JP2003200141A - Method for treating waste garlic residue - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To efficiently subject garlic residue to methane fermentation. <P>SOLUTION: The garlic residue 1 is added with iron 6 and hydrogen peroxide 7, the mixture is subjected to Fenton's oxidation treatment, and a substance having a sterilization (antibacterial) effect is oxidized/decomposed by OH radicals to be biodegradable and subjected to methane fermentation treatment by a fermentation treatment apparatus 9. The substance having the sterilization effect in a waste garlic residue is oxidized/decomposed, and the methane fermentation treatment is done efficiently. By the methane fermentation treatment of the waste garlic residue which has been treated by incineration or reclamation so far, the discharge of carbon dioxide, SOX, and NOX which cause environmental problems can be reduced, and methane useful as an energy source can be produced. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a treatment method capable of efficiently treating garlic residue waste.

[0002]

2. Description of the Related Art Conventionally, methane fermentation treatment has been known as a method for treating organic waste. A typical example of this type of processing method is shown in FIG. In the figure, organic waste 10
Is subjected to pretreatment in a pretreatment device 13 such as mechanical crushing or heat treatment, and for example, solid matter is crushed into slurry 14. When the solid content is large and the water content is small, it is mixed with the dilution water 12 to form the slurry 14. Pretreatment device 1
The slurry 14 obtained in 3 is then introduced into the methane fermentation treatment apparatus 15. In the methane fermentation treatment device 15,
Medium temperature methane fermentation treatment performed at 36-38 ° C or 50
The organic waste contained in the slurry 14 is fermented by the high temperature methane fermentation process performed at ˜55 ° C. Biogas 17 is generated during this fermentation process, and the rest is discharged as the desorbed liquid 16. The generated biogas 17 can be converted into heat or electricity and used. On the other hand, the desorbed liquid 16 is used as a compost and a soil conditioner, and after being dehydrated, it is incinerated or landfilled. Further, there is also a treatment method in which the organic waste is fermented to be composted or incinerated without performing the methane fermentation.

[0003]

By the way, since food residue waste contains a large amount of residual organic matter in the above-mentioned methane fermentation and a heavy post-treatment load, methane fermentation is not performed and the above-mentioned composting, incineration treatment, and landfill treatment are not performed. Mainly performed. However, this method does not have the advantage that useful biogas is obtained in methane fermentation, and carbon dioxide, SO _X , and NO _X are used in the incineration process.
It has been pointed out that there is a problem for the preservation of the global environment because the landfill treatment has a limited remaining life.
By the way, the applicant of the present application is applicable to the above-mentioned methane fermentation treatment in the garlic residue extracted from the extract and the waste containing the garlic residue generated in the food processing industry, etc., and the methane fermentation with reduced residual organic matter is possible. I found it possible. There is an advantage that useful biogas can be obtained by application to this methane fermentation process.

However, garlic contains an odorless component called alliin, and when garlic is cut or crushed, cells are broken, and this alliin has an odor peculiar to garlic due to the enzyme allinase contained in garlic. Change to allicin which has (antibacterial) action. When garlic in such a state is subjected to microbial treatment such as methane fermentation treatment, the activity of microorganisms contributing to microbial treatment is stopped or reduced due to the above allicin having a strong bactericidal (antibacterial) action. In the case of microbial treatment, it is generally practiced to crush, crush and fluidize the waste for efficient fermentation, and in the garlic residue waste, the crushing and crushing causes the above-mentioned cell destruction and formation of allicin. Is inevitable.
Therefore, there is a problem that the methane fermentation treatment for garlic residue waste is inefficient.

