).

[0065] [Comparative Experiment 1] In Comparative Experiment 1, 10 g (0.056 mol) of coffee bean extraction residue (medium roast, finely ground, assumed to be 162 g / mol) was hydrolyzed in a pressure vessel (TEM-D1000M, 1550 mL capacity, manufactured by Pressure Glass Industry Co., Ltd.) with 300 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) without using lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.). During this decomposition reaction, the concentration of the coffee bean extraction residue was 0.2 mol / L, assuming that it was completely dissolved. The decomposition reaction was carried out at 200°C for 2.5 hours while stirring at a rotation speed of 200 rpm. As a result, 0.0077 mol (12.1 mol%) of carbon dioxide and 0.00010 mol (0.16 mol%) of carbon monoxide were detected in the gas phase. On the other hand, no hydrogen was generated. Figure 6 shows the chromatogram of the components contained in the filtrate obtained in comparative experiment 1. As shown in Figure 6, hydroxyacetone was obtained as an aqueous solution from the liquid phase at concentrations of 0.0092 mol / L (4.4 mol%), acetic acid at 0.012 mol / L (5.5 mol%), and furfural at 0.0008 mol (0.4 mol%). On the other hand, acetone, methanol, and ethanol were below the detection limit.

[0066] Experiments 23-26 show that monosaccharides other than glucose and their polymers, polysaccharides, can be effectively decomposed using metal oxides and metal hydroxides, including lead oxide, to easily obtain industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones. Experiment 26 also shows that coffee bean extraction residue itself can be a source of hydrogen and alcohols. Comparative experiment 1 shows that when coffee extraction residue is hydrothermally decomposed without using PbO2 or the like, hydrogen, methanol, and ethanol are not obtained; carbon dioxide is the main component. When monosaccharides and polysaccharides are decomposed using lead oxide or the like with water as the medium, no carbon dioxide is produced.

[0067] [Experiment 27] In Experiment 27, 3.0378 g (0.019 mol) of unused paper coffee filters (cellulose, assumed molecular weight 180 g / mol, 3 filters), 27.2352 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), 0.0974 g of sodium hydroxide (0.002435 mol, manufactured by Kishida Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, assuming that all of the paper coffee filters were dissolved, the concentration was 0.375 mol / L, and the pH was 13. In this state, the decomposition reaction was carried out at 200°C for 4 hours while stirring at a rotation speed of 200 rpm. As a result, 0.003 mol (16.1 mol%) of hydrogen and 0.0001 mol (0.54 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0019 mol / L, 0.5 mol%), methanol (0.005 mol / L, 1.4 mol%), ethanol (0.00026 mol / L, 0.07 mol%), acetic acid (0.0063 mol / L, 1.7 mol%), formic acid (0.0038 mol / L, 1.0 mol%), ethylene glycol (0.0020 mol / L, 0.56 mol%), and diethylene glycol (0.0019 mol / L, 0.5 mol%) were obtained.

[0068] Experiment 27 shows that industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones can be easily obtained by decomposing paper filters (cellulose) used for coffee dripping with metal oxides and metal hydroxides, including lead oxide. The results of the decomposition experiment of insoluble powdered cellulose have already been shown in Experiment 22, but it can be seen that even with the same cellulose, the yield of decomposition products differs depending on whether it is in the form of paper or powder.

[0069] [Experiment 28] In Experiment 28, 3.0426 g (0.017 mol) of fructose (approximately 180 g / mol, manufactured by Kishida Chemical Co., Ltd.), 27.0261 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, the concentration of fructose was 0.338 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1.5 hours while stirring at a rotational speed of 200 rpm. As a result, 0.002 mol (13.2 mol%) of hydrogen and 0.0001 mol (0.60 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, the following aqueous solutions were obtained: 0.00096 mol / L (0.28 mol%) of acetone, 0.0024 mol / L (0.07 mol%) of methanol, 0.00071 mol / L (0.21 mol%) of ethanol, 0.034 mol / L (10.1 mol%) of acetic acid, 0.0092 mol / L (2.7 mol%) of formic acid, 0.0020 mol / L (0.56 mol%) of ethylene glycol, and 0.00034 mol / L (0.001 mol%) of diethylene glycol.

[0070] [Experiment 29] In Experiment 29, 10.1350 g (0.03 mol) of sucrose (approximately 342 g / mol, manufactured by Nacalai Tesque Co., Ltd.), 91.6667 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 300 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D1000M, manufactured by Pressure Glass Industry Co., Ltd., capacity 1550 mL) and sealed. At this point, the concentration of sucrose was 0.099 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1.5 hours while stirring at a rotational speed of 200 rpm. As a result, 0.031 mol (105.27 mol%) of hydrogen and 0.0026 mol (8.67 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0057 mol / L, 5.8 mol%), methanol (0.015 mol / L, 14.9 mol%), ethanol (0.016 mol / L, 16.6 mol%), acetic acid (0.039 mol / L, 39.3 mol%), formic acid (0.00073 mol / L, 0.74 mol%), and ethylene glycol (0.00035 mol / L, 0.35 mol%) were obtained.

[0071] Fructose is an important monosaccharide of biological origin. It forms disaccharides with glucose to become sucrose (table sugar, sugar). A large amount of sucrose remains in food waste (garbage). Experiments 28 and 29 show that fructose and sucrose can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones.

[0072] [Experiment 30] In Experiment 30, 3.0044 g (0.0083 mol) of maltose monohydrate (approximately 360 g / mol, manufactured by Kishida Chemical Co., Ltd.), 29.4174 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, the concentration of maltose monohydrate was 0.17 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour and 35 minutes while stirring at a rotational speed of 300 rpm. As a result, 0.012 mol (143.8 mol%) of hydrogen and 0.00015 mol (1.8 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, the following aqueous solutions were obtained: 0.0046 mol / L (2.7 mol%) of acetone, 0.0021 mol / L (1.2 mol%) of methanol, 0.0011 mol / L (0.67 mol%) of ethanol, 0.023 mol / L (13.5 mol%) of acetic acid, 0.013 mol / L (7.9 mol%) of formic acid, 0.00068 mol / L (0.041 mol%) of ethylene glycol, and 0.00088 mol / L (0.053 mol%) of diethylene glycol.

