JP7240552B1 - Organic acid production method and organic acid iron production method - Google Patents

Abstract

A method for efficiently extracting and separating organic acids including fulvic acid from waste is provided. SOLUTION: After the organic waste is put into the pressure vessel 1, superheated steam or a mixed gas of superheated steam and saturated steam is supplied into the pressure vessel 1, the pressure vessel 1 is sealed, and the temperature is 100 to 300° C. and the pressure is 0. Organic acids including fulvic acid are extracted from the waste by stirring under conditions of 1 to 4.0 MPa while adjusting the water content with an external heating device and superheated steam (dry steam). Since the steam from the pressure vessel 1 does not contain solid matter and contains a large amount of organic acids including fulvic acid, the steam is sent to the heat exchanger (cooler) 9 through the exhaust steam pipe 8. By cooling, organic acids including fulvic acid are separated and recovered. [Selection drawing] Fig. 2

Description

The present invention relates to a method for extracting organic acids including fulvic acid and pyroligneous acid from organic wastes such as agricultural and forestry wastes under high temperature and high pressure conditions, and producing organic acid iron from the extracted organic acids.
Here, organic wastes include plastics and garbage in addition to agricultural and forestry wastes. Agricultural and forestry wastes include, for example, wood chips containing fulvic acid and waste mushroom beds, as well as fallen leaves and pruned branches of broad-leaved trees.

Fulvic acid is a corrosive substance produced when plants, etc. are decomposed by microorganisms. It is not a single molecule with a fixed chemical structure, but a polyvalent organic acid containing many carboxyl groups and phenolic hydroxyl groups in its molecule. It is a soil improver with excellent chelating power that traps harmful substances by chelating power. When it comes to administration to the human body, although there are few researchers, there are also reports that effects such as curing cancer have been observed because mineral components bound to fulvic acid can be permanently ion-exchanged.

Pyroligneous liquid refers to a liquid obtained by cooling the steam and smoke emitted when burning charcoal, and the acetic acid and alcohol contained in pyroligneous liquid are said to have bactericidal and insect repellent effects. Although it has not yet been clarified what components of pyroligneous acid act, it is said to be useful for improving soil and promoting plant growth.

In addition, iron fulvic acid (iron organic acid) reacts with hydrogen sulfide ions, which are odorous and harmful to organisms, to become harmless iron sulfide. It is said to improve the amount and biodiversity.

Fulvic acid can be produced by extracting humic acid (humic substance) from soil with an alkaline or weak acid alkali salt, and then adding acid to precipitate and separate humic acid. It has been proposed to obtain it from trees with decaying fungi attached, waste mushrooms and wood ear mushroom beds, etc.). Specific prior art includes the following.

In Patent Document 1, a raw material such as wood chips is put into a closed container equipped with a high-temperature and high-pressure steam ejection means, and steam at a temperature of 120 to 250 ° C. and a pressure of 12 to 35 atm is introduced into the closed container, and the raw material is introduced. It is described that a solution containing fulvic acid and humic acid is obtained by performing subcritical water reaction treatment while stirring and cooling.

Patent Document 2 describes a method for producing fulvic acid, in which a fungal bed whose main component is wood chips is enclosed in a container together with wood vinegar, bamboo vinegar, or a mixture of wood vinegar and bamboo vinegar, and the solution is eluted at the bottom of the container. there is

In Patent Document 3, by immersing a solid raw material containing humic substances in alkaline electrolyzed water, fulvic acid and humic acid among the humic substances are extracted into alkaline electrolyzed water, and fulvic acid and humic acid are separated from humin. has been proposed.

Japanese Patent No. 6285605 Japanese Patent No. 6331206 JP 2018-127413 A

In the case of the extraction method using an acid as shown in Patent Documents 2 and 3, the efficiency is low and the problem of post-treatment of the acid used for the extraction also arises. In this regard, the subcritical water reaction treatment disclosed in Patent Document 1 is industrially excellent.

