JP2021170981A - Method for producing useful substance using livestock manure burning ash and plant biomass, and useful substances produced by this manufacturing method - Google Patents

Abstract

To provide a method for producing a useful substance from livestock manure burning ash and plant biomass and to provide a useful substance produced by the method.SOLUTION: A method for producing a useful substance comprises mixing and reacting livestock manure burning ash and plant biomass in the presence of water. The useful substance is produced by the method for producing the useful substance.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a useful substance using livestock manure burning ash and plant biomass and a useful substance produced by this production method, and relates to a technique for producing a useful substance from livestock manure burning ash and plant biomass.
More specifically, the technique of the present invention relates to livestock manure burning ash as a by-product obtained after weight reduction treatment (and energy recovery) of livestock manure biomass such as chicken manure, pig manure, and cow manure. Regarding modification / purity improvement and advanced utilization of calcium. Further, the technique of the present invention relates to a wet storage / pretreatment technique for the purpose of expanding the use of agricultural residues such as rice straw and plant biomass mainly for cellulosic resource crops.

Livestock manure derived from chickens, pigs, cows, etc., if left untreated, causes foul odors due to alteration of the nitrogen source and greenhouse gases such as dinitrogen monoxide, and is discarded because it is routinely discharged during breeding. Since a large amount of substances are produced, there are an increasing number of cases in which calcium carbonate, wood, etc. are mixed as necessary and then used for the production of thermal energy, etc. by combustion, in order to suppress malodor and reduce the weight.
Since the livestock manure burning ash obtained by this treatment is rich in potassium, calcium and phosphorus, it is expected to have fertilizer value and feed value.
In particular, the recycling of phosphorus in feces and urine is attracting attention as an important process in resource recycling, and the development of effective phosphorus recycling technology from the obtained livestock manure burning ash is underway.
In that case, the coexistence of potassium in the ash becomes a problem in stabilizing the fertilizing effect of phosphorus (see Non-Patent Document 1). When the phosphorus present in the ash is recovered, it is generally dissolved by acid treatment, but the calcium salt coexisting in the ash wastes the acid.

On the other hand, since livestock manure burning ash is alkaline, there is a concern about environmental impact when directly using fertilizer. This alkalinity is thought to be mainly due to the abundance of calcium.
Therefore, a livestock manure burning step at a relatively low temperature has been proposed in which the improvement of alkalinity is suppressed by suppressing the change from calcium carbonate to calcium oxide (see Patent Document 1).
Furthermore, there is a need for technology for using this alkali that contributes to advanced resource recycling in the region.

On the other hand, plant biomass obtained as agricultural waste and food production by-products such as rice straw, straw, corn stover, and sugar cane bagasse is required to be highly utilized as an organic resource other than fertilizer and feed. In particular, there are high expectations for conversion to biofuels or plastic alternatives to reduce dependence on fossil resources. At the beginning of the 21st century, it attracted attention as a raw material for producing ethanol for second-generation fuels, and competition for technological development was fought in each country.
Such plant biomass contains polysaccharides such as cellulose as fibrous polysaccharides.
Therefore, efforts have been made to recover water-soluble oligosaccharides and monosaccharides obtained by reducing the molecular weight of these substances and convert them into valuable resources such as ethanol and lactic acid.

Plant biomass is composed of a strong cell wall containing lignin, and in order to reduce the molecular weight of polysaccharides existing in the cell wall, pretreatment with acid, alkali, high-temperature water treatment or the like is required.
In addition, in the case of agricultural waste that is produced all at once during the harvest season, raw material storage and year-round supply are required to operate the conversion system efficiently. In order to store raw materials obtained in a wet state in areas where sun drying or forced drying is difficult, it is important to introduce a simple wet storage technique.
In the case of plant biomass containing a large amount of easily degradable sugar, wet storage is performed using silage technology that induces a decrease in pH by lactic acid fermentation, but for raw materials that do not contain a large amount of easily decomposable sugar. There is a need to develop a simple wet storage technology that can also be applied.

Furthermore, as for plant biomass, rice straw, straw, bagasse, bamboo, etc., which are known as straw paper, have been used as pulp, and hemp has been used as fiber for a long time. In recent years, high-performance fiber materials such as cellulose nanofibers have been attracting attention.
Currently, the development of applications for cellulose nanofibers is being energetically promoted mainly in Japan, so the supply range will be expanded so that various plant biomass in each region can be used as a unique fiber raw material. Is important.

By the way, in order to recover phosphorus from livestock manure combustion ash, the combustion ash is reacted with an aqueous sulfuric acid solution to solubilize the phosphoric acid, and after sufficiently washing and removing calcium as a plaster, calcium hydroxide is added. A method of precipitating again has been developed (see, for example, Patent Documents 2 and 3).
In addition, a method has been proposed in which a solution obtained by reacting combustion ash such as chicken manure with hydrochloric acid is brought into contact with a phosphoric acid collecting material coated with polyvinyl alcohol crosslinked with a zirconium compound to adsorb and recover phosphorus. (See Patent Document 4).

On the other hand, regarding plant biomass, in the old days, when producing pulp from raw materials such as mulberry and mitsumata, a process of boiling with wood ash was adopted, but a process of producing pulp of livestock manure burning ash has not been studied.
In addition, calcium hydroxide pretreatment, which is one of the pretreatments for improving the saccharification property of plant biomass, has an advantage that calcium hydroxide is cheaper than sodium hydroxide and ammonia and is easy to handle. It becomes.
In particular, by mixing plant biomass and calcium hydroxide and storing them at room temperature after sealing, putrefaction is suppressed by high pH, storage in a wet state becomes possible, and the structure can be altered. For example, as shown in Patent Document 5, it is known that the enzyme saccharification efficiency after pH adjustment is improved.

In these phosphorus recovery methods, all alkalis in livestock manure combustion ash are neutralized with sulfuric acid or hydrochloric acid, and then phosphoric acid is eluted and recovered through reprecipitation or adsorption. In that case, livestock manure burning Large amounts of calcium salts that are thought to exhibit the appearance of calcium carbonate or calcium oxide in the ash will also react with the acid.
After this reaction, calcium sulfate becomes water-insoluble gypsum and calcium chloride becomes an electrolyte and solubilizes, but in the above-mentioned prior arts related to phosphorus recovery, advanced utilization technology of these products is mentioned. Since there is no such technology, it is considered that it will be discarded without being highly utilized, as with other industrial technologies.

As described above, in the above-mentioned prior art, it is necessary to add a large amount of acid corresponding to the amount in order to neutralize the calcium salt contained in a large amount before dissolving the phosphoric acid in the livestock manure burning ash. Not only that, but the problem is that the industrial utility value of salts such as gypsum and calcium chloride contained in the neutralized product is low.
It is considered that calcium salts bound to phosphoric acid, calcium carbonate and calcium oxide are mainly present as calcium salts in livestock manure burning ash.

When this livestock manure burning ash is suspended in water, most of the potassium salts dissolve, so when using livestock manure burning ash as fertilizer, the total amount of fertilizer applied can be adjusted by mixing two types of fertilizers, potassium and phosphorus. The required problem is that after suspending livestock manure burning ash in water, the insoluble fraction is improved as a phosphate-rich fraction (see, for example, Patent Document 6), and the aqueous fraction is potassium-rich. It is improved by collecting (see, for example, Patent Document 7).
On the other hand, since calcium salts have extremely low water solubility in both carbonates and hydroxides, it is extremely difficult to significantly reduce the calcium / phosphorus ratio by the water suspension and washing steps.

A method of adding phosphoric acid or silicic acid has been proposed as a method for treating livestock manure burning ash in order to effectively give fertilizer value while reducing the strong alkalinity of livestock manure burning ash (for example, patent). Refer to Documents 8 and 9).
However, these methods require the acid to be brought in from the outside when preparing the fertilizer, which limits the component properties and uses of the product. In order to flexibly use phosphoric acid in the production area of livestock manure combustion ash, it is necessary to reduce the alkalinity and improve the applicability in the phosphoric acid purification process by the conventional method such as acid extraction.

Further, in the wet storage / pretreatment technique of plant biomass using calcium hydroxide (see Patent Document 5 above), a mixture of both is left to stand for a long period of time in a sealed state.
Assuming a large-scale conversion process, a raw material storage facility can be constructed to store carbon dioxide in the air under conditions that are blocked.
On the other hand, when performing simple sealed storage outdoors, as in silage manufacturing, a method of stuffing into a silo and consolidating it, a method of covering it with a sheet for a bunker silo after stacking, or a rappy silo-like portability. The method by the one with a high price will be adopted.