[0073] [Experiment 31] In Experiment 31, 3.0774 g (0.0083 mol) of lactose monohydrate (approximately 360 g / mol, manufactured by Kishida Chemical Co., Ltd.), 27.5832 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, the concentration of lactose monohydrate was 0.17 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour and 35 minutes while stirring at a rotation speed of 450 rpm. As a result, 0.0044 mol (51.3 mol%) of hydrogen and 0.00015 mol (1.8 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, the following aqueous solutions were obtained: 0.0059 mol / L (3.5 mol%) of acetone, 0.0014 mol / L (0.81 mol%) of methanol, 0.0053 mol / L (3.1 mol%) of ethanol, 0.029 mol / L (16.7 mol%) of acetic acid, 0.014 mol / L (8.3 mol%) of formic acid, 0.0019 mol / L (1.1 mol%) of ethylene glycol, and 0.0029 mol / L (1.7 mol%) of diethylene glycol.

[0074] Maltose and lactose are important disaccharides consumed by humankind and are found in large quantities in waste. Maltose is abundant in barley and has the same structure as the linear component of starch, with two glucose molecules linked together. Lactose is a disaccharide of glucose and galactose. Experiment 30 shows that maltose, like starch and glucose, can be easily decomposed by metal oxides and metal hydroxides, including lead oxide, resulting in the easy acquisition of industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones. Experiment 31 also shows that lactose, like glucose and galactose, can be decomposed by metal oxides and metal hydroxides, including lead oxide, resulting in the easy acquisition of industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones.

[0075] [Experiment 32] In Experiment 32, 3.0710 g (0.009 mol) of cellobiose (approximately 342 g / mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 27.2601 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 300 mL of ultrapure water (resistance 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, the concentration of cellobiose was 0.18 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour and 50 minutes while stirring at a rotational speed of 200 rpm. As a result, 0.002 mol (23.1 mol%) of hydrogen and 0.0013 mol (14.9 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0063 mol / L, 3.5 mol%), methanol (0.0045 mol / L, 2.5 mol%), ethanol (0.0011 mol / L, 0.63 mol%), acetic acid (0.054 mol / L, 30.2 mol%), formic acid (0.04 mol / L, 20.6 mol%), and ethylene glycol (0.00045 mol / L, 0.25 mol%) were obtained.

[0076] Cellobiose is a disaccharide formed when cellulose is broken down. Experiment 32 shows that cellobiose can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, and as a result, industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones can be easily obtained.

[0077] [Experiment 33] In Experiment 33, 10.0037 g (0.052 mol) of citrus pectin (approximately 194 g / mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 90.5170 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 300 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D1000M, manufactured by Pressure Glass Industry Co., Ltd., capacity 1550 mL) and sealed. At this point, the pectin concentration was 0.17 mol / L. In this state, the decomposition reaction was carried out at 200°C for 2 hours while stirring at a rotation speed of 200 rpm. As a result, 0.025 mol (48.5 mol%) of hydrogen and 0.0015 mol (2.9 mol%) of carbon monoxide were obtained from the gas phase. Figure 7 is a chromatogram of the components contained in the filtrate obtained in Experiment 33. As shown in Figure 7, aqueous solutions of acetone (0.0043 mol / L, 2.5 mol%), methanol (0.096 mol / L, 56.1 mol%), ethanol (0.0058 mol / L, 3.4 mol%), acetic acid (0.022 mol / L, 12.7 mol%), and formic acid (0.01 mol / L, 5.7 mol%) were obtained from the liquid phase.

[0078] Pectin is one of the representative complex polysaccharides. Pectin is always found in the cell walls of plants and stabilizes the morphology of plant cells by being located between cellulose fibers. It is especially abundant in fruits and is used as a thickening agent in foods such as jams. Therefore, pectin is a polyol that is found in very large quantities not only in household food waste but also in industrial waste and sludge from food factories. According to Experiment 33, pectin can be decomposed with metal oxides and metal hydroxides, including lead oxide, to easily obtain industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones.

[0079] [Experiment 34] In Experiment 34, 3.0241 g (0.017 mol) of lignin dealkalization (approximately 182 g / mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 27.2113 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure vessel (TEM-D100M, manufactured by Pressure Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, the lignin concentration was 0.33 mol / L. Under these conditions, the decomposition reaction was carried out at 200°C for 3 hours while stirring at a rotational speed of 200 rpm. As a result, 0.016 mol (9.4 mol%) of hydrogen and 0.000076 mol (0.45 mol%) of carbon monoxide were obtained from the gas phase. Figure 8 is a chromatogram of the components contained in the filtrate obtained in Experiment 34. As shown in Figure 8, aqueous solutions of acetone (0.0058 mol / L, 1.7 mol%), methanol (0.089 mol / L, 26.6 mol%), and acetic acid (0.020 mol / L, 6.1 mol%) were obtained from the liquid phase.

[0080] The molecular weight of lignin in wood is said to be several thousand to tens of thousands, but the molecular structure of the smallest unit after hydrolysis was considered to be phenol glycerol. That is, an ideal form was considered as HO<C6H4>C*(OH)CH(OH)C*H(OH) = 182 g / mol (<C6H4>: benzene ring, *: crosslinking point) (see Patent Document 3).

[0081] [Experiment 35] In Experiment 35, 10.2407 g (0.06 mol) of cypress powder (172 g / mol (the molar mass was calculated from the molecular weight of cellulose, 162, and the molecular weight of lignin, 182)), 90.8575 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 300 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure vessel (TEM-D1000M, manufactured by Pressure Glass Industry Co., Ltd., capacity 1550 mL) and sealed. At this point, the concentration of the wood powder was 0.2 mol / L, assuming it was completely dissolved. In this state, the decomposition reaction was carried out at 200°C for 4 hours while stirring at a rotational speed of 200 rpm. As a result, 0.02 mol (33.5 mol%) of hydrogen and 0.0015 mol (2.6 mol%) of carbon monoxide were obtained from the gas phase. Figure 9 shows the chromatogram of the components contained in the filtrate obtained in Experiment 35. As shown in Figure 9, aqueous solutions of acetone (0.00019 mol / L, 0.09 mol%), methanol (0.031 mol / L, 15.6 mol%), and acetic acid (0.016 mol / L, 7.8 mol%) were obtained from the liquid phase.

[0082] [Experiment 36] In Experiment 36, 3.0685 g (0.02 mol) of xylan ([C5H8O4] nXylan (C5H8O4 = 132 g / mol, the main component of hemicellulose, manufactured by Tokyo Chemical Industry Co., Ltd.), 27.3635 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, the xylan concentration was 0.4 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1 hour while stirring at a rotation speed of 350 rpm. As a result, 0.0049 mol (23.8 mol%) of hydrogen and 0.00010 mol (0.49 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, the following aqueous solutions were obtained: 0.0046 mol / L (1.1 mol%) of acetone, 0.0016 mol / L (0.28 mol%) of methanol, 0.0057 mol / L (1.4 mol%) of ethanol, 0.039 mol / L (9.6 mol%) of acetic acid, 0.0058 mol / L (1.4 mol%) of formic acid, 0.015 mol / L (3.8 mol%) of ethylene glycol, and 0.00045 mol / L (0.11 mol%) of diethylene glycol.