However, Patent Document 1 describes the temperature and pressure of the steam introduced into the sealed container as 120 to 250° C. and 12 to 35 atm.
At the lowest pressure of 12 atm (1.22 MPa), it becomes gaseous when the temperature is 188° C. or higher, and when the temperature is in the range of 120 to 188° C., it is in the state of water (high-temperature water). Moreover, it is even more difficult for water to maintain the vapor state at a pressure of 12 atm or higher.
Taking this into consideration, under the conditions of Patent Document 1, the sealed container is filled with a large amount of condensed water, and most of the treatment is considered to be in liquefied water. In addition, our experiments have shown that when we try to decompose organic substances in liquefied water, the substances that should be in a radical state are stabilized, making it difficult to decompose organic substances.

To decompose a substance, the reactant, that is, water (H ₂ O) is divided into protons (H) and hydroxy groups (-OH), and the combination and separation are repeated to decompose organic substances. Decomposition in water causes a reaction between protons and water to form hydronium (H ₃ O ⁺ ), which slows down the reaction. In addition, the highly hydrophilic hydroxy group also forms a stable substance, slowing down the decomposition of organic matter.

Because fulvic acid is highly soluble in water, it will be found in condensate and solid matter as well as steam. Condensed water contains suspended solids and the like in addition to fulvic acid, and it is difficult to remove suspended solids and the like from this condensed water.

Thus, when fulvic acid is eluted in the subcritical water treatment of Patent Document 1, the water content increases by about 30% or more in terms of weight ratio to the treated substance, most of the fulvic acid is eluted into the condensed water, and diluted fulvic acid The acid solution is discharged and must be separated from large volumes of water to extract the fulvic acid. Similarly, the amount of water treated after separating fulvic acid also increases.

When mushrooms are produced, a "waste mushroom bed" is generated as a residue, which is about two to three times the amount of the edible part. Nakano City, Nagano Prefecture is one of Japan's leading mushroom-producing areas, producing more than 50,000 tons of mushrooms annually.
As a method of consuming these waste fungal beds as waste, bioethanol refining and pelletization have been studied, but the costs involved in recycling are extremely high, and they have not yet been put to practical use.
The simplest method is incineration, but since the combustion energy is low, it is simply burned, which leads to a huge amount of CO2 emissions, and has a large impact on global warming. Considering the fact that the incinerated ash, which is produced by the incinerator, has a considerable impact on the environment, it is difficult to say that it is an appropriate disposal method.
As a result, it was thought that the best method would be to return it to the farmland as compost, which has been practiced in the past. However, since the fungus remains and the raw material of the waste fungus bed is fiber such as sawdust, it contains substances that are extremely difficult to decompose in the natural world. Usually, it takes at least one year or more, and this point becomes a bottleneck, and there is a current situation where the recycling process cannot catch up with the amount of discarded fungal bed.
Therefore, in order to maintain the production of mushrooms, waste mushroom beds are distributed as immature compost, causing serious soil acidification in the surrounding farmlands.
In addition, mushroom fungi remain in the waste mushroom bed, and it is possible to humus ripen even if left unattended. It is very difficult to handle unless you are familiar with it because it has problems such as easy to release and easy to acidify the soil due to its strong acidity.

For these reasons, the treatment of mushroom beds and the like is essential.
Here, the raw material of the mushroom bed is a broad-leaved tree, and since the fungus has already been inoculated, it was found that the amount of fulvic acid increased.
Thinned wood, pruned branches, weeds, etc., which are woody wastes, are difficult to dispose of because they are not distributed as valuables even if they are collected.
If fungi such as rotting fungi are propagated in these abandoned wood-based agricultural and forestry wastes, the elution amount of fulvic acid can be increased.

In order to solve the above problems, the method for producing an organic acid containing fulvic acid and pyroligneous acid according to the present invention involves putting organic waste into a pressure vessel for high-temperature and high-pressure treatment, and adding saturated steam and dry steam ( Superheated steam) is introduced, and the temperature is 100 to 300 ° C and the pressure is 0.1 to 4.0 MPa in a sealed state. After extracting from the organic waste and extracting the vapor containing the organic acid containing the extracted fulvic acid from the pressure vessel, the vapor is cooled to separate the organic acid containing the fulvic acid and pyroligneous acid.

