WO2002064274A1

WO2002064274A1 - Method of recoverying garbage and waste materials into resources

Info

Publication number: WO2002064274A1
Application number: PCT/JP2002/001339
Authority: WO
Inventors: Kenji Mishima
Original assignee: Itec Co., Ltd.
Priority date: 2001-02-16
Filing date: 2002-02-15
Publication date: 2002-08-22
Also published as: JP2004188229A

Abstract

A method of producing organic acids such as gluconic acid from wastes such as garbage and waste materials at a high selectivity, a high speed and a high yield to thereby efficiently utilize the wastes as resources. In producing organic acids such as gluconic acid from wastes such as garbage and waste materials, an inorganic salt such as calcium carbonate or magnesium carbonate is added to carry out a hydrothermal reaction. Thus, cellulose and glucose contained in the starting materials are selectively decomposed at a high speed and a high yield to thereby give organic acids such as gluconic acid. These organic acids thus produced are used as materials for biodegradable polymers.

Description

Specification

Method of recycling garbage and waste materials

The present invention uses a hydrothermal reaction (a method of synthesizing and growing crystals in the presence of high-temperature, high-pressure water) to produce garbage, waste materials, and paper waste discharged from the home, food industry, and agricultural and livestock industries. The present invention relates to a method for recycling garbage and waste materials for producing organic matter such as dalconic acid from waste containing cellulose or glucose such as waste paper and fiber chemical products, and a method for using the organic matter produced thereby. Conventional technology

Currently, garbage, starch, sugar, wood, and other waste materials, household waste, waste paper, waste paper, textiles, chemical fibers, and other waste from the household, food industry, and agricultural and livestock industries are mainly incinerated and landfilled. Have been done. However, incineration requires large-scale facilities, and also causes environmental pollutants such as dioxins and odors. In addition, there is a shortage of landfills for landfilling of garbage. In some cases, a method has been proposed in which compost is not directly disposed of but recycled as compost.However, the method of recycling raw garbage as compost takes a long time to process, and the demand for compost and the raw garbage to be processed Due to the imbalance in quantity, it is not an effective solution from the viewpoint of resource recycling.

On the other hand, organic acids such as dalconic acid have a great demand in the chemical and food industries as a raw material for various useful substances, and can be used as a raw material for biodegradable plastics that are degraded in the natural environment. There is a strong need for cost reduction.

The industrial production of dalconic acid from glucose has conventionally been carried out by fermentation, but fermentation requires about 12 hours for fermentation and the productivity is poor. There have been proposed various methods for oxidizing the compound in a short time. However, most of this method is described in, for example, Japanese Patent Application Laid-Open No. 55-23030, Japanese Patent Application Laid-Open No. 62-228103, Japanese Patent Laid-Open No. As shown in the publications of 3—7 6 29 9 and Japanese Patent Publication No. 4-199 9 85, a method of oxidizing glucose in an aqueous solution with oxygen or an oxygen-containing gas in the presence of a noble metal catalyst. Dalconic acid can be produced in about 4 hours. A method has also been reported that can efficiently produce dalconic acid from glucose without using a catalyst. In this method, an enzyme oxidation catalyst, glucose oxidase and catalase are added to an aqueous glucose solution, and the aldehyde group of glucose is oxidized to a carboxyl group by the former while supplying oxygen or an oxygen-containing gas. The public corporation decomposes hydrogen peroxide, a by-product of the process, to prevent the former from participating, and maintain the activation of the former to produce dalconic acid by an enzymatic reaction.

In these methods, when the enzyme is directly added to and dispersed in an aqueous solution, the separation from dalconic acid is complicated as in the case of the fermentation method.In addition, catalase is inactivated by replicating hydrogen peroxide, Due to insufficient decomposition, the concentration of hydrogen peroxide gradually increased over the course of the reaction, causing the problem of inactivating glucose-rich oxidase.

As described above, conventional production of dalconic acid from glucose is based on microbial luminescence, electrochemical, chemical, and enzymatic (enzymatic systems are used by separating them from the microbe (s) that are their source. It can be implemented using processes that can be broadly classified as any of the systems. Despite the most widespread use of microbial fermentation in these methods, microbial fermentation has drawbacks associated with slow reaction times and processing conditions required for the fermenting microorganism used. It has a number of disadvantages, limiting its commercial applicability.