[0083] [Experiment 37] In Experiment 37, 3.0478 g (0.02 mol) of xylose (a monosaccharide that makes up xylan, approximately 150 g / mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 27.3635 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (Pressure-Resistant Glass Industry TEM-D100M, capacity 128 mL) and sealed. At this point, the concentration of xylose was 0.4 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1.5 hours while stirring at a rotation speed of 350 rpm. As a result, 0.0026 mol (12.9 mol%) of hydrogen and 0.00008 mol (0.38 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0082 mol / L, 2.0 mol%), methanol (0.0021 mol / L, 0.52 mol%), ethanol (0.000082 mol / L, 0.20 mol%), acetic acid (0.027 mol / L, 6.7 mol%), and formic acid (0.0093 mol / L, 2.3 mol%) were obtained.

[0084] Experiment 34 shows that lignin, a polyol obtained from wood, can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones. Furthermore, Experiment 35 shows that wood itself can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones.

[0085] Hemicellulose is also an important polyol in wood. According to Experiment 36, xylan, the main component of hemicellulose, can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones. Considering that hemicellulose is a mixture containing various sugars while xylose is the main component, it can be said that hemicellulose can be decomposed by applying the method described in Experiment 36. Furthermore, according to Experiment 37, xylose, the smallest unit (monosaccharide) of xylan, can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones.

[0086] By applying experiments 34-37, woody waste originating from forests can be converted into industrial resources.

[0087] [Experiment 38] In Experiment 38, 3.0832 g (0.019 mol) of domestic sludge (162 g / mol; molecular weight of starch and cellulose was used) collected from a wastewater treatment plant and processed into a cake-like state using a screw-type dewatering device, 27.2927 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of industrial purified water were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, assuming all of the domestic sludge was dissolved, the concentration was 0.38 mol / L. In this state, the decomposition reaction was carried out at 200°C for 1.5 hours while stirring at a rotational speed of 430 rpm. As a result, 0.00093 mol (4.9 mol%) of hydrogen and 0.0001 mol (0.54 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0013 mol / L, 0.33 mol%), methanol (0.0018 mol / L, 0.47 mol%), ethanol (0.00056 mol / L, 0.15 mol%), acetic acid (0.0079 mol / L, 2.1 mol%), formic acid (0.0063 mol / L, 1.6 mol%), ethylene glycol (0.00045 mol / L, 0.12 mol%), and diethylene glycol (0.0012 mol / L, 0.31 mol%) were obtained.

[0088] [Experiment 39] In Experiment 39, 3.0719 g (0.0095 mol of polyol component) of dry papermaking sludge in the form of balls approximately 10-20 mm in diameter, collected from a paper mill (the polyol component was set at 162 g / mol based on cellulose. Half of the weighed sample was the polyol component, and the other half was inorganic salts such as alumina, silica, and calcium oxide. See Non-Patent Literature 1.), 27.2927 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of industrial purified water were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, assuming all of the papermaking sludge was dissolved, the concentration was 0.19 mol / L. In this state, the decomposition reaction was started with a rotation speed of 250 rpm and a set temperature of 200°C. Even after the reaction vessel reached 200°C, the temperature inside the container continued to rise and reached 280°C after 10 minutes. At this point, the safety device of the temperature control device activated and the heater stopped. Natural cooling was then allowed to proceed. Therefore, the reaction time was 10 minutes, from 200°C to 280°C. As a result, from the gas phase, 0.00093 mol (10.8 mol%) of hydrogen and 0.000051 mol (0.54 mol%) of carbon monoxide were obtained. From the liquid phase, the following aqueous solutions were obtained: acetone 0.00017 mol / L (0.09 mol%), methanol 0.0016 mol / L (0.84 mol%), ethanol 0.00023 mol / L (0.12 mol%), acetic acid 0.0073 mol / L (3.8 mol%), formic acid 0.0061 mol / L (3.2 mol%), ethylene glycol 0.00048 mol / L (0.26 mol%), and diethylene glycol 0.0012 mol / L (0.62 mol%).

[0089] Experiments 38 and 39 show that actual household sludge and papermaking sludge can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain flammable gases, alcohols, organic acids, ketones, and other industrially useful chemical components.

[0090] [Experiment 40] In Experiment 40, 3.0194 g (0.033 mol) of glycerol (approximately 92 g / mol, SIGMA-ALDRICH), 27.2749 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of ultrapure water (resistance 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, the concentration of glycerol was 0.66 mol / L. The reaction was carried out at 200°C for 1 hour while stirring at a rotational speed of 200 rpm. As a result, 0.013 mol (38.5 mol%) of hydrogen and 0.000092 mol (0.28 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.00039 mol / L, 0.06 mol%), methanol (0.039 mol / L, 6 mol%), ethanol (0.0044 mol / L, 0.67 mol%), acetic acid (0.011 mol / L, 17.4 mol%), formic acid (0.0048 mol / L, 0.73 mol%), and ethylene glycol (0.0019 mol / L, 2.9 mol%) were obtained.

[0091] [Experiment 41] In Experiment 41, 10.2482 g (0.047 mol) of triacetin (218 g / mol, manufactured by Hayashi Pure Chemical Industries, Ltd.), 90.2412 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 300 mL of ultrapure water (resistance 18.2 MΩ・cm, manufactured by ELGA Corporation) were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure Glass Industry Co., Ltd., capacity 128 mL) and sealed. At this point, the concentration of triacetin was 0.16 mol / L. The reaction was carried out at 200°C for 1 hour and 40 minutes while stirring at a rotational speed of 200 rpm. As a result, 0.015 mol (32.0 mol%) of hydrogen and 0.0010 mol (2.2 mol%) of carbon monoxide were obtained from the gas phase. Figure 10 is a chromatogram of the components contained in the filtrate obtained in Experiment 41. As shown in Figure 10, the following aqueous solutions were obtained from the liquid phase: acetone at 0.00041 mol / L (0.26 mol%), methanol at 0.017 mol / L (11.1 mol%), ethanol at 0.0023 mol / L (1.5 mol%), acetic acid at 0.14 mol / L (90.4 mol%), formic acid at 0.077 mol / L (49.6 mol%), and ethylene glycol at 0.00036 mol / L (0.23 mol%).