However, these coating / packaging materials do not have high carbon dioxide blocking properties. Then, the gradual reaction between carbon dioxide in the air and calcium hydroxide causes the pH to rapidly drop to near neutrality, which causes the growth of mold. In addition, air is exchanged from the gaps during coating and packaging, and there is concern about the same problem.

Under these circumstances, there is a demand for wet storage / pretreatment technology that can reduce the risk of a decrease in alkalinity during storage.
In addition, calcium hydroxide, which is industrially synthesized from fossil resources, has a large environmental load during manufacturing, and when it is continuously transported, procured and used, it becomes an obstacle in increasing the environmental value of the product. ..

Japanese Unexamined Patent Publication No. 2012-92270 Japanese Unexamined Patent Publication No. 2014-117241 Japanese Unexamined Patent Publication No. 2012-201722 Japanese Unexamined Patent Publication No. 2011-78870 Japanese Unexamined Patent Publication No. 2011-4730 Japanese Unexamined Patent Publication No. 2005-126252 Japanese Unexamined Patent Publication No. 2019-147717 Japanese Unexamined Patent Publication No. 2013-253000 Japanese Unexamined Patent Publication No. 2010-202491

Yukio Chiba et al., "Use of incinerated chicken manure ash", Tohoku Agricultural Research, 39, 139-140 (1986).

An object of the present invention is to provide a method for producing a useful substance from livestock manure burning ash and plant biomass.
Another object of the present invention is to provide a useful substance produced by the above method.
In other words, it is an object of the present invention to provide a technique for modifying and improving the purity of phosphorus, which is the main component of the combustion ash of livestock manure, and highly utilizing calcium.
Another object of the present invention is to provide a wet storage / pretreatment technique for expanding the use of agricultural residues such as rice straw and plant biomass mainly for cellulosic resource crops.

As a result of diligent studies to solve the above problems, the present inventors transfer calcium in livestock manure combustion ash, which has low solubility in water, into the plant biomass or solution in the coexistence of plant biomass. I confirmed the phenomenon.
Then, (1) after recovery and drying of the fraction containing the component derived from livestock manure burning ash as the main component after this treatment, the calcium / phosphorus ratio and the potassium / phosphorus ratio are higher than those of the original livestock manure burning ash. It decreases, and the alkalinity decreases accordingly, and (2) after recovery and pH adjustment of the fraction containing the component derived from the plant biomass after this treatment as the main component, the enzyme is compared with the original plant biomass. By confirming that the saccharification efficiency and the dissociability of the fibers are increased, it was found that the ash and the plant biomass were modified by one migration phenomenon, and the present invention was completed based on this finding.

That is, the present invention relates to the following (1) to (14).
(1) The present invention relates to a method for producing a useful substance, which comprises mixing livestock manure burning ash and plant biomass in the presence of water and reacting them.

(2) The reaction is carried out by at least one of a method of heating a mixture of livestock manure burning ash, plant biomass and water, or a method of holding the mixture without heating for 1 day or more. 1) Regarding the method for producing a useful substance described in 1).

(3) The method for producing a useful substance according to (1) or (2) above, which comprises a step of recovering a useful substance from the reaction product obtained by the reaction.

(4) The step of recovering useful substances is a fraction in which water is added after the reaction and the main component is a water-insoluble inorganic substance derived from the livestock manure combustion ash, and a fraction containing the water-insoluble component derived from the plant biomass as a main component. The present invention relates to the method for producing a useful substance according to (3) above, which comprises a step of solid-solid separation of biomass.

(5) The usefulness according to any one of (1) to (4) above, wherein the useful substance is a fraction produced after the reaction and containing a water-insoluble inorganic substance derived from the combustion ash of livestock manure as a main component. Regarding the manufacturing method of substances.

(6) The useful substance according to any one of (1) to (4) above, wherein the useful substance is a fraction generated after the reaction and containing a water-insoluble component derived from the plant biomass as a main component. Regarding the manufacturing method.

(7) The present invention relates to a useful substance produced by the method for producing a useful substance according to any one of (1) to (6) above.

(8) Among the useful substances, the dried product of the fraction containing the water-insoluble inorganic substance derived from the livestock manure burning ash as the main component has a low calcium / phosphorus ratio as compared with the value of the livestock manure burning ash before the reaction. The useful substance according to (7) above.

(9) Among the useful substances, the dried product of the fraction containing the water-insoluble inorganic substance derived from the livestock manure burning ash as the main component has a low potassium content as compared with the value of the livestock manure burning ash before the reaction. It relates to the useful substance according to (7) or (8) above.

(10) Among the useful substances, the dried product of the fraction containing the water-insoluble inorganic substance derived from the combustion ash of livestock manure as the main component has the same phosphorus amount when it is suspended in water and an acid is added. The useful substance according to any one of (7) to (9) above, which exhibits the property of dissolving phosphorus with a smaller amount of acid added as compared with the value in the combustion ash of livestock manure before the reaction.

(11) Of the useful substances, the dried product of the fraction containing the water-insoluble inorganic substance derived from the combustion ash of livestock manure as the main component has the same phosphorus amount when it is suspended in water and an acid is added. The useful substance according to any one of (7) to (10) above, which exhibits the property of dissolving phosphorus at a higher pH as compared with the value in the combustion ash of livestock manure before the reaction.

(12) The useful substance according to (7) above, wherein a fraction of the useful substances containing a water-insoluble inorganic substance derived from the combustion ash of livestock manure or a dried product thereof is used as a phosphorus supply source.

(13) Of the useful substances, the fraction containing the water-insoluble component derived from the plant biomass as the main component or a dried product thereof is compared with the value of the plant biomass before the reaction, and the enzyme of the cell wall polysaccharide after pH adjustment. The useful substance according to (7) above, which has improved saccharification efficiency.

(14) Of the useful substances, the fraction containing the water-insoluble component derived from the plant biomass as a main component or a dried product thereof has a dissociative property of the fibrous constituents of the plant tissue as compared with the plant biomass before the reaction. (7) or the useful substance according to the above (13), wherein the above (7) or (13) is improved.

According to the present invention, useful substances can be obtained from livestock manure burning ash and plant biomass.
That is, according to the present invention, the main component of phosphorus is modified with respect to livestock manure burning ash as a by-product obtained after weight reduction treatment (and energy recovery) of livestock manure biomass such as chicken manure, pig manure, and cow manure. -Purity can be improved and calcium can be highly utilized.
Further, according to the present invention, it is possible to provide a wet storage / pretreatment technique for agricultural residues such as rice straw and plant biomass centered on cellulosic resource crops, and to expand the applications thereof.

In Test Example 4, it is a graph which shows the relationship between the alkali concentration before heat treatment at the time of reaction of chicken manure burning ash and rice straw powder, and the enzyme saccharification yield of the treated rice straw produced after reaction. FIG. 5 is a graph showing the results of an enzyme saccharification test (48 h) using rice straw recovered after treatment with chicken manure burning ash under each condition in Example 4. In Example 5, the phosphoric acid solubilization rate (FIG. 3A) when hydrochloric acid was added to the suspension of chicken manure burning ash A (PA) or treated ash A (PTA) and the measured pH value of the suspension under each treatment condition. It is a graph which shows the relationship between and a phosphate solubilization rate (FIG. 3B), respectively.

Hereinafter, embodiments of the present invention will be described in detail.
The first embodiment relates to a method for producing a useful substance.
The method for producing a useful substance according to the first embodiment is characterized in that livestock manure burning ash and plant biomass are mixed and reacted in the presence of water.
According to the method for producing a useful substance according to the first embodiment, livestock manure burning ash is reformed and plant biomass is also reformed.

Here, the livestock manure used as a raw material for the livestock manure burning ash is preferably, but is not limited to, manure derived from chicken, pig, cow, sheep and horse.
As livestock manure, for the purpose of improving combustion characteristics, storage, etc., if necessary, it is possible to use livestock manure whose water content has been reduced and its volume has been reduced through sun drying, forced drying, fermentation treatment, etc. ..
Livestock manure generates greenhouse gases such as dinitrogen monoxide as sun drying, fermentation and composting progress, so it is burned to generate heat energy, and livestock manure burning ash is utilized to create an environment. The load can be reduced.
In addition, if necessary, at the start of combustion, woody components such as sawdust may be added to the livestock manure combustion ash for the purpose of adjusting the water content and combustion characteristics, or calcium carbonate or the like may be added to adjust the combustion characteristics. Conditioners can be added and multiple types of livestock manure can be mixed.
As described above, the first ash also contains ash derived from substances added to ensure desirable combustion characteristics during combustion of livestock manure and charcoal-containing substances that may be mixed due to incomplete combustion thereof. Included in livestock manure burning ash in embodiments.