In an attempt to produce an organic acid such as lactic acid-succinic acid using garbage as a raw material, a method for producing an organic acid as disclosed in Japanese Patent Application Laid-Open Nos. A method for producing lactic acid using organic waste as a raw material as shown in 11-285397, a method for treating garbage as shown in Japanese Patent Application Laid-Open No. 2000-3109419 There are resource methods that have waited for cell fermentation.However, even with these methods, it takes time to manufacture, and when processing large quantities, the processing tank becomes too large. Had a problem.

On the other hand, there are wet oxidation methods, supercritical water decomposition methods, supercritical water oxidation methods, etc., as wet processing techniques for organic substances, and hydrothermal solidification methods, etc., as detoxification techniques for residues. In these methods, for example, an apparatus for continuous hydrothermal oiling of hard-to-break waste as disclosed in Japanese Patent Application Laid-Open No. H10-080805, and a method disclosed in Japanese Patent Application Laid-Open No. 08-332479 is disclosed. A method for decomposing organic chlorine waste, gasification of plastic as disclosed in Japanese Patent Application Laid-Open No. 06-29169, and the like are disclosed. There were no reports that organic acids were produced from raw materials.

In addition, straw, stalks, sugarcane marc are treated with lime, and microbes living in cattle are mixed and fermented under oxygen-free conditions. Attempts have been made to produce and use it as a raw material for chemical products (Chang, VS, Burr, B. and Hoitzapple, MT, Apply.Biochem.Biotech., 63-5, 3-19, (1997)). However, these methods make it difficult to achieve anoxic conditions and produce a large amount of by-products other than the target substance, resulting in poor selectivity. There is a disadvantage that the production is costly.

In view of the above, the present invention is a technology for selectively producing organic acids such as dalconic acid from waste such as garbage and waste materials at high speed and with high yield, and effectively utilizing the produced organic acids such as dalconic acid. The purpose of the present invention is to provide the following and is characterized by the following configuration.

Disclosure of the invention

That is, in the present invention, organic waste such as dalconic acid is removed from waste such as garbage and waste materials. In the method of manufacturing a product, dalconic acid is selectively decomposed at high speed and high yield by decomposing cellulose and glucose contained in raw materials by adding an inorganic salt such as calcium carbonate and conducting a hydrothermal reaction. And other methods for producing organic acids.

In addition, the gist of the present invention is that, in the above-described method, dalconic acid is produced with higher yield by adding an acid such as hydrochloric acid or an additive such as carbon dioxide to high-temperature and high-pressure water. There is also.

The additives used in the present invention are not particularly limited, and for example, substances that generate inorganic salts such as calcium carbonate, magnesium carbonate, barium carbonate, sodium carbonate, calcium acetate, and sodium acetate can be used.

The high-pressure fluids such as water and carbon dioxide, supercritical fluids, high-pressure gases and liquids used in the present invention are different from dimethylformamide-tetrahydrafuran in chemical species such as liquids and other solvents and gases. No worries about

The raw material used in the present invention is not particularly limited, and may include waste containing a basic skeleton of cellulose and glucose. This includes, for example, at least one or more of the waste containing cellulose or glucose, such as garbage, waste, waste paper, waste paper, fiber, and chemical products from the household, food industry, and agricultural and livestock. Can raise substances.

A technical feature of the present invention is that an inorganic salt such as calcium carbonate is added when utilizing the high decomposability of high-temperature, high-pressure water, and thus, organic acids such as dalconic acid have been conventionally used. Organic acids such as dalconic acid can be selectively produced from waste such as garbage, which was not considered to be produced, at high yields.

In the present invention, the temperature for hydrothermal decomposition is from 37.3 K to 52.3.15 K, especially 47.8.15. To 48.3.15Κ. It is preferable in that it can be manufactured in a special way.

BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a graph showing the relationship between the yield of dalconic acid obtained by the present invention and the amount of added calcium carbonate, and FIG. 2 is a graph showing the relationship between the yield of dalconic acid obtained by the present invention and the added amount of carbon dioxide. It is a figure showing a relation.

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1

In a reaction vessel containing a stirrer, 0.5 g of a dried sample of the cellulose-containing material and calcium carbonate as an additive were added, and then about 3.0 Og of distilled water was added with a syringe.