[0092] [Experiment 42] In Experiment 42, 1.0420 g (0.0011 mol) of soybean oil (approximately 917 g / mol (Non-Patent Literature 2), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 9.0995 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of industrial purified water were placed in a pressure-resistant container (TEM-D100M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., with a capacity of 128 mL) and sealed. At this point, the concentration of the soybean oil was 0.023 mol / L. The reaction was carried out at 200°C for 1.5 hours while stirring at a rotational speed of 200 rpm. As a result, 0.0017 mol (146.4 mol%) of hydrogen, 0.000050 mol (4.4 mol%) of carbon monoxide, and 0.00020 mol (17.7 mol%) of methane were obtained from the gas phase. Figure 11 is a chromatogram of the components contained in the water filtrate obtained in Experiment 42. As shown in Figure 11, the following aqueous solutions were obtained from the liquid phase: acetone 0.0018 mol / L (7.7 mol%), methanol 0.0014 mol / L (6.3 mol%), ethanol 0.00029 mol / L (1.3 mol%), acetic acid 0.0049 mol / L (21.7 mol%), formic acid 0.0018 mol / L (8.1 mol%), ethylene glycol 0.00031 mol / L (1.4 mol%), 1-butanol 0.0004 mol / L (1.7 mol%), and hydroxyacetone 0.0005 mol / L (2.2 mol%). In addition, the water-insoluble components attached to the lead oxide were quantified by drying the lead oxide powder separated by filtration at 80°C for 7 hours, adding 50 mL of hexane to extract the water-insoluble components, and measuring the hexane solution by GC-MS. The GCMS apparatus, column, helium flow rate, and measurement temperature were all the same as those used for the analysis of aqueous solution components. Figure 12 is a chromatogram of the components contained in the hexane extract obtained in Experiment 42. As shown in Figure 12, clear GCMS peaks were obtained for 3-hexanol, 2-hexanol, pentadecane, octadecane, 8-heptadecene, hexanoic acid, heptanoic acid, and octanoic acid. It is clear that these components originate from fatty acids in soybean oil.

[0093] [Experiment 43] In Experiment 43, 2.1 g (0.0025 mol) of crude palm oil (CPO: Crude Palm Oil, approximately 850 g / mol (see Non-Patent Documents 3 and 4), from Indonesia), 9.02 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation), and 1 mL of 0.1 mol / L sulfuric acid were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, the concentration of the crude palm oil was 0.049 mol / L. The reaction was carried out at 200°C for 2 hours while stirring at a rotational speed of 400 rpm. As a result, from the gas phase, 0.0029 mol (115.8 mol%) of hydrogen, 0.00015 mol (6.1 mol%) of carbon monoxide, and 0.0020 mol (81.3 mol%) of methane were obtained. From the liquid phase, aqueous solutions of acetone, 0.0018 mol / L (3.7 mol%), methanol, 0.0029 mol / L (5.9 mol%), ethanol, 0.0019 mol / L (3.4 mol%), acetic acid, 0.0041 mol / L (8.4 mol%), formic acid, 0.0065 mol / L (13.5 mol%), ethylene glycol, 0.0017 mol / L (3.5 mol%), diethylene glycol, 0.0013 mol / L (2.6 mol%), and 1-propanol, 0.066 mol / L (133.2 mol%) were obtained.

[0094] [Experiment 44] In Experiment 44, 2.03 g (0.013 mol) of palm kernel shell (PKS, approximately 162 g / mol as it is similar to cellulose, sourced from Indonesia), 9.02 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA Corporation), and 1 mL of 0.1 mol / L sulfuric acid were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, assuming all of the PKS had dissolved, the concentration was 0.25 mol / L. The reaction was carried out at 200°C for 2 hours while stirring at a rotation speed of 400 rpm. As a result, from the gas phase, 0.0037 mol (29.6 mol%) of hydrogen, 0.00005 mol (0.4 mol%) of carbon monoxide, and 0.0005 mol (4 mol%) of methane were obtained. From the liquid phase, aqueous solutions of acetone, 0.0026 mol / L (1.0 mol%), methanol, 0.0066 mol / L (2.6 mol%), ethanol, 0.0027 mol / L (1.1 mol%), acetic acid, 0.0084 mol / L (3.4 mol%), formic acid, 0.0021 mol / L (0.85 mol%), ethylene glycol, 0.0028 mol / L (1.1 mol%), and diethylene glycol, 0.0016 mol / L (0.63 mol%) were obtained.

[0095] [Experiment 45] In Experiment 45, 2.1 g (0.013 mol) of sludge components settled in slightly damp palm oil mill wastewater (POEM: Palm Oil Mill Effluent, 162 g / mol as it is similar to cellulose, from Indonesia), 9.02 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), 50 mL of ultrapure water (resistance value 18.2 MΩ・cm, manufactured by ELGA), and 1 mL of 0.1 mol / L sulfuric acid were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. At this point, assuming all of the POEM sludge was dissolved, the concentration was 0.26 mol / L. The reaction was carried out at 200°C for 2 hours while stirring at a rotational speed of 400 rpm. As a result, 0.0010 mol (7.7 mol%) of hydrogen and 0.000050 mol (0.39 mol%) of carbon monoxide were obtained from the gas phase, and from the liquid phase, aqueous solutions of acetone (0.0017 mol / L, 0.64 mol%), methanol (0.0030 mol / L, 1.2 mol%), ethanol (0.0018 mol / L, 0.71 mol%), acetic acid (0.0053 mol / L, 2.0 mol%), formic acid (0.0015 mol / L, 0.59 mol%), ethylene glycol (0.0019 mol / L, 0.72 mol%), and diethylene glycol (0.0018 mol / L, 0.68 mol%) were obtained.

[0096] [Experiment 46] In Experiment 46, 50 mL of an aqueous solution of POME from Indonesia (solid content was 4% of the total (see Non-Patent Document 5), equivalent to 3 g of cellulose; 162 g / mol, 1.5 g / mL, 0.019 mol, 0.37 mol / L), 9.02 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 1 mL of 0.1 mol / L sulfuric acid were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., capacity 120 mL) and sealed. In this state, the decomposition reaction was carried out at 200°C for 2 hours while stirring at a rotational speed of 400 rpm. As a result, the following aqueous solutions were obtained from the gas phase: 0.072 mol (391.2 mol%) of hydrogen, 0.0012 mol (6.7 mol%) of carbon monoxide, and 0.016 mol (88.9%) of methane. From the liquid phase, the following aqueous solutions were obtained: 0.0049 mol / L (1.3 mol%) of acetone, 0.022 mol / L (6.2 mol%) of methanol, 0.0089 mol / L (2.4 mol%) of ethanol, 0.023 mol / L (6.2 mol%) of acetic acid, 0.0014 mol / L (0.39 mol%) of formic acid, 0.0023 mol / L (0.62 mol%) of ethylene glycol, 0.0018 mol / L (0.48 mol%) of diethylene glycol, and 0.75 mol / L (202.0 mol%) of 1-propanol.