A solid-liquid separator is used to separate the organic acid into a liquid and a solid component containing carbonized substances. Since organic acids including fulvic acid and pyroligneous acid are contained not only in the liquid but also in the solid component, the organic acid may be recovered from the solid component.

In the present invention, organic acids including fulvic acid and pyroligneous acid are mainly extracted from the gas phase, but the organic acids also dissolve in condensed water and solid substances. Organic acids dissolved in the condensed water or solid substances are extracted by centrifugation, vortexing, or the like, and separated from the solid components.

Examples of the organic waste include felled trees, trees with rotting fungi, mushrooms, and waste mushroom beds, but are not limited to these, as long as they contain fulvic acid. In addition, the yield of fulvic acid is higher when fungi such as rotting fungi are propagated.

Further, in the method for producing an organic acid iron from an organic acid according to the present invention, an organic acid containing fulvic acid or pyroligneous acid and ionized iron are put into a pressure vessel for high-temperature and high-pressure treatment, and saturated steam and Superheated steam is introduced, and the organic acid and ionized iron are reacted under the conditions of a temperature of 100 to 300 ° C. and a pressure of 0.1 to 4.0 MPa in a closed state, and an organic acid iron containing iron fulvic acid (chelated iron, divalent iron).

According to the present invention, an organic acid containing high-concentration fulvic acid or pyroligneous acid can be efficiently produced without using an acid or the like. For example, from mixed waste that combines radical substances obtained from wood chips and mushroom waste mushroom beds, fallen leaves and pruned branches, and general organic waste including plastics, solids containing high concentrations of fulvic acid, fulvic acid liquids, and Organic acids such as pyroligneous acid can be freely extracted according to the application.

That is, the moisture content of superheated steam (dry steam) is set to 0.59 to 5.15 kg/m ³ . This amounts to 50-65% compared to the moisture content of saturated steam. In addition, the amount of discharged water, which is condensed water, is about 1/20. More than 35% increase. In addition, by allowing the solid component to absorb water while adjusting the water content with superheated steam or the like, zero water discharge can be achieved.

In addition, the high-temperature and high-pressure treatment equipment is equipped with a moisture adjustment capability and a superheated steam generator, which are not available in conventional subcritical water treatment equipment. It is possible to collect the extract of the state, and the water treatment process is almost unnecessary. Furthermore, since the treatment medium is only water, procurement costs and waste liquid treatment costs are lower than those of acidic substances, etc. At the same time, treatment can be performed in a short period of time, and the treatment capacity per unit time is high. The cost is low, and the initial investment for the equipment is also low.

In addition, by adopting a unique heating structure (double structure) as the pressure vessel for high temperature and high pressure treatment of the present invention, most of the waste water is not polluted, so waste heat can be used, making it an environmentally friendly treatment method. .

According to the present invention, a radical substance forming an organic acid reacts with a carbonyl group and a hydroxy group that bind the radical substance to form a carboxyl group that is a component of fulvic acid, which is bound to the above-mentioned radical substance, and further absorbed. rate increases.

In addition, since protons and hydroxy groups, which are radical substances, move at high speed in the high-temperature and high-pressure tank, the diameter of the carbon component is physically reduced, and a state in which plants can easily absorb it can be created.

Since fulvic acid activates plants and supplies carbon and mineral components, which are the basic constituents of organic matter, at the same time, the plants can grow plants that are resistant and do not wither even in winter.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an overall configuration diagram of a high-temperature and high-pressure treatment system used for producing an organic acid or an organic acid iron according to the present invention; The whole block diagram of the high-temperature/high-pressure processing system which concerns on 2nd Example. Organic acid treatment flowchart. Organic acid iron processing flow chart. The whole block diagram of the high-temperature/high-pressure processing system which concerns on 3rd Example. FIG. 11 is an organic acid treatment flowchart using the system according to the third embodiment. The figure explaining the processing procedure using the system which concerns on 3rd Example.