After the inside of the reaction vessel was replaced with nitrogen, the reaction vessel was shaken well, water was mixed well with the experimental sample, the reaction vessel was placed in a preheating salt bath (low-temperature salt bath), and then shaken until the temperature was stabilized. After 1 minute, it was immediately placed in a salt bath for reaction (high-temperature salt bath) to start the reaction. At this time, the reaction vessel was continuously shaken. When the reaction time had come, the reaction was taken out, immediately put in a water bath and rapidly cooled to stop the reaction. When the temperature dropped to 30.15 K inside the reaction vessel, the reaction was deemed to have been completed, and the reaction vessel was removed from the water bath.

A beaker was prepared below the reaction vessel, the reaction vessel was removed, and the contents were transferred to a beaker. At this time, distilled water was poured from a replacement valve to collect the reactant blown up to the upper part of the reaction vessel. The solid remaining in the reaction vessel was collected in a beaker using a microspatula and washed with distilled water. Pour the liquid in the suction bottle into a flat-bottomed flask set in a rotary evaporator, and reduce the pressure in the reaction solution in a constant temperature water tank set at 33. I flew the water. Thereafter, the outside of the flat-bottomed flask was wiped with paper moistened with acetone, dried, and collected in a sample tube.

The degradation products were quantitatively analyzed using high performance liquid chromatography. The results were: conversion (%): 100, dalconic acid yield (%): 90, and by-product yield (%): 10

Selective use of dalconic acid using a hydrothermal reaction involving inorganic salts such as calcium carbonate It was shown that it can be manufactured. In addition to dalconic acid, the formation of organic acids such as malic acid and pyruvate was also confirmed. Also, by controlling the reaction conditions, the type and concentration of the substance to be produced could be adjusted.

Example 2

An experiment was performed in the same manner as in Example 1, except that calcium carbonate was used as an additive. Figure 1 shows the effect of adding calcium carbonate.

It was shown that the yield of dalconic acid can be controlled by controlling the amount of calcium carbonate added. As can be seen from FIG. 1, the optimal amount of inorganic salt added is 1%.

Example 3

Hydrothermal reaction was performed by introducing carbon dioxide in the same manner as in the example. In addition, calcium carbonate was used as an additive. Figure 2 shows the effect of adding carbon dioxide.

It was shown that the addition of carbon back oxide increased the yield of dalconic acid. This indicates that dalconic acid can be produced more efficiently by introducing carbon dioxide.

Example 4

Hydrothermal reaction was conducted by introducing an acid such as hydrochloric acid in the same manner as in Example 1, and as a result, it was confirmed that dalconic acid could be produced by adding hydrochloric acid. This shows that the introduction of an acid can produce dalconic acid more efficiently.

Example 5

Polydalconic acid, polydarconolactone and the like were produced from the dalconic acid synthesized in the present invention as a raw material. The produced substance became a brownish solid, and the production of polydalconic acid and polydarconolactone was confirmed.

ADVANTAGE OF THE INVENTION According to the present invention, dalcon is selectively and rapidly and with high yield from resources including cellulose or glucose such as garbage, waste materials, waste paper, waste paper, fiber, and chemical products discharged from the household, food industry, agricultural and livestock. Organic acids such as acids can be produced. Also made Biodegradable plastics and the like can be produced from the produced organic acids. Further, the produced organic acid can be used as a raw material for a cleaning agent, a drier, a cement aid, a dentifrice composition, a developer composition, a food additive, a food preservative, and a mouthwash.

Claims

The scope of the claims

1. Add inorganic salts to resources such as garbage, waste materials, waste paper, waste paper, textiles, chemicals, and other cellulose- or glucose-containing resources discharged from the household, food industry, and agricultural and livestock industries. A method for recycling garbage and waste materials, comprising selectively decomposing cellulose and glucose contained therein to produce organic acids such as gluconic acid, pyruvic acid and malic acid.

2. The raw material according to claim 1, wherein the additive is at least one selected from the group consisting of inorganic salts such as calcium carbonate, magnesium carbonate, barium carbonate, sodium carbonate, calcium acetate, and sodium acetate. How to recycle garbage and waste materials.

3. The method for recycling garbage and waste materials according to claim 1, wherein the yield of organic acids is increased by adding a compound having an acid such as hydrochloric acid or carbon dioxide.

4. The method according to claim 3, wherein the additive is at least one selected from the group consisting of compounds having an acid such as acetic acid, hydrochloric acid, and sulfuric acid.

5. The organic acid produced by the method according to claim 1 is used as a biodegradable plastic material, a detergent, an antibacterial agent, a cement aid, a dentifrice composition, a developer composition, a food additive, a food. How to use organic acids for preservatives, mouthwashes, etc.