[0097] Fats and oils derived from plants and animals, such as cooking oil (vegetable oil) and lard, are now considered waste. Chemically, lipids are triacylglycerols, where fatty acids are ester-bonded to the three hydroxyl groups of glycerol. Since glycerol is a polyol with three carbon atoms, lipids are essentially polyol esters.

[0098] Experiment 40 showed that glycerol can be easily decomposed with metal oxides, including lead oxide, and metal hydroxides to obtain industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones. This result revealed that polyol esters can also be decomposed with water and metal oxides. Whether the hydroxyl groups of a hydrated polyol remain as they are, or whether the hydroxyl groups are esterified, metal oxides have the function of cleaving carbon-carbon bonds.

[0099] Triacetin is a compound in which three hydroxyl groups of glycerol are esterified with acetate. According to Experiment 41, triacetin can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain flammable gases, alcohols, organic acids, ketones, and other industrially useful chemical components. Furthermore, according to Experiment 42, soybean oil can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain flammable gases, alcohols, organic acids, ketones, alkanes, alkenes, and other industrially useful chemical components. In addition, according to Experiment 43, crude palm oil can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain flammable gases, alcohols, organic acids, ketones, and other industrially useful chemical components. From these results, it can be seen that there are various types of fatty acids in vegetable oils, and these are bonded in various combinations depending on the type of plant. Regardless of these conditions, it is possible to decompose glycerol esters with water and metal oxides or metal hydroxides to convert them into energy resources and chemical raw materials.

[0100] Experiment 44 shows that PKS can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain flammable gases, alcohols, organic acids, ketones, and other industrially useful chemical components.

[0101] Experiment 45 shows that POME sludge can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain flammable gases, alcohols, organic acids, ketones, and other industrially useful chemical components.

[0102] Experiment 46 shows that an aqueous solution of POME can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain flammable gases, alcohols, organic acids, ketones, and other industrially useful chemical components.

[0103] Tables 5 to 8 summarize the substances to be decomposed, metal oxides or metal hydroxides, solvents, the presence or absence of acids or bases, and the types of products involved in Experiments 21 to 46 and Comparative Experiment 1.

[0104] Biologically derived polyols are a collection of sugar skeletons formed by the polymerization of glucose and various other monosaccharides produced by plant photosynthesis, as well as disaccharides and oligosaccharides, which are combinations of monosaccharides. The basic unit of the sugar skeleton is the extremely simple chemical structure [HCOH], but because there are various combinations of conformation, configuration, and the bonding positions of monosaccharides, biologically derived polyols are extremely diverse. Enzymes promote ordered chemical reactions within cells based on substrate specificity, and polyols contained in waste have chemical structures that are difficult to decompose by enzymes. Therefore, decomposing the diverse biologically derived polyols contained in waste by enzymes is not efficient except in specific reaction systems. Furthermore, biologically derived polyol esters are triglycerides. There are various types of triglycerides, and there are also many different types of lipases, which are enzymes that decompose them. It is not desirable from a cost perspective to prepare a corresponding lipase for every type of triglyceride contained in waste and process the waste accordingly. In other words, the substrate specificity of each lipase is actually detrimental from the perspective of waste disposal. Furthermore, similar to polyols, polyol esters that remain as waste are not easily decomposed by enzymes. According to Experiments 1-46, the oxidizing or reducing action of metal oxides and metal hydroxides in water, which have different standard oxidation-reduction potentials from water, and the hydrolysis action of organic matter in acidic or alkaline environments near the surface, have the advantage of not exhibiting the structural selectivity, such as the substrate specificity of enzymes, towards a wide variety of polyols and polyol esters.

[0105] [Experiment 47] In Experiment 47, 3.0195 g (0.070 mol) of polyvinyl alcohol (PVA, 43 g / mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 27.0079 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of industrial purified water were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., with a capacity of 120 mL) and sealed. At this point, the concentration of PVA was 0.14 mol / L. The reaction was carried out at 200°C for 1.5 hours while stirring at a rotational speed of 400 rpm. As a result, 0.0093 mol (13.3 mol%) of hydrogen and 0.00025 mol (0.36 mol%) of carbon monoxide were obtained from the gas phase. Figure 13 is a chromatogram of the components contained in the filtrate obtained in Experiment 47. As shown in Figure 13, the following aqueous solutions were obtained from the liquid phase: acetone 0.026 mol / L (18.4 mol%), methanol 0.0049 mol / L (3.5 mol%), ethanol 0.00054 mol / L (0.39 mol%), acetic acid 0.0075 mol / L (5.3 mol%), formic acid 0.0063 mol / L (4.5 mol%), and ethylene glycol 0.00046 mol / L (0.33 mol%).

[0106] Polyvinyl alcohol (PVA) is an example of an artificial polyol, and it is widely used in various industrial processes as a thickener, adhesive, and emulsifier. Therefore, it is often found in waste liquids, waste materials, and sludge. According to Experiment 47, PVA can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain industrially useful chemical components such as flammable gases, alcohols, organic acids, and ketones.

[0107] [Experiment 48] In Experiment 48, 1.0097 g of crushed PET bottle material (average 5 mm square, provided by Otsuka Pharmaceutical Co., Ltd., washed), 6.5113 g of powdered lead(IV) oxide (PbO2, manufactured by Kanto Chemical Co., Ltd., purity 97.0%), 50 mL of ultrapure water (18.2 MΩ・cm, manufactured by ELGA), and a 25 mm long rugby ball-shaped stirring bar (Teflon coated) were placed in a pressure vessel (NR0218, manufactured by Flon Chemical Co., Ltd., capacity 100 mL) and sealed. The pressure vessel was then heated to 190°C using a temperature control device, and the reaction was carried out for 1 hour while maintaining the temperature at 190°C (±5°C) and rotating the stirring bar at 20 rpm. After that, the pressure vessel was allowed to cool naturally to room temperature, and then suction filtration was performed to measure the components contained in the filtrate. The pH of the filtrate was 6-7. Furthermore, a large amount of crushed PET bottle material (hereinafter also referred to as PET crushed material) remained on the filter along with lead oxide powder. Figure 14 is a chromatogram showing the GCMS measurement results of the filtrate. As can be seen from this chromatogram, the dominant component in the filtrate was ethylene glycol (82%), with only small amounts of diethylene glycol (9%) and methanol (9%) present. A small amount of formic acid was also observed.