The present invention has been made in order to solve the above-mentioned problems of the conventional ones. Firstly, it is proposed to subject a garlic residue to a methane fermentation treatment, and further, the methane fermentation. It is an object of the present invention to provide a treatment method that prevents the activity of microorganisms from being inhibited by garlic components during treatment and enables efficient methane fermentation treatment. Preferably, the reaction between divalent iron and hydrogen peroxide (Fe ²⁺
+ H ₂ O ₂ → Fe ³⁺ + OH ·) produces OH.
By oxidatively decomposing the garlic residue waste by utilizing the Fenton oxidation treatment that oxidatively decomposes with (OH radical),
It is an object of the present invention to provide a treatment method capable of microbial treatment by oxidizing and decomposing a substance having a bactericidal (antibacterial) action.

[0006]

In order to solve the above-mentioned problems, the method for treating garlic residue waste according to the present invention is defined by Claim 1
The described invention is characterized in that the garlic residue waste is subjected to methane fermentation treatment.

The garlic residue of the present invention is usually the residue after squeezing an extract from garlic. However, the present invention is not limited to this raw material, but can be applied to garlic itself or a residue discharged when garlic is processed. In addition, the garlic residue waste may be a waste that is substantially solely a garlic residue or a waste mainly containing a garlic residue. Mainly containing garlic residue is, for example, those containing 2% or more garlic residue by mass%. When the methane fermentation treatment is a high temperature methane fermentation treatment, the treatment temperature is usually 50 to 55 ° C.

According to the invention described in claim 1, useful methane gas can be obtained by subjecting the garlic residue to methane fermentation treatment, and the amount of the treated material can be reduced.
Subsequent disposal, etc., will also be easier.

The method for treating garlic residue waste according to claim 2 is characterized in that the garlic residue waste is subjected to oxidative decomposition treatment with OH radicals prior to the microbial treatment of the garlic residue waste.

By the oxidation treatment with this OH radical,
Allicin or the like contained in garlic having a strong bactericidal (antibacterial) action is prevented from being decomposed or reduced to a low molecular weight, and the activity of the microorganism contributing to the treatment of the microorganism is inhibited by the garlic component. The microbial treatment includes the above-mentioned methane fermentation treatment, but the present invention is not limited to this and may be other microbial treatment such as composting treatment or activated sludge treatment.

According to a third aspect of the present invention, in the garlic residue waste treatment method according to the second aspect of the invention, the garlic residue waste is crushed or crushed to form a slurry, and then OH.
It is characterized in that the oxidative decomposition treatment by radicals is performed.

The above-mentioned garlic residue waste is crushed and crushed by
It can be carried out using a known crusher or the like, and the means is not particularly limited in the present invention. Further, when making a slurry, diluting water may be added if necessary.

According to the invention described in claim 3, crushing,
Although crushing promotes allicinization of the garlic component, this crushing and crushing of alliin causes the formation of allicin, which adversely affects microbial treatment, by aggressively forming allicin in a later step (such as stirring in a fermenter). It can be prevented from occurring, and the oxidative decomposition treatment is effectively performed by crushing and crushing. Furthermore, the efficiency of the methane fermentation treatment in the subsequent treatment is also improved.

In the method of treating garlic residue waste according to claim 4, in the invention according to any one of claims 1 to 3, the garlic residue waste is subjected to Fenton oxidation treatment prior to the high temperature methane fermentation treatment. Is characterized by.

According to the invention of claim 4, the substance having a bactericidal (antibacterial) action contained in the garlic residue waste is oxidatively decomposed and / or the garlic residue waste is reduced in molecular weight by the Fenton oxidation treatment, To reduce the degree of inhibition of microorganisms that contribute to methane fermentation processing. Furthermore, by increasing the efficiency of the methane fermentation process by oxidatively decomposing wastes into acetic acid that is directly converted to methane in the methane fermentation process.

According to a fifth aspect of the present invention, in the method of treating garlic residue waste according to the fourth aspect of the invention, in the Fenton oxidation treatment, the iron concentration is 0.01 to 0.5 mass% and the treatment temperature is 15 to 120 ° C. It is characterized by adjusting within the range of.