The high-temperature and high-pressure processing system according to the first embodiment, as shown in FIG. 1, includes a pressure vessel 1 for performing high-temperature and high-pressure processing. A stirring device is arranged inside the pressure vessel 1, an inlet 2 for waste containing fulvic acid, which is a raw material, is provided in the upper center, and an outlet 3 for condensed water, etc. is provided in the lower center. there is

A saturated steam generating boiler 4 is arranged adjacent to the pressure vessel 1, and the saturated steam generated by this saturated steam generating boiler 4 is sent to a superheated steam generator (heating unit) 6 via a pipe 5, and is converted into superheated steam or superheated steam. It is supplied to the pressure vessel 1 through the pipe 7 as a mixed gas of steam and saturated steam. The supply method is not limited to the ceiling portion of the pressure vessel 1, but may be supplied through the hollow shaft of the stirring device.

A steam discharge pipe 8 is led out from the ceiling of the pressure vessel 1 and connected to a heat exchanger (cooler) 9 for removing heat from the steam. The heat (waste heat) absorbed by the heat exchanger (cooler) 9 is circulated to the boiler 4 , and the steam is liquefied in the heat exchanger (cooler) 9 and taken out through the pipe 10 .

FIG. 2 is a general block diagram of a high-temperature and high-pressure treatment system according to another embodiment. In this another embodiment, the pressure vessel 1 has a double structure partially or wholly of the outer shell. Superheated steam or a mixed gas of superheated steam and saturated steam from a superheated steam generator (heating unit) 6 is fed into this double-structured portion through a pipe 11 to prevent uneven heating.

Further, the condensed water generated in the double structure portion is returned to the saturated steam generating boiler 4 through the pipe 12, thereby effectively utilizing the condensed water (energy).
That is, the heat possessed by the steam supplied through the pipe 11 is used to heat only the pressure vessel 1, and the steam passing through the outer double structure does not pass through the inside of the pressure vessel, so it is not polluted. It can be reused while retaining its heat.

In the above, waste generated in agriculture and forestry, such as felled trees, trees with decaying fungi attached, mushrooms and cloud ear waste mushroom beds (preferably, wastes with fungi such as decaying fungi propagated) are fed from the inlet 2 into the pressure tank. Put in 1.

After the waste is put into the pressure vessel 1, superheated steam or a mixed gas of superheated steam and saturated steam is supplied into the pressure vessel 1, sealed, and the temperature is 100 to 300° C. and the pressure is 0.1 to 4.0 MPa. Under the conditions of , stir while adjusting the water content with an external heating device and superheated steam (dry steam). Under the above temperature and pressure, organic acids such as fulvic acid contained in the waste are extracted into the mixed gas. Also, the waste is hydrolyzed to some extent in the pressure vessel 1 .

The amount of water in the pressure vessel 1 must be maintained appropriately. Adjustment of the moisture content is covered by saturated steam, superheated steam and condensed water. If it is judged that the amount of water contained in the waste is excessive, only heating steam is added without adding saturated steam while operating the external heating device. Increase the amount of saturated steam. Also, the processing time varies depending on the amount of waste and the state of decay.

The steam in the pressure vessel 1 does not contain solid matter and contains a large amount of organic acids including fulvic acid. Therefore, the steam after the reaction is sent to the heat exchanger (cooler) 9 through the exhaust steam pipe 8 and cooled to separate and recover organic acids including fulvic acid.

On the other hand, condensed water in which organic acids including fulvic acid are dissolved, and carbonized substances, ash, inorganic substances, etc., which are solid substances, are discharged from the discharge port 3 . Therefore, it is separated into condensed water and carbonized substances by a solid-liquid separator.

The separated carbonized material is used as a fuel or soil conditioner. On the other hand, from the condensed water in which the organic acid containing fulvic acid is dissolved, fulvic acid and humic acid are separately purified, or they are made into the form of organic acid iron which is more easily used.