[0108] [Experiment 49] In Experiment 49, the same procedure as in Experiment 48 was followed, except that the amount of crushed used PET bottle material added was changed to 1.0160g, the amount of powdered lead(IV) oxide added was changed to 6.5110g, and the reaction time was changed to 3 hours. The same materials and containers used in the experiment were also used as in Experiment 48. After the reaction, the pressure vessel was allowed to cool naturally to room temperature, and then suction filtration was performed to measure the components contained in the filtrate. The pH of the filtrate was 6-7. A small amount of PET crushed material remained on the filter along with the lead oxide powder. The chromatogram obtained by GCMS is shown in Figure 15. As can be seen from this chromatogram, ethylene glycol (57%) was the dominant component in the filtrate. Compared to the results of Experiment 48, the proportion of ethylene glycol decreased, and instead the proportions of diethylene glycol (14%) and methanol (29%) increased. In particular, the proportion of methanol was about three times that of Experiment 48 (9%). Acetic acid and formic acid were also observed.

[0109] [Experiment 50] The experiment was conducted using the same procedure as in Experiment 48, except that the amount of crushed used PET bottle material added was changed to 1.0155 g, the amount of powdered lead(IV) oxide added to 6.5139 g, and the reaction time was changed to 6 hours. The same materials and containers used in the experiment were also used as in Experiment 48. After the reaction, the pressure vessel was allowed to cool naturally to room temperature, and then suction filtration was performed to measure the components contained in the filtrate. The pH of the filtrate was 6-7. Furthermore, no lead oxide powder or PET crushed material was found on the filter. From this, it was found that when the reaction temperature is 190°C, the depolymerization of PET is completed within 6 hours. The chromatogram obtained by GCMS is shown in Figure 16. From this chromatogram, it was found that the main component of the components contained in the filtrate was methanol (88%), and ethylene glycol was below the detection limit. From this, it was considered that almost all of the ethylene glycol was converted to methanol. On the other hand, diethylene glycol (12%) remained without being converted to ethanol.

[0110] To confirm that terephthalic acid was adhering to the surface of the lead oxide powder on the filter, the lead oxide powder was placed back into a pressure vessel, to which 50 mL of ultrapure water (18.2 MΩ·cm, ELGA) and 0.44 g of sodium hydroxide were added. A 25 mm long rugby ball-shaped stirring bar (Teflon coated) was then placed in the pressure vessel, sealed, and the mixture was reacted at 190°C (±5°C) for 4 hours.

[0111] Afterward, the pressure vessel was allowed to cool naturally to room temperature, and then suction filtration was performed. Lead oxide powder remained on the filter. The filtrate was then placed in a 90°C drying oven and the water was completely removed over 8 hours. As a result, 0.95 g of a slightly creamy white powder was obtained. The XRD spectrum obtained from the X-ray diffraction data of this powder is shown in Figure 17. Figure 18 shows the XRD spectrum of disodium terephthalate (Tokyo Chemical Industries, Ltd.), a commercially available experimental reagent.

[0112] Figures 17 and 18 show that the substance attached to the lead oxide powder was disodium terephthalate, and that the yield of disodium terephthalate derived from used PET was 85%.

[0113] Furthermore, to confirm that the lead oxide powder remaining on the filter was the same as the original lead oxide (PbO2), X-ray diffraction measurements were performed on this powder and the unused lead oxide powder. The XRD spectra of the lead oxide remaining on the filter and the unused lead oxide are shown in Figures 19 and 20.

[0114] A comparison of Figures 19 and 20 shows that lead oxide remained unchanged before and after the depolymerization reaction of PET, indicating that it acted as a solid-liquid interface catalyst. Figure 10 shows an electron microscope (SEM) image of unused lead oxide powder. Figure 21 shows that the lead oxide powder used in this experiment had a maximum length of approximately 0.1 to 3.0 μm.

[0115] [Experiment 51] The experiment was conducted in the same manner as in Experiments 48-50, except that the temperature at which the PET pulverized material and water were reacted in the reaction vessel using lead oxide as a solid-liquid interface catalyst was changed to 200°C (±5°C). In this experiment, when the reaction time was 1 hour, the amount of used PET bottles added was 1.0037 g and the amount of powdered lead oxide added was 6.5046 g. When the reaction time was 3 hours, the amount of used PET bottles added was 1.0027 g and the amount of powdered lead oxide added was 6.5103 g. When the reaction time was 6 hours, the amount of used PET bottles added was 1.0026 g and the amount of powdered lead oxide added was 6.5123 g. In all cases, the amount of ultrapure water added was 50 mL. The chromatograms of the components contained in the filtrate obtained as a result of the experiment, measured by GCMS, are shown in Figures 22-24. Figures 22, 23, and 24 show the results when the reaction time between the PET pulverized material and water was 1 hour, 3 hours, and 6 hours, respectively.

[0116] As can be seen from comparing Figures 11-13 with Figures 3-5, the same results were obtained when the reaction temperature was set to 200°C as when it was set to 190°C.

[0117] [Comparative Experiment 2] As a second comparative experiment, the same experiment as in Experiments 48-50 was conducted without using powdered lead oxide. Specifically, 1.0134 g of crushed recycled used PET bottle material (average 5 mm square, provided by Otsuka Pharmaceutical Co., Ltd., washed) was placed in a pressure vessel (NR0218, manufactured by Flon Chemical Co., Ltd., 100 mL capacity). 50 mL of ultrapure water (18.2 MΩ・cm, manufactured by ELGA) was added. A 25 mm long rugby ball-shaped stirring bar (Teflon coated) was then placed in the pressure vessel and sealed. The pressure vessel was heated to 200°C using a temperature control device, and then the reaction was carried out for 72 hours while maintaining the temperature at 200°C (±5°C) and rotating the stirring bar at 20 rpm. After that, the reaction vessel was allowed to cool naturally to room temperature, and then suction filtration was performed to measure the components contained in the filtrate. The pH of the filtrate was 4-5. A white powder remained on the filter. GCMS, similar to that used in experiments 48-50, was used to measure the components contained in the filtrate. The GCMS measurement conditions were the same as those in experiments 48-50, but the column heating rate was set to 5°C / min, slower than in experiment 48, in order to carefully investigate whether or not the conversion from ethylene glycol to methanol was occurring. Figure 25 is a chromatogram showing the measurement results of the filtrate. From Figure 25, it was found that ethylene glycol could be obtained from PET by increasing the reaction time, even without lead oxide powder. On the other hand, it was confirmed that without lead oxide powder, even with an increased reaction time, the ethylene glycol obtained from PET was hardly converted to methanol. In addition, to confirm that the white powder remaining on the filter was terephthalic acid, X-ray diffraction measurements were performed on the white powder. The resulting XRD spectrum is shown in Figure 26, and the XRD spectrum of the standard substance is shown in Figure 27. As can be seen from Figures 26 and 27, when PET was depolymerized with water alone, terephthalic acid could be recovered, but almost no methanol was obtained. This result was consistent with the result in Figure 14.