Then, an ash in which a plurality of types of livestock manure burning ash are mixed (for example, a mixture of two or more kinds of different livestock manure burning ash such as chicken manure burning ash and cow manure burning ash, and chicken manure burning ash are also chicken manure types. However, a mixture of two or more types of combustion ash) can also be used.
The description of elements such as potassium, calcium, and phosphorus shown in the present specification includes those in the ionic state or in the form of salts.

Examples of the device used for producing livestock manure combustion ash include, but are not limited to, a rotary kiln furnace, a fluidized bed furnace, a stoker furnace, a swivel incinerator, and a fixed bed furnace.
In the device used for producing livestock manure combustion ash, it is preferable to supply 1.0 times or more of the theoretical air amount to the material and completely burn it in order to suppress carbonization of organic matter.
In addition, the equipment used to produce livestock manure combustion ash must meet regulatory standards and structural conditions such as the Air Pollution Control Act and, in some cases, the Waste Management Law.
In particular, in order to suppress the generation of dioxins, it is necessary to burn at a combustion gas temperature of 800 ° C. or higher, and if it is treated as an industrial waste incinerator, it must be a furnace equipped with a combustion assisting device.
In addition, for the equipment used for the production of livestock manure combustion ash, a system for recovering the heat energy at the time of combustion and using it for heating, drying, etc., and a system for converting the heat energy into electric energy will be installed. be able to.

As described above, it is desirable that most of the calcium carbonate is converted into calcium oxide by burning the livestock manure under the conditions of 800 ° C. or higher, preferably 900 ° C. or higher.
However, even if livestock manure combustion ash is prepared by burning at 900 ° C, it is necessary to consider the possibility that calcium carbonate may not be completely decomposed due to non-uniformity of reaction conditions such as temperature unevenness.

In addition, the titer of calcium oxide may decrease as livestock manure burning ash is stored for a long period of time and absorbs water and carbon dioxide.
Therefore, it is desirable that a small amount of the obtained livestock manure combustion ash is placed in an evaporating dish and heated at 900 ° C. for 1 hour, and then the weight loss is preferably 10% or less. It is desirable to remove water, carbon dioxide, etc. by heat treatment again and reduce the weight loss in the reheating test to 10% or less. By removing carbonates and increasing the proportion of oxides, the amount of calcium that can be removed from livestock manure burning ash will increase.

The first embodiment is characterized in that such livestock manure burning ash and plant biomass are mixed and reacted in the presence of water (preferably in water), and livestock manure burning ash is mixed with plant biomass and water. By reacting with the containing mixture, calcium is transferred from the livestock manure burning ash into the plant biomass or solution.

Next, as the plant biomass used in the first embodiment,
Agricultural waste such as rice straw, straw, corn stover (corn foliage), buckwheat foliage, vegetable foliage, etc.;
Sugar cane bagasse, sorghum bagasse, sugar beet pomace, pomace pomace, rice husk, bran, etc., which are the primary processing residues of foods, etc.;
Tea leaves, coffee grounds, okara, shochu residue, etc., which are manufacturing residues of foods, etc.;
Resource crops such as Erianthus, Miscanthus, Giant Miscanthus (Ogisski), Switchgrass, Napiergrass, etc.;
Other herbaceous residues such as weeds, turfgrass, riversides, roadsides, wastelands, etc.
Woods derived from broad-leaved trees such as beech, oak, oak, hippopotamus, zelkova, willow, poplar, bark, branches and leaves;
Materials derived from coniferous trees such as sugi, cypress, and pine, bark, foliage;
Algae such as sargassum, kelp, wakame seaweed, gelidiaceae, sea lettuce, and acetabularia ryu;
Furthermore, aquatic plants and microalgae;
Can be widely used.

In particular, the plant biomass used in the first embodiment is a plant biomass of the Gramineae family, specifically, the entire above-ground part of the plant body of a Gramineae crop such as rice, wheat, and corn, or an edible portion thereof. Examples include foliage as agricultural waste after collecting grain. In addition, the whole sugarcane plant, which is a gramineous plant, the upper part of the stem and leaves that are excised at the time of harvest, the stem part that is transported to a sugar factory, and bagasse after squeezing can be mentioned as raw materials. Furthermore, the foliage of Erianthus, Miscanthus, Giant Miscanthus, Napiergrass, and Switchgrass, which are cellulosic resource crops of the Gramineae family, can be used. Then, it is desirable to use grasses, reeds, bamboo and other gramineous plants that are cultivated or grow naturally on riversides, roadsides, wastelands, etc. In addition, it is preferable to use sawdust, wood chips and the like.

As the plant biomass used in the first embodiment, it is desirable that the plant biomass is cut to a length of about several centimeters so that a component containing calcium sufficiently permeates and reacts with the cell wall.
In that case, it is desirable to enhance the ability of the liquid to permeate into the inside and exchange the liquid inside and outside by a method such as grinding plant biomass to introduce a crevice into the tissue. For example, in order to enhance this ability, after cutting the plant biomass, it is passed through a discifier-like device, brought into contact with protrusions, or the cut product of the plant biomass and the above-mentioned livestock manure burning ash are mixed as needed. From the viewpoint of preventing inconvenience due to overdrying, after adding water, livestock manure burning ash can be used like an abrasive to grind plant biomass.
On the other hand, if it is crushed too finely, it will be difficult to collect the treated ash and plant biomass separately by solid-solid separation using a sieve or the like due to the difference in shape between the two, so caution is required. ..

By mixing livestock manure burning ash and plant biomass in the presence of water, the components derived from livestock manure burning ash, especially calcium, are transferred to plant biomass (in other words, in livestock manure burning ash. (Although it happens that the calcium moves toward the plant biomass and is adsorbed on it), in this case, not only mixing but also heat treatment or long-term standing treatment after mixing promotes the migration and reaction. It is desirable to do.
This treatment is performed under favorable conditions according to the characteristics of the raw material, for example, for rice straw, which is one of the herbaceous agricultural wastes, by heat treatment at 95 ° C. for 10 minutes or more, or at outside temperature without heating. By allowing the mixture to stand for more than a day, more preferably for a week or more, the chemical reaction accompanied by the transfer of the components derived from the combustion ash of livestock manure to the plant biomass and the alteration (modification) of the plant biomass proceeds. Since the conditions differ depending on the raw material quality, the alkali titer, and the quality required for the product, any conditions can be adopted, including a combination of heating and non-heating and standing.
When not heating, the mixture reacts with carbon dioxide in the outside air, and in order to suppress the phenomenon that the alkali titer decreases, cover the mixture with a sheet such as a polyolefin sheet to block it from the outside air. It is desirable to take measures such as consolidation to minimize air flow.
Therefore, in the first embodiment, livestock manure burning ash and plant biomass are mixed and reacted in the presence of water (preferably in water), and as described in (2) above, this reaction is carried out on livestock. It is preferable to carry out by at least one of a method of heating a mixture of manure burning ash, plant biomass and water, or a method of holding the mixture without heating for 1 day or more.

Regarding the reactions that occur under these conditions, the reaction conditions include the same reaction conditions as the calcium hydroxide pretreatment conditions in the ethanol production process from plant biomass, and it is a guideline for the reaction that the liquid phase pH decreases with the consumption of alkali. Become.
At that time, since the alteration of the plant biomass has occurred, the fraction containing the plant biomass as the main component is recovered after the reaction, and after the pH is adjusted, it is enzymatically saccharified using an enzyme preparation containing cellulase and xylanase. The improvement in saccharification can be confirmed.
In this regard, the consumption of alkali, which is characterized by a decrease in pH, occurs even after the reaction under high-concentration alkaline conditions such that the improvement in enzyme saccharification efficiency is not observed (see Test Example 2 below). , Both seem to be similar, but they are completely different phenomena with different optimum points for pretreatment and calcium adsorption.