By adjusting the amount within the above range, the Fenton oxidation treatment is effectively performed. The iron concentration must be 0.01% by mass or more in the garlic residue in order to effectively carry out the Fenton oxidation treatment.
If it is less than mass%, the Fenton oxidation treatment is not effectively performed. Further, even if the iron concentration exceeds 0.5 mass%, the Fenton oxidation effect does not change, but the Fenton oxidation process becomes a steady state. Therefore, the iron concentration is preferably adjusted to 0.01 to 0.5 mass% during the Fenton oxidation treatment. The concentration may be one that is satisfied immediately before the Fenton oxidation treatment. Further, when the garlic residue waste itself contains iron, the iron concentration is adjusted in consideration of the concentration. The garlic residue, which means the iron concentration, is just before the Fenton oxidation treatment, and when diluting water is added, the slurry-like waste to which the diluting water is added is targeted.

Further, in order to effectively carry out the Fenton oxidation treatment, the treatment temperature is set to 15 ° C. or higher. If the temperature is lower than 15 ° C, inhibitors such as allicin will not be decomposed, and solids will not be solubilized. On the other hand, even if the temperature exceeds 120 ° C, there is no problem in decomposing inhibitors such as allicin,
In the high temperature range, the acetic acid produced is oxidatively decomposed to carbon dioxide, and the biogas yield in the subsequent methane fermentation is reduced. Therefore, the processing temperature is preferably adjusted to 15 to 120 ° C.

The treatment time of the Fenton oxidation treatment is not particularly limited, but is preferably 30 to 90 minutes. The reason is that the lower fatty acid increases in proportion to the treatment time when it is less than 30 minutes, and the increase becomes slower in 30 to 90 minutes. On the other hand, even when the treatment time exceeds 90 minutes, no increase in the lower fatty acid is observed and the reaction reaches a steady state. For this reason,
The Fenton oxidation treatment time is preferably 30 to 90 minutes.

According to a sixth aspect of the present invention, in the method for treating garlic residue waste according to the fourth or fifth aspect of the present invention, the Fenton oxidation treatment is performed in an amount of 10 to 100% by mass based on the solid substance amount of the garlic residue waste. It is characterized in that hydrogen peroxide is added to the garlic residue waste.

The above-mentioned addition of hydrogen peroxide is indispensable to the Fenton oxidation treatment, and in order to perform the treatment effectively, it is necessary to add 10 mass% or more to the solid substance amount of the garlic residue. If it is less than 10% by mass, effective Fenton oxidation treatment is not performed. On the other hand, since there is no particular problem even if the amount of hydrogen peroxide added exceeds 100% by mass, it may be determined in consideration of cost and the like. Therefore, the amount of hydrogen peroxide added is preferably 10 to 100% by mass. In addition,
The amount of solid substance of garlic residue means the mass of garlic residue waste, which is excluded when other solid substances are included.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention will be described below with reference to the accompanying drawings. As an example, the garlic residue waste 1 after squeezing the extract is crushed together with the dilution water 2 by the mechanical crushing device 3 to form a slurry 4. In the present invention, when the water content is large, the dilution water may not be added. The configuration of the crushing device and the degree of crushing can be appropriately selected.

The slurry 4 produced as described above is introduced into the Fenton oxidation treatment apparatus 5, and first, the iron concentration is 0.0
Ferrous chloride tetrahydrate is supplied from the iron storage tank 6 so as to be 1 to 0.5 mass% and added. Note that the material added for adjusting the iron concentration is not limited to this, and ferrous sulfate or the like can also be used. Next, 35 mass% hydrogen peroxide was supplied from the hydrogen peroxide storage tank 7 to the slurry 4 so that the amount of hydrogen peroxide was in the range of 10 to 100 mass% with respect to the amount of solid substance in the slurry 4. ,Added. The concentration of hydrogen peroxide itself is not particularly limited in the present invention.