[0118] Patent Document 1 reports that by using a temperature of 200°C to 300°C, PET can be hydrolyzed with water as a medium to obtain terephthalic acid and ethylene glycol. However, it is said that the temperature conditions when utilizing thermal energy (waste heat energy) discharged from chemical plants, food factories, steel mills, cement factories, etc. are at most 200°C, and at temperature conditions of 200°C to 300°C, it is not possible to cope with the situation by using only waste heat energy, and an additional heat source is required. In contrast, in this embodiment, even at a temperature of 190°C to 200°C, PET can be sufficiently hydrolyzed to obtain terephthalic acid and ethylene glycol, and moreover, by extending the reaction time, it is possible to convert ethylene glycol into methanol. In other words, in this embodiment, waste heat energy from chemical plants, food factories, etc. can be utilized without adding an additional heat source, and therefore it can be said to be a method that can contribute to reducing carbon dioxide emissions.

[0119] [Experiment 52] In Experiment 52, 10.35725 g (0.054 mol) of polyester resin (PET) flakes (approximately 192 g / mol, crushed recycled PET bottles, average 5 mm square), 90.2639 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 300 mL of industrial purified water were placed in a pressure-resistant container (TEM-D1000M, manufactured by Pressure-Resistant Glass Industry Co., Ltd., capacity 1550 mL) and sealed. At this point, the concentration of PET was 0.18 mol / L, assuming that it had all dissolved. The reaction was carried out at 200°C for 8 hours while stirring at a rotation speed of 200 rpm. As a result, from the gas phase, 0.013 mol (23.7 mol%) of hydrogen, 0.00041 mol / L (0.76 mol%) of carbon monoxide, and 0.00021 mol (0.38 mol%) of methane were obtained. From the liquid phase, 0.059 mol / L (32.5 mol%) of methanol and a trace amount of diethylene glycol were obtained as an aqueous solution.

[0120] [Experiment 53] In Experiment 53, 3.0165 g (0.486 mol) of ethylene glycol (EG, 62 g / mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 27.5042 g of lead oxide (PbO2, manufactured by Kanto Chemical Co., Ltd.), and 50 mL of industrial purified water were placed in a pressure-resistant container (MMJ-100, manufactured by OM Labtec Co., Ltd., with a capacity of 120 mL) and sealed. At this point, the concentration of EG was 0.97 mol / L. The reaction was carried out at 200°C for 30 minutes while stirring at a rotational speed of 400 rpm. As a result, 0.36 mol (36 mol%) of hydrogen and 0.0021 mol / L (0.2 mol%) of carbon monoxide were obtained from the gas phase, and 0.79 mol / L (80.9 mol%) of methanol, 0.029 mol / L (3.0 mol%) of acetic acid, and 0.069 mol / L (7.1 mol%) of ethylene glycol were obtained as aqueous solutions from the liquid phase.

[0121] Experiments 48-51 show that polyester resin (PET) can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain EG and other substances. Experiment 52 shows that flammable gases and other industrially useful chemical components such as alcohols and organic acids can also be easily obtained.

[0122] According to Experiment 53, EG can be easily decomposed with metal oxides and metal hydroxides, including lead oxide, to obtain flammable gases, alcohols, organic acids, and other industrially useful chemical components.

[0123] Table 9 summarizes the substances to be decomposed, metal oxides or metal hydroxides, solvents, presence or absence of acids or bases, and the types of products involved in Experiments 47-53 and Comparative Experiment 2.

[0124] Food waste, including leftovers, industrial waste, and sludge discharged from food processing plants, sewage treatment plants, or paper mills, is more than 80% water. Furthermore, the organic matter in these wastes is of plant and animal origin and has a very high affinity for water. Therefore, conventionally, vast amounts of fossil fuels have been consumed to dry and incinerate these wastes. To utilize these wastes as resources, it was necessary to efficiently dispose of or utilize this 80% water content. By applying Experiments 1-49, a clear vision can be envisioned for extracting hydrogen, carbon monoxide, and useful chemical substances such as methanol and ethanol using the water that accounts for 80% of the total weight of the waste. Moreover, Experiments 1-49 do not require expensive chemicals, drugs, or complex equipment. Therefore, Experiments 1-49 can be rapidly implemented in society using inexpensive, mass-produced materials.

[0125] The oxidizing or reducing action of metal oxides and metal hydroxides, which have different standard oxidation-reduction potentials from water, on water, and the hydrolysis of organic matter in acidic or alkaline environments near the surface, occur only near the solid-liquid interface, regardless of the pH of the bulk aqueous phase or the presence of inorganic salts. Therefore, as shown in Experiments 10, 11, 13, 14, 27, and 43-46, the mixture may contain acids (sulfuric acid, phosphoric acid, carbonic acid, etc.), alkalis and salts (sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, sodium bicarbonate, etc.), and water-soluble oxides (calcium hypochlorite, sodium percarbonate, etc.) that have been conventionally used to hydrolyze polymer compounds. By including these acids, alkalis, and inorganic salts, high molecular weight polyols and polyol esters can be hydrolyzed to a certain extent in the bulk aqueous phase to reduce their molecular weight, thereby improving the efficiency of hydrolysis and changing the product formation ratio. For similar reasons, it is also possible to pre-degrade high molecular weight polyols and polyol esters in the bulk aqueous phase by coexisting them with metal oxides using water-soluble oxides (such as calcium hypochlorite and sodium percarbonate). Calcium hypochlorite (bleaching powder) and sodium percarbonate are commonly used for cleaning in ordinary households and have the advantages of being highly safe and inexpensive.

[0126] [Embodiments] It will be apparent to those skilled in the art that the exemplary embodiments described above are specific examples of the following embodiments.

[0127] (Section 1) A method for decomposing a polyol or polyol ester according to one aspect of the present invention is a decomposition method in which a substance to be decomposed, which includes at least one of a polyol and a polyol ester, is brought into contact with a solid of a metal oxide or metal hydroxide having a different standard oxidation-reduction potential from water in a predetermined reaction water, wherein the substance to be decomposed is heated to a temperature of 100°C or higher and 250°C or lower while in contact with the solid in the predetermined reaction water.

[0128] (Paragraph 2) The method for decomposing a polyol or polyol ester according to Paragraph 2 is the method for decomposing a polyol or polyol ester according to Paragraph 1, wherein the substance to be decomposed is a polysaccharide which is any of glucose, starch, cellulose, galactose, mannose, arabinose, fructose, sucrose, maltose, lactose, cellobiose, pectin, lignin, xylan, or xylose; a polyhydric alcohol which is any of glycerol, triacetin, glyceride, polyvinyl alcohol, polyester, or ethylene glycol; or an ester of the polysaccharide or the polyhydric alcohol.