The amount of calcium that can react with plant biomass depends on the chemical structure of the plant biomass, the surface area that can react, and the like.
The calcium hydroxide equivalent contained in livestock manure combustion ash depends on the type of livestock manure, the amount of combustion improver, modifier, etc. added, and the combustion conditions.
Some of the calcium elements may be salts with phosphoric acid, and only some of the amounts evaluated as acid-soluble calcium elements react as alkalis similar to calcium hydroxide.
The titer as calcium hydroxide can be converted by assuming that the alkaline titer of the supernatant of the water suspension is the titer derived from calcium hydroxide, but coexisting potassium hydroxide, etc. It should be noted that the potassium salt of is highly alkaline in an aqueous solution.

The amount of livestock manure burning ash input during the reaction between livestock manure burning ash and plant biomass is 0.1 to 8 weight, preferably 0.15 to 4 weight, based on the dry weight of plant biomass.
If the amount of livestock manure combustion ash input is too small, the pH will not be improved sufficiently, resulting in inefficiency of the reaction. In addition, if the treatment is performed at room temperature without heat treatment, the pH will decrease as the reaction progresses. By lowering the pH to a pH at which microorganisms can easily grow, the risk of deterioration of plant biomass due to biological reactions increases.
On the contrary, if the amount of livestock manure combustion ash input is too large, the amount of residual calcium hydroxide increases, and the effect of reducing the calcium / phosphorus ratio in the treated ash becomes dull.

In addition, the amount of water to be added during this reaction may be sufficient for the transfer of alkali in livestock manure combustion ash, but the higher the alkali concentration, the more the reaction with plant biomass proceeds. It is desirable in that it does.
Specifically, the amount of water to be added during this reaction is about one-third or more and 100 times or less, preferably equal or more and 10 times or less, based on the dry weight of the plant biomass.

As the water added during this reaction, distilled water, ion-exchanged water, tap water, retreated water, rainwater and the like can be used, and those in the neutral to alkaline (pH 6 or higher) range are preferably used.
However, in the first embodiment, since the livestock manure combustion ash and the plant biomass may be mixed and reacted in the presence of water, water is generally added, but the biomass having a high water content is used. When used, it is in the presence of water, so water may not be added. In addition, alkaline water generated during washing of solids and solid-solid separation after the reaction is added to the plant biomass, and if necessary, excess water is removed to add water to the plant biomass. While doing so, it is possible to wash plant biomass, reduce the alkaline titer of alkaline water, and reduce the amount of water used.
Then, in order to promote the transfer of alkali in the presence of water, it is desirable to perform operations such as stirring, consolidation, consolidation and pressure release repeatedly.

After the reaction, the treated livestock manure burning ash (hereinafter, sometimes referred to as "treated ash") is solid-solid-separated from the reaction-reacted plant biomass and aqueous solution from these mixtures to obtain treated ash. By recovering and measuring the calcium / phosphorus ratio, it is possible to confirm the elution and removal of calcium, in other words, the transfer of calcium into plant biomass.
At the time of recovery of this treated ash, at least one separation method can be used, that is, separation due to the difference in specific gravity (difference in sedimentation rate) from the plant biomass after the reaction or separation due to the difference in particle size.
In that case, if necessary, water is added, stirring, impact, etc. are used to disperse both the treated ash and the plant biomass after the reaction in the aqueous phase, and an appropriate operation is performed from among sieving and fractional sedimentation. It is desirable to do.
When the treated ash fraction with high floating property coexists, it can be forcibly recovered as a sediment by adding a natural sediment in the sedimentation tank or a coagulant.
Recovery can also be facilitated by centrifugation.
On the contrary, when the drying process can be introduced, it is completely dried or partially dried, and each of the component derived from livestock manure combustion ash and the component derived from plant biomass is made into a solid, if necessary. It is possible to disperse in the vapor phase and separate by wind power sorting while promoting the separation of both by methods such as vibration and impact.

The obtained treated ash may contain a small amount of plant biomass-derived fiber and the like.
When it is necessary to remove organic matter derived from plant biomass from the treated ash, methods such as combustion decomposition of organic matter and removal of fiber by solid-solid separation again after drying and crushing can be applied.

In the first embodiment, livestock manure burning ash and plant biomass are mixed and reacted in the presence of water (preferably in water), but as described in (3) above, the reaction product obtained by the reaction. Includes a step of recovering useful substances from the inside.
Here, as a step of recovering the useful substance, as described in (4) above, a fraction obtained by adding water after the reaction and containing a water-insoluble inorganic substance derived from the combustion ash of livestock manure as a main component and the plant biomass-derived Includes a step of solid-solid separation from the fraction containing the water-insoluble component as the main component.

The treated ash thus obtained can be stored in a wet state and used in the state of a slurry having excellent dispersibility and mixability, but when precipitated particles coexist, it is necessary to homogenize the characteristics. It is desirable to grind those particles as appropriate.
Further, by partially or completely dehydrating, it is possible to reduce the weight and improve the handleability. However, since the dehydrated product may agglomerate into a lump, it is possible to improve the dispersability, mixing / moldability, and chemical processability by pulverizing the dehydrated product again.
Further, in order to improve the handleability of the powdered treated ash, a binder such as polyvinyl alcohol, carboxymethyl cellulose, starch, lignosulfonate, molasses is added to the treated ash in a wet state or a dry state for molding. This improves the stability as a grain.

Calcium, which is the main component of livestock manure combustion ash, has low water solubility in the state of calcium hydroxide, but it is adsorbed by migrating to plant biomass and reacting, and the amount of calcium in the treated ash decreases.
In addition, since part of potassium is water-soluble, the amount of potassium in the treated ash also decreases.
As described above, the reduction of the potassium / phosphorus ratio facilitates the fertilizer application design when fertilized.
On the other hand, most of phosphorus is considered to be in an alkali-insoluble state such as calcium phosphate, so that it is difficult to transfer from livestock manure burning ash.

For this reason, the treated ash has a lower calcium / phosphorus ratio and a lower alkalinity when suspended in water than the original livestock manure burning ash.
Therefore, when treated ash is used as a phosphorus source, the environmental impact of alkali is reduced and work safety is improved as compared with the original livestock manure burning ash.
Further, as the alkalinity becomes lower, the liberation of phosphoric acid occurs even if a small amount of acid is added, and the extraction of phosphoric acid is easy.
Then, phosphorus elution at a higher pH is observed. The cause of this phenomenon is unknown, but the lower calcium / phosphorus ratio in the treated ash than in the chicken manure burning ash may moderate the increase in free calcium concentration associated with acid addition and increase the solubility of calcium phosphate. May be related.

In this way, livestock manure burning ash (treated ash), whose functionality has improved as the calcium / phosphorus ratio decreases, is a new material with a lower environmental load than phosphorus fertilizer obtained from phosphorus ore, which is a fossil resource. As a raw material for phosphoric acid recovery / purification, phosphorus fertilizer with low residual calcium or its value as a source thereof.

On the other hand, plant biomass that has reacted with components such as calcium transferred from livestock manure combustion ash is given new value after recovery due to alteration of its cell wall structure.
After the reaction and recovery, the plant biomass has increased fiber dissociability and has value as a fibrous raw material. In addition, the enzymatic saccharification property after pH adjustment is improved, and the compost raw material, feed, enzyme saccharified raw material, mushrooms. The applicability to a medium or the like is improved.
Further, it is known that organic acids such as ferulic acid and p-coumaric acid are liberated in water with the alkaline treatment of plant biomass (see, for example, Japanese Patent Application Laid-Open No. 2013-220067).
By reacting the alkali derived from livestock manure combustion ash with plant biomass, valuable resources such as these organic acids are extracted into water as in this prior art.

Compared with the plant biomass storage / pretreatment technique at room temperature using calcium hydroxide as shown in the example of Patent Document 9 (Japanese Unexamined Patent Publication No. 2010-202491), the method according to the first embodiment is The advantage is that the pH reduction by carbon dioxide in the air is slower than the treatment with calcium hydroxide, and the degree of pH reduction is also small.
As a result, even if a polyolefin sheet or rappi silo is used without using a special coating material such as an aluminum bag, which has extremely high carbon dioxide blocking property, or by replacing with decarbonized air. Compared with the calcium hydroxide treatment method, it is expected that the risk of putrefaction due to a decrease in pH can be reduced and that it can play a more advanced role as a simple wet storage technique.
In such a simple plant biomass storage system, the pH is lowered due to the contact with carbon dioxide in the air near the surface to be covered, and the deterioration of the storage quality of the plant biomass in that part can be avoided. No. However, it is expected that a high pH will be maintained in the inner part where air does not flow directly. It is expected that the gradual decrease in pH of the stored product will suppress the deterioration of the quality of the portion near the surface and also the influence on the inside thereof.