FIG. 4 is a flow diagram illustrating a means for forming an easily usable form of organic acid iron, and the steam and condensed water from the pressure vessel 1 contain organic acids including fulvic acid. Organic acids including fulvic acid are recovered from these.

Ionized iron is added to the recovered organic acid, and the mixture is put into the pressure vessel 1 again. Then, superheated steam or a mixed gas of superheated steam and saturated steam is supplied into the pressure vessel 1, sealed, and stirred at a temperature of 100 to 300° C. and a pressure of 0.1 to 4.0 MPa. In addition, this step can be reacted even at room temperature, but the time is greatly increased.

By the above-mentioned treatment, the organic acid and iron react with each other to obtain readily available forms of organic acid iron such as chelated iron containing fulvic acid and divalent iron.

5 to 7 show a third embodiment which is a further improvement of the first and second embodiments. The same reference numerals are given to the same members as those of the above embodiment, and the description thereof is omitted.
In this third embodiment, a hopper having a cylindrical lower half is used as a waste inlet 2, and a scoop (stirring) device is arranged inside the pressure vessel 1. As shown in FIG.

In this embodiment, the waste heat of the pressure vessel 1 is used to heat the boiler 4 for generating saturated steam, and the waste heat of the heat exchanger (cooler) 9 is used to heat the pressure vessel 1 .

Furthermore, a heat medium boiler 13 is arranged adjacent to the pressure vessel 1 . This heat medium boiler 13 heats a heat medium sent to an external heating device 14 provided outside the pressure vessel 1 . Oil with a low boiling point, for example, is used as the heat medium. As for the structure of the external heating device 14, the outer shell of the pressure vessel 1 may have a double structure as in the above-described embodiment, or it may be arranged independently outside the pressure vessel 1 separately.

After transferring heat to the pressure vessel 1, the heat medium in the external heating device 14 is returned to the heat medium boiler 13 through the recovery pipe 15, heated in the heat medium boiler 13, and then sent to the external heating device 14 through the pipe 16. sent again.

The heat possessed by the heat transfer medium is used to heat the pressure vessel, and also serves as a heat accumulator that increases the temperature of the treated material and maintains the temperature of the pressure vessel. Since the heat medium does not pass through the inside of the pressure vessel, it is not polluted and circulates while maintaining a temperature of 150° C. or higher and a heat amount corresponding to the amount of heat medium.

In the above, in the third embodiment, agricultural and forestry waste (preferably, fungi such as decaying fungi are propagated) such as felled trees, trees with decaying fungi attached, mushrooms and cloud ear waste mushroom beds, and general organic waste Waste materials are sequentially accumulated in a hopper 2 and introduced into a pressure vessel 1 through an inlet 3.

After the mixed waste is introduced into the pressure vessel 1, the pressure vessel 1 is sealed, and saturated steam, superheated steam, or a mixed gas of superheated steam and saturated steam is supplied into the pressure vessel 1 at a temperature of 100 to 300° C. and a pressure of 0.1. Under the condition of up to 4.0 MPa, hydrolysis is performed while adjusting the water content with the external heating device 14 and superheated steam (dry steam) and uniformly touching the steam with the scoop function.

In the reaction within the pressure vessel 1, carbonyl groups and hydroxyl groups constituting the mixed waste are combined to form carboxyl groups, which are constituents of organic acids. This increases the production of organic acids.

Since the reaction performed in the pressure vessel 1 is a hydrolysis reaction, an appropriate amount of water is required to maintain saturated steam and dry steam, but these are saturated steam, superheated steam, condensed water, and decomposed It is covered by the moisture content of the If it is judged that the amount of water contained in the waste is excessive, only superheated steam is added without adding saturated steam while operating the external heating device. Increase the amount of saturated steam. Also, the treatment time varies depending on the amount of persistent waste, the state of decay, the state of discharge, and whether it is liquid or solid.