After that, the Fenton oxidation treatment apparatus 5 is heated, and the Fenton oxidation treatment is performed under the conditions of a treatment temperature of 15 to 120 ° C. and a treatment time of 1 hour. Next, the Fenton oxidation treatment liquid 8 is introduced into a methane fermentation treatment device 9 equipped with seed sludge, and high temperature methane fermentation treatment is performed at an appropriate fermentation temperature (for example, fermentation temperature 55 ° C). Biogas 17 is generated in the fermentation treatment device 9, and the rest becomes desorbed liquid 16. These biogas and desorbed liquid can be used and disposed of in the same manner as known methane gas fermentation treatment methods.

[0025]

EXAMPLES Next, examples in which garlic residue waste is treated based on the treatment method of the above embodiment will be described. Diluting water was added to the garlic residue waste after squeezing the extract to obtain a slurry having a solid concentration of 4.7 mass%, and the slurry was subjected to Fenton oxidation treatment. In the Fenton oxidation treatment, the iron concentration was adjusted to 0.01% by mass, and 50% by mass of hydrogen peroxide solution was added to the amount of garlic residue solid substance in the slurry. This was subjected to Fenton oxidation treatment at a treatment temperature of 105 ° C. and a treatment time of 1 hour. Further, for comparison, a sample that was not subjected to Fenton oxidation treatment was prepared. The slurries of the respective test materials (with and without Fenton oxidation treatment) were put into the fermentation treatment apparatus so that the mass ratio with the seed sludge was 19: 1, and methane fermentation treatment was performed at a fermentation temperature of 55 ° C.
Figure 2 shows the cumulative amount of biogas generated over the course of days.
It was shown to. The amount of biogas generated in the blank (seed sludge only) without adding the slurry is also shown in FIG. As is clear from the figure, when the Fenton oxidation treatment is not performed, the amount of biogas generated is smaller than that of the seed sludge, and it is understood that biogas is not sufficiently generated from the waste. On the other hand, with the Fenton oxidation treatment, a large amount of biogas was generated in a few days, and it can be seen that the waste is effectively fermented.

Incidentally, in order to verify the oxidation treatment action under various conditions in the Fenton oxidation treatment, tests were conducted under various conditions. First, the above-mentioned slurry comprising garlic residue waste was prepared. Lower fatty acid content of this slurry, p
The H value was measured and is shown in Table 1. The substances having a bactericidal action in the garlic residue waste are said to be allyl sulfides, and the amount of sulfate ions that are considered to be decomposed and produced from them is also shown in Table 1. The degree of oxidation treatment can be evaluated by the change in these numerical values.

The iron concentration of the above slurry was adjusted to 0.01% by mass, hydrogen peroxide was added to the slurry at various addition amounts to prepare a plurality of test materials, and these were treated at a treatment temperature of 105.
The Fenton oxidation treatment was performed at a temperature of 1 hour for 1 hour. The amount of hydrogen peroxide was changed in the range of 0 to 100% by mass% with respect to the amount of the solid substance of the garlic residue in the slurry. Table 1 shows the amounts of lower fatty acids, sulfate ion amounts and pH values after the Fenton oxidation treatment in these test materials.

As is clear from Table 1, when the amount of hydrogen peroxide is set to 10% or more, the amount of lower fatty acid and the amount of sulfate ion are increased, and the pH value is also increased in acidity. It can be seen that various oxidation treatments have been performed. On the other hand, when the amount of hydrogen peroxide is less than 10%, the oxidation treatment is not sufficiently performed.

[0029]

[Table 1]

Next, using the same slurry as described above, the iron concentration of the slurry was variously changed, and hydrogen peroxide was added at 50% by mass.
After the addition, a Fenton oxidation treatment was performed at a treatment temperature of 105 ° C. and a treatment time of 1 hour. Table 2 shows the amounts of lower fatty acids and pH values after the Fenton oxidation treatment in each test material.