Most plant biomass contains fiber as a main component, and the fiber can be dispersed and used as pulp or fiber.
In addition to that, the added value can be further improved by processing into fibers having characteristics such as cellulose nanofibers.
In the process of producing crushed wood pulp by dissociating plant biomass using a mechanical dissociation method such as a grinder or refiner, efficiency is improved by treatment with sodium sulfite and sodium carbonate.
The pulp produced in this way is called chemical-treated crushed wood pulp, semi-chemical pulp, chemical mechanical pulp, etc. [For example, pulp pulp manufacturing technology series (2) "mechanical pulp" (first edition published in 1997, Pulp Technology Association). Hen, Shin Nihon Printing Co., Ltd.)].

The treated plant biomass obtained by the method according to the first embodiment has the same effect as such alkaline treatment, and is valuable as a fibrous material capable of easily dissociating into fibers. Has. This fibrous material is made into pulp by a method such as mechanical pulping by mechanical fiberization or chemical pulping by treatment with an alkali, an oxidizing agent, etc., and then further fiber is obtained by a mechanical method, a chemical method, or the like. After being broken, it can be processed into useful substances such as paper, non-woven fabric, and cellulose nanofibers.

Therefore, the useful substance obtained by the method according to the first embodiment is the livestock manure burning ash produced after the reaction by mixing and reacting livestock manure burning ash and plant biomass in the presence of water. It is a fraction containing a water-insoluble inorganic substance derived from the main component, and a fraction generated after the reaction and containing a water-insoluble component derived from the plant biomass as a main component, which may be recovered.

Next, the second embodiment relates to a useful substance produced by the method for producing a useful substance according to any one of (1) to (6) above, as described in (7) above.

The useful substance according to the second embodiment is for a so-called product-by-process (PBP) claim.
In the second embodiment, the useful substances are defined in the PBP claim, for example, depending on the type of livestock manure (chicken manure, cow manure, etc.; livestock age; sex, etc.), combustion conditions, combustion facility, etc. Not only is it difficult to unambiguously define useful substances by composition, etc. due to their different compositions, but also the work of creating all possible livestock manure burning ash and investigating them for its measurement. This is because it is considered impossible and unrealistic to do this before filing an application.
In addition, for example, the useful substance itself contained in the treated ash may contain a small amount of fiber derived from plant biomass.
Furthermore, useful substances are also present in the treated plant biomass as described above.
Therefore, not only is it difficult to unambiguously define useful substances by composition, etc., but it is impossible and unrealistic to carry out the work of investigating them before filing for their measurement. Therefore, it is a so-called product-by-process (PBP) claim.

Here, the useful substances are basically those mainly contained in the treated ash after the reaction and those mainly contained in the plant biomass after the reaction.
Therefore, the useful substance in the second embodiment is generated after the reaction by mixing and reacting the livestock manure burning ash and the plant biomass in the presence of water as shown in the first embodiment. Further, it is a fraction containing a water-insoluble inorganic substance derived from the combustion ash of livestock manure as a main component, and a fraction containing a water-insoluble component derived from the plant biomass generated after the reaction as a main component.
Therefore, with respect to these contents, the description in the first embodiment is quoted as it is.

Then, as described in the first embodiment and described in (8) above, the dried product of the fraction containing the water-insoluble inorganic substance derived from the combustion ash of livestock manure as the main component among the useful substances is used. It shows a low calcium / phosphorus ratio compared to the value of livestock manure burning ash before the reaction.

Next, as described in the first embodiment and described in (9) above, the dried product of the fraction containing the water-insoluble inorganic substance derived from the combustion ash of livestock manure as the main component among the useful substances , Shows a low potassium content compared to the value of livestock manure burning ash before the reaction.

Further, as described in the first embodiment and described in (10) above, the dried product of the fraction containing the water-insoluble inorganic substance derived from the combustion ash of livestock manure as the main component among the useful substances is used. When it was suspended in water and acid was added, it showed the property of dissolving phosphorus with a smaller amount of acid addition compared to the value of livestock manure burning ash before the reaction, which had the same amount of phosphorus. There is.

Further, as described in the first embodiment and described in (11) above, the dried product of the fraction containing the water-insoluble inorganic substance derived from the combustion ash of livestock manure as the main component among the useful substances is used. When it is suspended in water and acid, especially hydrochloric acid, is added, it has the same phosphorus content and exhibits the property of dissolving phosphorus at a higher pH compared to the value in pre-reaction livestock manure burning ash. ing.

Then, as described in the first embodiment and described in (12) above, the fraction of the useful substances containing the water-insoluble inorganic substance derived from the combustion ash of livestock manure as a main component or a dried product thereof is used. , Used as a phosphorus source.

As described in the first embodiment, calcium, which is the main component of livestock manure combustion ash, has low water solubility in the state of calcium hydroxide, but is adsorbed by migrating to plant biomass and reacting. The amount of calcium in the treated ash is reduced.
In addition, since part of potassium is water-soluble, the amount of potassium in the treated ash also decreases.
On the other hand, most of phosphorus is considered to be in an alkali-insoluble state such as calcium phosphate, so that it is difficult to transfer from livestock manure burning ash.
For this reason, the treated ash has a lower calcium / phosphorus ratio and a lower alkalinity when suspended in water than the original livestock manure burning ash.
Therefore, when treated ash is used as a phosphorus source, the environmental impact of alkali is reduced and work safety is improved as compared with the original livestock manure burning ash.
Further, as the alkalinity becomes lower, the liberation of phosphoric acid occurs even if a small amount of acid is added, and the extraction of phosphoric acid is easy.
Then, phosphorus elution at a higher pH is observed.
As a new material, livestock manure combustion ash (treated ash) whose functionality has improved as the calcium / phosphorus ratio decreases can be used as a raw material for phosphoric acid recovery / purification, phosphorus fertilizer with low residual calcium, or a source thereof. As a low environmental load material, it can be effectively used in the fields of fertilizer, chemical industry, etc.

Further, as described in the first embodiment and described in (13) above, the fraction of the useful substances containing the water-insoluble component derived from the plant biomass as a main component or a dried product thereof reacts. Compared with the previous value of plant biomass, the enzymatic saccharification efficiency of the cell wall polysaccharide after pH adjustment is improved.

That is, the plant biomass that has reacted with the components transferred from the combustion ash of livestock manure is given new value after recovery by deteriorating its cell wall structure.
After the reaction and recovery, the plant biomass has increased fiber dissociability and has value as a fibrous raw material. In addition, the enzymatic saccharification property after pH adjustment is improved, and the compost raw material, feed, enzyme saccharified raw material, mushrooms. The applicability to a medium or the like is improved.
In addition, it is known that organic acids such as ferulic acid and p-kumalic acid are liberated in water due to the alkali treatment of plant biomass. However, the alkali derived from livestock manure combustion ash reacts with plant biomass. Similar to this prior art, these valuable resources such as organic acids are extracted into the water.

As described in the first embodiment, the method according to the first embodiment has a pH reduction due to carbon dioxide in the air, as compared with the plant biomass storage / pretreatment technique using calcium hydroxide at room temperature. The advantage is that it is slower than the treatment with calcium hydroxide and the degree of pH decrease is small.
As a result, even if a polyolefin sheet or rappi silo is used without using a special coating material such as an aluminum bag, which has extremely high carbon dioxide blocking property, or by replacing with decarbonized air. Compared with the calcium hydroxide treatment method, it is expected that the risk of putrefaction due to a decrease in pH can be reduced and that it can play a more advanced role as a simple wet storage technique.

Most plant biomass contains fiber as a main component, and the fiber can be dispersed and used as pulp or fiber.
In addition to that, the added value can be further improved by processing into fibers having characteristics such as cellulose nanofibers.
In the process of producing crushed wood pulp by dissociating plant biomass using a mechanical dissociation method such as a grinder or refiner, efficiency is improved by treatment with sodium sulfite and sodium carbonate.

Further, as described in the first embodiment and described in (14) above, the fraction of the useful substances containing the water-insoluble component derived from the plant biomass as a main component or a dried product thereof reacts. Compared with the previous plant biomass, the dissociability of the fibrous material constituting the plant tissue is improved, and since it has the same effect as the alkaline treatment, the fibrous material can be easily dissociated into fibers. It has value as a material.