After the hydrolysis treatment in the pressure vessel 1 is completed, the product after the reaction is taken out from the discharge port 3 . From the discharge port 3, condensed water containing fulvic acid, etc., and carbonized substances, which are solids containing fulvic acid, etc., are discharged. is discharged. For this reason, the condensed water and the carbonized substance are sometimes separated by a solid-liquid separator.

The separated solid matter is used as a soil conditioner containing fuel and fulvic acid. On the other hand, from the condensed water containing fulvic acid and the like, fulvic acid and humic acid are separately purified, or they are made into the form of organic acid iron which is more easily used.

The steam that has undergone the hydrolysis treatment in the pressure vessel 1 does not contain solid matter, but contains a large amount of fulvic acid and the like. Therefore, the steam after the reaction is sent to the heat exchanger (cooler) 9 through the exhaust steam pipe 8 and cooled to separate and recover fulvic acid and the like.

FIG. 6 is a flow chart explaining the means for making the form of organic acid iron that is easy to use, and the steam and condensed water after the hydrolysis treatment in the pressure vessel 1 contains fulvic acid and the like. . Fulvic acid and the like are recovered from these.

In the second step (step of making organic acid iron from organic acid such as fulvic acid), as shown in FIG. Then, saturated steam, superheated steam, or a mixed gas of superheated steam and saturated steam is supplied into the pressure vessel 1, sealed, and scooped under conditions of a temperature of 100 to 300 ° C. and a pressure of 0.1 to 4.0 MPa. By, organic acid iron can be produced. In addition, this step also reacts at room temperature, but in that case, the time is greatly increased.

By the above treatment, the organic acid and iron react with each other to obtain readily available forms of organic acid iron such as fulvic acid iron, chelated iron, and divalent iron.

DESCRIPTION OF SYMBOLS 1... Pressure tank, 2... Waste inlet, 3... Condensed water outlet, 4... Saturated steam generating boiler, 5... Piping, 6... Superheated steam generator (heating unit), 7... Piping, 8... Exhaust steam piping 9 Heat exchanger (cooler) 10 Piping 11 Piping from external heating device 12 Energy circulation piping to boiler 13 Heat medium boiler 14 External heating device 15 ... collection piping, 16 ... piping.

Claims (5)

Put the organic waste into a pressure vessel for high-temperature and high-pressure treatment, introduce saturated steam and superheated steam into the pressure vessel, and seal it under conditions of a temperature of 100 to 300 ° C. and a pressure of 0.1 to 4.0 MPa. Then, the organic acid containing fulvic acid is extracted from the organic waste into the mixed steam of the saturated steam and the superheated steam by stirring in the steam whose moisture content is adjusted with the superheated steam, and the extracted organic acid A method for producing an organic acid, characterized in that the vapor containing is taken out from the pressure vessel and cooled, and the organic acid is obtained from the liquid substance after cooling. 2. In the method for producing an organic acid according to claim 1, the extraction of the organic acid in the pressure vessel activates the movement of protons and hydroxyl groups in the gas phase, bonds the carbonyl group and the hydroxyl group, and produces the organic acid. A method for producing an organic acid, characterized in that a carboxyl group, which is a constituent, is formed, thereby increasing the amount of production of the organic acid. 2. The method for producing an organic acid according to claim 1, wherein the liquid organic acid and the organic acid contained in the solid substance are arbitrarily extracted by controlling the moisture content of the steam. Method. 2. The method for producing an organic acid according to claim 1, wherein a heating device is provided outside said pressure vessel so that said pressure vessel is also heated from outside. Ionized iron is added to the organic acid obtained by the method according to claim 1, then the organic acid to which the ionized iron is added is put into a pressure vessel for high-temperature and high-pressure treatment, and saturated steam and superheated steam are introduced into this pressure vessel. Then, in a sealed state, the organic acid and ionized iron are reacted in steam conditioned at a temperature of 100 to 300 ° C. and a pressure of 0.1 to 4.0 MPa, and an organic acid iron containing iron fulvic acid (chelated iron, di A method for producing an organic acid iron, characterized by obtaining a valuable iron).

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