As is clear from Table 2, the iron concentration is 0.0
By setting the content to 1% by mass or more and 0.5% by mass or less, it is shown that the amount of lower fatty acid is sufficiently increased and the pH value is also increased in acidity, and it can be seen that sufficient oxidation treatment is performed. . On the other hand, when the iron concentration is less than 0.01% by mass, the above effect is not sufficiently obtained, and the iron concentration is 0.5
On the contrary, when the content exceeds the mass%, the amount of the lower fatty acid decreases.

[0032]

[Table 2]

Next, using the same slurry as above, the iron concentration of the slurry was adjusted to 0.01% by mass, and hydrogen peroxide was added at 50% by mass. The test material was subjected to Fenton oxidation treatment for various treatment temperatures of 1 hour.
Table 3 shows the amount of lower fatty acid, the amount of sulfate ion, and the pH value after the Fenton oxidation treatment in each test material.

As is apparent from Table 3, the treatment temperature is 15 to
At 120 ° C, the amount of lower fatty acid and the amount of sulfate ion are sufficiently increased, and the pH value also shows that the acidity is increased.
It can be seen that sufficient oxidation treatment has been performed.

[0035]

[Table 3]

[0036]

As described above, according to the present invention, garlic residue waste can be subjected to methane fermentation treatment.
Further, by oxidizing and decomposing a substance having a bactericidal action in the garlic residue waste, it is possible to efficiently perform microbial treatment such as methane fermentation treatment. By this method, garlic residue waste that was originally incinerated or landfilled can be treated by microorganisms such as methane fermentation, and the emission of carbon dioxide, SO _X and NO _X , which cause global environmental conservation problems, can be reduced. It has the effect of reducing and producing methane that can be used as an energy source.

[Brief description of drawings]

FIG. 1 is a flow diagram illustrating an example of a system that performs a processing method according to an embodiment of the present invention.

FIG. 2 is a graph showing a biogas production amount in a high temperature methane fermentation treatment test using garlic residue waste in the same example.

FIG. 3 is a flowchart showing a conventional system.

[Explanation of symbols]

1 Garlic residue waste 2 dilution water 3 Pretreatment equipment 4 slurry 5 Fenton oxidation equipment 6 iron storage tanks 7 Hydrogen peroxide storage tank 8 Fenton oxidation treatment liquid 9 Methane fermentation treatment equipment 16 Desorbed liquid 17 biogas

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tatsuo Nagai             4 Chatsu-cho, Muroran-shi, Hokkaido Japan Co., Ltd.             Inside the steel mill F-term (reference) 4D004 AA04 BA03 BA04 CA17 CA36                       CC11 DA03 DA06 DA10                 4D059 AA07 BA12 BA21 BA28 BC02                       BK11 CC03 DA22 DA44 EA06                       EA20 EB06

Claims (6)

[Claims] 1. A method for treating garlic residue waste, which comprises subjecting garlic residue waste to methane fermentation treatment. 2. A method for treating garlic residue waste, which comprises subjecting the garlic residue waste to oxidative decomposition with OH radicals prior to microbial treatment of the garlic residue waste. 3. The method for treating garlic residue waste according to claim 2, wherein the garlic residue waste is crushed or crushed to form a slurry, and then the oxidative decomposition treatment with OH radicals is performed. 4. The method of treating garlic residue waste according to claim 1, wherein the garlic residue waste is subjected to Fenton oxidation treatment before the garlic residue waste is treated with microorganisms. 5. The garlic residue waste according to claim 4, wherein the iron concentration is adjusted to 0.01 to 0.5 mass% and the processing temperature is adjusted to 15 to 120 ° C. during the Fenton oxidation treatment. Processing method. 6. The garlic residue waste product according to claim 4, wherein 10 to 100% by mass of hydrogen peroxide is added to the garlic residue waste during the Fenton oxidation treatment. Garlic residue waste treatment method.