The present invention is as described above.
As the effects of the present invention as described above, the acceleration of the creation of small-scale new industries in the region and the sophistication of resource recycling through agricultural and livestock cooperation are expected.
By utilizing the transition technique in the present invention, it becomes possible to supply a fraction containing livestock manure combustion ash after alkali donation / reaction as a main component as a new phosphorus supply source.
Then, it becomes possible to supply a fraction containing plant biomass after alkali reception as a main component, which is produced after the reaction, as a material having improved saccharification efficiency or defibration.
Such regional efforts will accelerate efforts to control the generation of greenhouse gases such as methane and dinitrogen monoxide in the composting and drying processes of livestock manure and to burn livestock manure for the production of renewable energy. In addition to encouraging exports from the field to curb greenhouse gas generation due to the introduction of agricultural waste, efforts to manufacture fossil resource substitutes such as biofuels and plastic substitutes, import of phosphorus ore, Through efforts to produce alternatives to phosphorus fertilizers, which have a high environmental load through processing, and alternatives to lime, which has a high environmental load, we will pave the way for the creation of diverse environmental value from the region.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[Test Example 1: Production of livestock manure burning ash]
(1) Manufacture of burning ash from chicken manure Egg-collected chicken manure (moisture content 10.7%, high calorific value 12.78 MJ / kg) after being dried by blowing air for one week is put into a rotary kiln furnace (model: Joule-R, MI. Combustion ash from chicken manure was obtained by using it for use (manufactured by S).
That is, in the rotary kiln furnace, after ignition and heating of the combustion furnace with wood (3.6 kg), the raw material input speed is 9 kg / h, the combustion temperature is 807 ° C, the primary air is 67 m ³ / h, and the secondary air is 30. Combustion of chicken manure was carried out for a treatment time of 4.85 h under the condition of m ³ / h, and the obtained burning ash of chicken manure was air-cooled and stored at room temperature. For the input chicken manure amount of 43.7 kg and the wood input amount of 3.6 kg, chicken manure burning ash 10.3 kg was obtained.

(2) Production of combustion ash from cow dung Manure from cow dung, ogakuzu, and calcium carbonate to prevent melting were mixed at a dry matter weight ratio of 5: 5: 1 and processed into pellets with a diameter of 8 mm and a length of 10 mm. Cow dung combustion ash was obtained by using a solid fuel (moisture content 9.4%, high calorific value 14.52 MJ / kg) as a solid fuel in a rotary kiln furnace (model: Joule-R, manufactured by MIS).
That is, in the rotary kiln furnace, the combustion furnace is sufficiently heated after ignition with wood (32.6 kg), and the conditions are that the primary air is 71 m ³ / h, the secondary air is 25 m ³ / h, and the raw material input speed is 8.0 to 13.3 kg / h. As a result of burning cow dung for a treatment time of 7.53 h, the combustion gas temperature was 864 to 916 ° C.
The obtained cow dung combustion ash was air-cooled and then stored at room temperature. Cow dung burning ash 5.1 kg was obtained for 43.9 kg of solid fuel input and 32.6 kg of wood input.
Table 1 shows the calcium element content (Ca content:%), phosphorus element content (P content:%), and Ca / P (weight ratio).
As shown in Table 1, the calcium element content was 26.0% and the phosphorus element content was 4.48%.

[Test Example 2: Production of double-baked ash (chicken manure burning ash A, chicken manure burning ash B, and chicken manure burning ash C)]
Since chicken manure burning ash is inhomogeneous depending on the location and absorbs water and CO2 during storage and changes its characteristics such as alkaline titer, it is heated (burned) before use (again) to make water or The operation of removing carbon dioxide was performed to produce double-baked ash.
That is, 100 g of the chicken manure combustion ash obtained in Test Example 1 was taken, placed on an evaporating dish, and heat-treated at 900 ° C. for 2 hours in a small program electric furnace (MMF-1, manufactured by AS ONE Corporation). Manufactured ashes.
Then, it was allowed to stand and cooled in a desiccator, and the weight loss was measured at room temperature.
As a result, a weight loss of 20% or more was observed.
In addition, this double-baked ash was heat-treated again at 900 ° C for 1 hour, but the weight loss was 5% or less.
Calcium element content (Ca content:%) for each of the three types of double-baked chicken manure burning ash (chicken manure burning ash A, chicken manure burning ash B, and chicken manure burning ash C) prepared separately at the time of use by this method. ), Phosphorus element content (P content:%), Ca / P (weight ratio), potassium element content (K content:%), K / P ratio (weight ratio) are shown in Table 1. show.

For phosphorus soluble in hydrochloric acid in solid samples, a quantification kit based on color development by forming a complex of malachite green-molybdic acid-orthric _{acid using phosphoric acid (H 3} PO _{4) as a standard substance (Malachite Green Phosphate Assay Kit,} Analysis was performed using Sigma Aldrich).
For calcium, which is soluble in aqueous hydrochloric acid, a quantitative kit (Metalloassay Calcium Measurement LS, Metallogenics) based on the coloration of the visible part by forming a chelate complex between Chlorophosphonazo-III and calcium, using calcium chloride as a standard substance. Analyzed using.
Further, water-soluble potassium was analyzed using a pH / ion meter (F-53, manufactured by HORIBA, Ltd.) equipped with a potassium electrode (model 6582, manufactured by HORIBA, Ltd.) using potassium chloride as a standard substance.

[Test Example 3: Alkali transfer test from livestock manure burning ash]
As plant biomass, rice straw [Koshihikari dried product. The contents of glucan and xylan in the dried product were 31.9% and 14.1%, respectively. This content is based on the analytical method described in "Shiroma R. et al., Bioresour. Technol. 102, 2943-2949 (2011)". ] Was pulverized with a willley mill (model MF-10, IKA) and a ball mill (model MM301, Lecce).

Separately, 13.5 mL of water and the chicken manure combustion ash (sample before the second heat treatment) obtained in Test Example 1 were added in a fixed amount in the range of 0.15 g to 6.0 g, and the pH was measured after stirring (). Concentration before adding rice straw).
Then, 1.5 g of the above-mentioned rice straw powder was added thereto, and the mixture was stirred at room temperature and then the pH was measured (concentration after addition of rice straw).
Further, the mixture was heated at 95 ° C. for 1 hour and allowed to cool to room temperature, and then the pH was measured (concentration after heat treatment).
These results are shown in Table 2 as hydroxide ion concentrations.

From the results in Table 2, it was confirmed that the alkalinity of the ash suspension was reduced by the addition of rice straw, and further reduced by heat treatment.
The reduction in alkalinity after the heat treatment occurred under all concentration conditions within the test concentration range, and the difference increased as the added alkali concentration increased.

[Test Example 4: Enzymatic saccharification of plant biomass produced after alkali test from ash]
To the sample after heat treatment in Test Example 2, add 5N hydrochloric acid to dissolve the ash, wash the solids present in the precipitate with water, and then add sodium acetate buffer (final concentration 50 mM). In addition, the pH was adjusted to 5.0.
After that, the enzyme solution [Product name Cellic CTec2, Novozyme Japan (6 FPU (filter paper decomposition activity) / g-solid (dry weight)) and Novozyme 188 [Novozyme Japan, 12 CbU (cellobiase activity) / g- Solid matter (dry weight))] was added and shaken at 50 ° C. for 48 hours for enzymatic saccharification.
Then, take the supernatant and follow the method of Ike M. et al., J. Appl. Glycosci. 60, 177-185 (2013). Divided by the amount of glucose residue contained in the treated straw product] or the liberation rate of xylan [the amount of xylose residue recovered from the aqueous phase by the amount of xylose residue contained in the treated rice straw product] Divided] was measured respectively.

The results are plotted with the alkali concentration before heat treatment (see Table 2) on the horizontal axis, which is shown in FIG. The alkali concentration is indicated by "μM" in Table 2, but is indicated by "M" in FIG. 1 from the drawing.
That is, FIG. 1 is a graph showing the relationship between the alkali concentration before the heat treatment and the enzymatic saccharification yield of the rice straw processed product produced after the reaction in the reaction between the chicken manure burning ash and the rice straw powder in Test Example 4. ..
According to FIG. 1, it was clarified that the enzymatic saccharification property of rice straw was improved by heat-treating rice straw using chicken manure burning ash in this way.
Furthermore, even at the alkali concentration (0.158 M and 0.251 M) before the heat treatment (indicated as “after adding rice straw” in Table 2), where the liberation rate is close to the plateau in FIG. 1, the alkali decreases after the heat treatment (Table 2, Table 2). The reduced concentrations were 0.133 M and 0.172 M), respectively, suggesting that the transfer of alkali from chicken manure burning ash to rice straw did not show the same tendency as the change in sugar release rate.