[0129] (Article 3) The method for decomposing a polyol or polyol ester according to Article 3 is the method for decomposing a polyol or polyol ester according to Article 1 or Article 2, wherein the solid includes one or more of the following: alumina (Al2O3), silica (SiO2), zeolite (Al2O3・SiO2), titania (TiO2), vanadium pentoxide (V2O5), manganese dioxide (MnO2), iron hydroxide (FeO(OH)), zinc oxide (ZnO), germanium oxide (GeO2), tin oxide (SnO2), lead oxide (PbO2), nickel oxide (NiO2, Ni3O4), and nickel hydroxide (Ni(OH)3).

[0130] In the decomposition methods for polyols or polyol esters described in paragraphs 1 to 3, a solid metal oxide or metal hydroxide having a different standard oxidation-reduction potential from water is placed in a predetermined reaction water. At this time, the reducing agent of the system with a lower standard oxidation-reduction potential readily releases electrons, while the oxidizing agent of the system with a higher standard oxidation-reduction potential readily accepts electrons. Therefore, on the surface of the solid metal oxide or metal hydroxide having a higher standard oxidation-reduction potential than water, water molecules (H2O) are spontaneously oxidized to protons (H2O). + ) and electrons (e - ) and oxygen (O2) are generated, and it is thought that the solid surface (solid-liquid interface) of the metal oxide or metal hydroxide becomes a strongly acidic environment. Furthermore, on the solid surface of the metal oxide or metal hydroxide, which has a lower standard oxidation-reduction potential than water, water molecules (H2O) are spontaneously reduced to hydrogen (H2) and hydroxide ions (OH). - ) occurs, and it is thought that the solid surface (solid-liquid interface) of the metal oxide or the metal hydroxide becomes a strongly alkaline environment.

[0131] However, the strong acidic or alkaline environment occurs only near the solid-liquid interface, and the entire water (bulk) does not become acidic or alkaline. Therefore, in the decomposition methods for polyols or polyol esters described in paragraphs 1 to 3, the substance to be decomposed, which includes at least one of polyols and polyol esters, is brought into contact with the surface of a solid metal oxide or metal hydroxide in a predetermined reaction water, and heated to a temperature of 100°C to 250°C. This causes the substance to be decomposed to undergo hydrolysis.

[0132] Therefore, according to the decomposition method for polyols or polyol esters described in paragraphs 1 to 3, a substance to be decomposed, which includes at least one of a polyol and a polyol ester, can be brought into contact with a solid metal oxide or metal hydroxide having a different standard oxidation-reduction potential from water in a predetermined reaction water, and heated to a temperature of 100°C to 250°C, thereby more easily decomposing the polyol or polyol ester.

[0133] (Paragraph 4) The method for decomposing a polyol or polyol ester according to Paragraph 4 is the method for decomposing a polyol or polyol ester according to any of Paragraphs 1 to 3, wherein the substance to be decomposed is in the form of small pieces.

[0134] (Paragraph 5) The method for decomposing a polyol or polyol ester according to Paragraph 5 is the method for decomposing a polyol or polyol ester according to any of Paragraphs 1 to 4, wherein the solid is in the form of granules or powder.

[0135] According to the decomposition method for polyols or polyol esters described in paragraph 4 or 5, the contact area between the substance to be decomposed and the solid metal oxide and metal hydroxide can be increased, thereby increasing the rate of the hydrolysis reaction.

[0136] (Paragraph 6) The method for decomposing a polyol or polyol ester according to paragraph 6 is the method for decomposing a polyol or polyol ester according to any of paragraphs 1 to 5, wherein the reaction water contains an acid, alkali, salt, or water-soluble oxide.

[0137] According to the method for decomposing polyols or polyol esters described in paragraph 6, the substance to be decomposed, including high molecular weight polyols or polyol esters, can be hydrolyzed to a certain extent in the bulk aqueous phase beforehand to a state with a low molecular weight, thereby improving the efficiency of hydrolysis and changing the ratio of product formation.

[0138] (Paragraph 7) The production method relating to Paragraph 7 involves producing one of the following: a flammable gas, an alcohol, an organic acid, a ketone, an aldehyde, a lactone, an alkane, or an alkene, using a decomposition method for a polyol or polyol ester relating to any of Paragraphs 1 to 6.

[0139] According to the production method described in paragraph 7, industrially useful chemical components such as flammable gases, alcohols, organic acids, ketones, aldehydes, lactones, and alkenes can be easily obtained by decomposing polyols and polyol esters.

Claims

1. A method for decomposing a polyol or polyol ester, comprising contacting a substance to be decomposed, which includes at least one of a polyol and a polyol ester, with a solid metal oxide or metal hydroxide having a different standard oxidation-reduction potential from water in a predetermined reaction water, wherein the substance to be decomposed is heated to a temperature of 100°C or higher and 250°C or lower while in contact with the solid in the predetermined reaction water.

2. The method for decomposing a polyol or polyol ester according to claim 1, wherein the substance to be decomposed is a polysaccharide which is any of glucose, starch, cellulose, galactose, mannose, arabinose, fructose, sucrose, maltose, lactose, cellobiose, pectin, lignin, xylan, or xylose; a polyhydric alcohol which is any of glycerol, triacetin, glyceride, polyvinyl alcohol, polyester, or ethylene glycol; or an ester of the polysaccharide or the polyhydric alcohol.

3. The method for decomposing a polyol or polyol ester according to claim 1, wherein the solid comprises one or more of the following: alumina (Al2O3), silica (SiO2), zeolite (Al2O3・SiO2), titania (TiO2), vanadium pentoxide (V2O5), manganese dioxide (MnO2), iron hydroxide (FeO(OH)), zinc oxide (ZnO), germanium oxide (GeO2), tin oxide (SnO2), lead oxide (PbO2), nickel oxide (NiO2, Ni3O4), and nickel hydroxide (Ni(OH)3).

4. The method for decomposing a polyol or polyol ester according to claim 1, wherein the substance to be decomposed is in the form of small pieces.

5. The method for decomposing a polyol or polyol ester according to claim 1, wherein the solid is in the form of granules or powder.

6. The method for decomposing a polyol or polyol ester according to claim 1, wherein the predetermined reaction water contains any of an acid, alkali, salt, and water-soluble oxide.

7. A method for producing any of the following: a flammable gas, an alcohol, an organic acid, a ketone, an aldehyde, a lactone, an alkane, and an alkene, using a method for decomposing a polyol or polyol ester according to any one of claims 1 to 6.

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