[Test Example 5: pH lowering behavior during storage of plant biomass using livestock manure burning ash]
As plant biomass, rice straw (Koshihikari) cut to a length of 4 cm in the longitudinal direction is 320 g (equivalent to the weight of dry matter), 614 mL of water and 89.0 g of chicken manure burning ash B (reactive calcium amount). Was mixed with 32 grams in terms of calcium in an aluminum bag, and after sealing, it was heat-treated at 95 ° C for 1 hour (chicken manure burning ash-treated sample).
As a control group, 528 mL of water and 32.0 g of slaked lime were mixed with 320 g of rice straw, and the same heat treatment as above was performed (slaked lime treated sample).
After the reaction, the sample was returned to room temperature in the room, opened, and each of the above samples with a dry weight equivalent to 12.5 g (wet weight 31.3 g) was placed in 6 glass wide-mouthed bottles (diameter 85 mm, height 100 mm), and the diameter was 18 mm. Covered with a lid with ventilation holes. Breathable typest paper was attached to the ventilation holes to prevent drying. To maintain humidity, leave the sample in an incubator (25 ° C) containing a platter containing water, take out the sample in the bottle immediately after standing (0 days), 7 days, and 14 days later, wrap it in a non-woven fabric, and then wrap it in a non-woven fabric. After squeezing the juice with a press to collect 5 to 10 mL of exudate, the pH was measured.
As a result, on the 0th day, the pH of the chicken manure burnt ash-treated sample and the decalcified sample were pH 12.1 and pH 11.4, respectively, whereas on the 7th day, the pH was 11.0 and pH 9.6, respectively. On the 14th day, the pH was 9.6 and pH 8.2, respectively.
As described above, the pH of the sample decreased due to the contact with the outside air during the closed storage, but the decrease in pH of the chicken manure burnt ash-treated sample was more gradual.
This result suggests that the sample using chicken manure burning ash takes a long time to drop to pH 8.5, which is the upper limit of the growth pH range of mold, and is more resistant to mold contamination. (Refer to the website of the Ministry of Education, Culture, Sports, Science and Technology; https://www.mext.go.jp/b_menu/shingi/chousa/sonota/003/houkoku/08111918/002.htm).

[Example 1]
79.4 mL of water and 12.2 g of chicken manure burning ash A are mixed in an aluminum bag with 40.7 g (equivalent to the weight of dry matter) cut from rice straw (Koshihikari) to a length of 4 cm in the longitudinal direction. After sealing, heat treatment was performed at 95 ° C. for 1 hour.
This was opened after air cooling, and while suspended in 2.1 L of water, the treated rice straw was washed, filtered and collected using three stainless meshes with an opening of about 5 mm. For the mesh-passing fraction, after sufficiently precipitating the ash in the water, the supernatant is removed by decantation, and the precipitated portion of the water fraction after centrifugation (8,000 xg, 5 minutes) is collected, and the precipitate is combined. It was collected in an aluminum dish and dried at 105 ° C. until it became constant.
After weighing and crushing the dried product (treated ash A), the amount of calcium ions and phosphate ions released when 10 mL of 1 N hydrochloric acid is added to 100 mg is defined as the total amount of calcium and total phosphorus. Calcium element content (Ca content:%), phosphorus element content (P content:%), Ca / P (weight ratio), potassium element, which were defined, quantified, and analyzed in the same manner as in Test Example 1. Table 3 shows the content rate (K content rate:%) and the K / P ratio (weight ratio).
Table 3 shows the ash / rice straw (weight ratio) and the P recovery rate (%).
Here, ash / rice straw (weight ratio) indicates the ratio at the time of treatment. The P recovery rate (%) indicates the ratio of the amount of P in the fraction recovered as the treated product to the amount of P in the charged chicken manure burning ash.
In Table 3, "/" means "not applicable" or "not measured".
Table 3 also shows the results of Table 1 described above.

As a result, as shown in Table 3, 75.5% of the phosphorus element in the added chicken manure burning ash A was recovered in the precipitate (treated ash A) recovered after the reaction with the plant biomass. The calcium / phosphorus weight ratio of chicken manure burning ash A (weight of Ca element / weight of P element) was 6.00, whereas that of treated ash A was significantly reduced to 2.82.
In addition, the pH of the supernatant when the chicken manure burning ash (1) was suspended in 10 times the weight of water was 13.3, whereas the pH of the treated ash A-3 was 11.0, which is apparent. The above alkali concentration decreased to 1/200.
Furthermore, the potassium / phosphorus weight ratio of chicken manure burning ash A (weight of K element / weight of P element) was 0.926, whereas that of treated ash A decreased to 0.494.

[Example 2]
Chicken manure burning ash B 16.8 g and water were added to 56 g of cut rice straw (equivalent to the weight of dry matter) prepared in the same manner as in Example 1 to adjust the final moisture content to 60%.
This mixture is sealed in an aluminum bag and allowed to stand at 25 ° C. for 10 days, then opened, separated by a mesh according to the method of Example 1, and separated into rice straw, a precipitate (treated ash B) and a cleaning solution. bottom.
The treated ash B was dried and pulverized according to the method of Example 1, and the amount of calcium and phosphorus was measured.

As a result, as shown in Table 3, 88.6% of phosphorus present in the chicken manure burning ash B was recovered in the treated ash B. The calcium / phosphorus weight ratio of chicken manure burning ash B was 5.18, whereas that of treated ash B decreased to 2.05.

[Example 3]
To 50 g of poplar-derived wood chips (equivalent to dried product), 97.5 mL of water and 15.0 g of chicken manure burning ash C were mixed in an aluminum bag, and after sealing, heat treatment was performed at 95 ° C. for 1 hour.
This is opened after air cooling, and while suspending a part (equivalent to a dry matter weight of 46.0 g) in 1.6 L of water, one stainless mesh with an opening of about 5 mm and two stainless mesh with an opening of 2 mm are used. The treated wood chips were washed and collected by filtration.
For the mesh-passing fraction, after sufficiently precipitating the insoluble matter mainly composed of ash in water, the supernatant is removed by decantation, and the supernatant is centrifuged (8,000 x g, 5 minutes). The precipitated part was recovered, combined with an insoluble matter containing ash as a main component, and recovered as a precipitate in an aluminum dish, and dried at 105 ° C. until the amount became constant.
The amount of calcium and the amount of phosphorus in this dried product (treated ash C) were measured in the same manner as in Example 1.

As a result, as shown in Table 3, the weight ratio of calcium / phosphorus decreased from the original value of chicken manure burning ash C of 5.63 to 3.22, and the recovery rate of phosphorus in treated ash C was 96.1%. ..

[Example 4]
The treated rice straw separated from the treated ash in Example 1 (heat-treated at 95 ° C. for 1 hour), and the treated rice straw separated from the treated ash in Example 2 (still at 25 ° C. for 10 days). 5 g of rice straw (untreated) recovered after mixing with water without adding chicken manure burning ash and storing at 4 ° C for 10 days under the conditions of Example 2 Using an equivalent amount, add 25 mL of water and twice the molar equivalent of hydrochloric acid of the contained calcium element to each of them, and after confirming that the pH is stable within the range of 4-5, sodium acetate buffer (final concentration 50). mM), sodium azide 0.05% (final concentration), chloramphenicol 50 μg / mL (final concentration)) Enzyme preparation [Cellic CTec2 (6 FPU / g-treated rice straw (dry weight)) and Novozyme 188 [ 12 CbU / g-Rice straw processed product (dry weight)], both of which were added by Novozyme Japan.
After that, water was added so that the total weight of each was 50 g, and the concentration of the substrate (processed rice straw) was set to 10% (w / w).
After shaking at 50 ° C for 48 hours, the release rate of glucan [the amount of glucose residue recovered from the aqueous phase divided by the amount of glucose residue contained in the rice straw processed product] or the release rate of xylose [water] The amount of xylose residue recovered from the phase divided by the amount of xylose residue contained in the processed rice straw product] was measured.

The results are shown in FIG. FIG. 2 is a graph showing the results of an enzyme saccharification test (48 h) using rice straw recovered after treatment with chicken manure burning ash under each of the above conditions in Example 4.
That is, in FIG. 2, among the fibrous glucan and xylan, the glucose / xylose equivalent recovered as a solubilized product after enzymatic saccharification is shown as a ratio to the glucose / xylose content in the substrate.

As a result, as shown in FIG. 2, it was confirmed that the enzyme saccharification property of the rice straw was improved after the treatment with the chicken manure burning ash by the treatment with the chicken manure burning ash as compared with the untreated rice straw.

[Example 5]
Weigh the chicken manure burning ash A (850 mg, equivalent to 54.0 mg of phosphorus element) and treated ash A (equivalent to 686 mg, equivalent to 48.2 mg of phosphorus element) used in Example 1, put them in a 100 mL beaker, and add 50 mL of water. rice field.
After stirring this with a magnetic stirrer for 3 minutes, 0.5 mL was taken out and the pH and phosphorus concentration were measured.
Then, using a 5 N aqueous hydrochloric acid solution, the mixture was added to a hydrochloric acid concentration of 0.05 M, and after stirring for 3 minutes, sampling was performed in the same manner to measure the pH and phosphorus concentration.
In the same manner, the operation was repeated so that the hydrochloric acid concentrations were 0.1 M, 0.15 M, 0.2 M, 0.3 M, 0.4 M, and 0.5 M.

The results are shown in FIG. 3 (FIGS. 3A and 3B).
FIG. 3A shows phosphorus in Example 5 when hydrochloric acid was added to the suspension of chicken manure burning ash A (denoted as “PA” in the figure) or treated ash A (denoted as “PTA” in the figure). It is a graph which shows the acid solubilization rate.
Further, FIG. 3B is a graph showing the relationship between the measured pH value of the suspension and the phosphoric acid solubilization rate for the chicken manure burning ash A and the treated ash A.

As a result, as shown in FIG. 3A, it can be seen that the treated ash A liberated phosphorus under a lower hydrochloric acid concentration than the chicken manure burning ash A.
Further, as shown in FIG. 3B, looking at the relationship between the measured pH value at each stage and the phosphorus release rate, the treated ash A (PTA) has a higher pH condition than the chicken manure burning ash A (PA). It was shown that phosphorus release was occurring in.

[Example 6: Examination of fiber dissociation of plant biomass after reaction]
As plant biomass, 960 mL of water and 148 g of burning ash from chicken manure were placed in an aluminum bag for 492 g (equivalent to the weight of dry matter) obtained by cutting rice straw (Koshihikari) to a length of 4 cm in the longitudinal direction. (Moisture content 60%), and after sealing, heat treatment was performed at 95 ° C. for 1 hour.
This is opened after air cooling, and while suspending a part (equivalent to 50 g of dry matter weight) in 2.0 L of water, one stainless mesh with an opening of about 5 mm and two stainless meshes with an opening of about 2 mm are used. The treated rice straw was washed, filtered and collected (rice straw after treatment with chicken manure burning ash).
As a control group, 320 mL of water was mixed with 320 g (equivalent to the weight of dry matter) of the same cut rice straw (moisture content 50%), and the same heat treatment as above was performed (control rice straw).
After the chicken manure burning ash treatment, take 5 g each of rice straw and control rice straw (equivalent to the weight of dry matter), suspend them in 250 mL of water, and defibrate them 4 times for 15 seconds using a mixer (Hitachi, VA-G15). Was done.
The defibrated product was resuspended in 3 L of water and passed through a sieve with a mesh size of 2.36 mm and a diameter of 20 cm (Nonaka Rikaki Seisakusho). The entire amount of the passing liquid was collected, passed through the same sieve again, the sample trapped on the sieve was collected, and then dried in a drying oven at 105 ° C. until the weight became constant.

This dried product was pulverized by the Willey mill and ball mill used in Test Example 2, and the total glucan content in the sample was followed by the method of Ike M. et al., J. Appl. Glycosci. 60, 177-185 (2013). Was measured (A).
Similarly, the total glucan weight (B) contained in 5 g (equivalent to dry matter weight) of rice straw after treatment with chicken manure burning ash was measured, and the total glucan weight contained in the sample trapped on the sieve was measured. The value (BA) minus ..

As a result, the short fiber recovery rates of the defibrated rice straw after the treatment with the burning ash of chicken manure and the defibrated product of the control rice straw were 41.3% and 17.9%, respectively.
From this result, it can be seen that the rice straw after the chicken manure burning ash treatment according to the present invention could be easily defibrated.

Although the embodiments and examples of the present invention have been described in detail above, the above-described embodiments and examples are merely examples of the present invention, and the present invention is limited to the configurations of the above-described embodiments and examples. It is not something that is done. Even if there is a design change or the like within a range that does not deviate from the gist of the present invention, it is included in the present invention.

The present invention pays attention to the element contained in the combustion ash of livestock manure and its transferability, produces a phosphorus-containing substance having improved utility value, and modifies the characteristics of plant biomass by the action of calcium element or the like to prepare a saccharified raw material or By supplying it as fiber, it will contribute to the sophistication of regional resource recycling and the creation of new industries. In addition, since the reaction in the present invention is effective even when left under conditions that do not require heat treatment, it can also serve as a storage technique for suppressing the decay of plant biomass in a wet state. can.

Claims (14)

A method for producing a useful substance, which comprises mixing livestock manure burning ash and plant biomass in the presence of water and reacting them. The first aspect of the present invention, wherein the reaction is carried out by at least one of a method of heating a mixture of livestock manure burning ash, plant biomass and water, or a method of holding the mixture without heating for 1 day or more. How to make useful substances. The method for producing a useful substance according to claim 1 or 2, which comprises a step of recovering the useful substance from the reaction product obtained by the reaction. The step of recovering the useful substance is to add water after the reaction to obtain a fraction containing the water-insoluble inorganic substance derived from the livestock manure combustion ash as a main component and a fraction containing the water-insoluble component derived from the plant biomass as the main component. The method for producing a useful substance according to claim 3, which comprises a step of solid-solid separation. The method for producing a useful substance according to any one of claims 1 to 4, wherein the useful substance is a fraction produced after the reaction and containing a water-insoluble inorganic substance derived from the combustion ash of livestock manure as a main component. The method for producing a useful substance according to any one of claims 1 to 4, wherein the useful substance is a fraction generated after the reaction and containing a water-insoluble component derived from the plant biomass as a main component. A useful substance produced by the method for producing a useful substance according to any one of claims 1 to 6. Among the useful substances, the dried product of the fraction containing the water-insoluble inorganic substance derived from the livestock manure burning ash as the main component shows a low calcium / phosphorus ratio as compared with the value of the livestock manure burning ash before the reaction. The useful substance according to claim 7. A claim that the dried fraction of the useful substances, which is mainly composed of a water-insoluble inorganic substance derived from the livestock manure burning ash, shows a low potassium content as compared with the value of the livestock manure burning ash before the reaction. Item 7. Useful substance according to Item 7. Of the useful substances, the dried product of the fraction containing the water-insoluble inorganic substance derived from the combustion ash of livestock manure as the main component has the same phosphorus content when suspended in water and acid is added, before the reaction. The useful substance according to any one of claims 7 to 9, which exhibits a property of dissolving phosphorus with a smaller amount of acid added as compared with the value of livestock manure burning ash. Of the useful substances, the dried product of the fraction containing the water-insoluble inorganic substance derived from the combustion ash of livestock manure as the main component has the same phosphorus content when suspended in water and acid is added, before the reaction. The useful substance according to any one of claims 7 to 10, which exhibits the property of dissolving phosphorus at a higher pH as compared with the value in livestock manure burning ash. The useful substance according to claim 7, wherein a fraction containing a water-insoluble inorganic substance derived from the combustion ash of livestock manure or a dried product thereof as a main component is used as a phosphorus supply source. Of the useful substances, the fraction containing the water-insoluble component derived from the plant biomass as the main component or a dried product thereof has an enzymatic saccharification efficiency of the cell wall polysaccharide after pH adjustment as compared with the value of the plant biomass before the reaction. The useful substance according to claim 7, which is improved. Of the useful substances, the fraction containing the water-insoluble component derived from the plant biomass as the main component or a dried product thereof has improved the dissociative property of the fibrous constituents of the plant tissue as compared with the plant biomass before the reaction. The useful substance according to claim 7 or 13.

Images