JPH02214539A - Production of catalytic material adsorbing low molecular gas - Google Patents

Abstract

PURPOSE:To enhance freshness maintaining function and antibacterial function by extracting a specified org. acid compd. from raw material for extracting the org. acid compd., impregnating the extracted org. acid compd. into a microporous material, drying and crushing the material. CONSTITUTION:Saccharides are added to diatomaceous earth and lactic acid fermentation is carried out. The earth is dried by the heat of the fermentation and crushed to obtain raw material for extracting an org. acid-rich org. acid compd. This org. acid compd. is extracted from the raw material and impregnated into a microporous material under reduced pressure. The material is then dried and crushed to produce a catalytic material adsorbing low molecular gas. The org. acid compd. is preferably extracted by adding warm water to the raw material, stirring them at a constant temp. and carrying out specific gravity separation and filtration.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a low-molecular gas adsorption catalyst material, and more specifically to a freshness-preserving material for fresh foods, a bacteriostatic material, a discoloration prevention material,
The present invention relates to a method for producing a low-molecular gas adsorption catalyst material in which an organic acid compound is impregnated into a fine porous material suitable for use as a deodorizing material, a dehumidifying material, or in a broader sense as a food preservation material.

[Conventional technology]

As is well known, food preservatives in the broad sense described above are applied to fresh foods such as vegetables, fruits, fish, meat, and the like. In other words, antibacterial materials, freshness preservation materials, discoloration prevention materials, deodorizing materials,
This is called a dehumidifying material. Of course, in terms of how this is applied, it may be used by being put into wrapping paper or packaging containers that contain food, or it may be used by being mixed into the composition of a film-like sheet. In some cases. These are supplied to the market in the form of laminate films, stretch films, etc., and when these films are applied to food packaging etc., they function as the above-mentioned freshness preserving material.

In addition, it may be mixed into a coating material or paste applied to the surface of a sheet-like body.

Several types of freshness-preserving materials of this kind have been proposed in the past and are in widespread use.

Among these, recently, low-molecular gas adsorption catalyst materials made by impregnating organic acid compounds into fine porous materials have been used as food preservation materials in a broad sense, as freshness-preserving materials, antibacterial materials, and for specific purposes. It is becoming recognized that it is useful as a discoloration prevention material, a deodorizing material, a dehumidifying material, etc. That is, fine porous materials such as coral, silica gel, activated alumina, synthetic and natural zeolites, white china clay, perlite obtained from vermiculite, maifan stone, especially sulfuric acid,
An organic acid compound containing 80% or more of an organic acid, more specifically a condensation product of a polyhydric phenol and a nitrogen-containing compound, in a fine powder of a natural porous material mainly composed of calcium sulfate, calcium carbonate, and calcium phosphate. A low-molecular gas adsorption catalyst material impregnated with a liquid organic acid compound containing a large amount of phenic acid, a carbohydrate, various metal ions, etc. as a polysaccharide, has been proposed as a useful material. The conventional manufacturing method for this low molecular gas adsorption catalyst material is as follows.

That is, diatoms containing diatoms are dried. In this case, conventionally 8
The original soil, which has a moisture content of 0% or more and is in a fluid state, is left at room temperature for about 6 months to reach a moisture content of about 65%, and then spread widely in a plastic greenhouse and allowed to air dry to reduce the moisture content. It was set at around 33%. After this, crush this,
Obtain raw materials for organic acid compound extraction. Thereafter, the above-mentioned liquid organic acid compound is extracted from this raw material according to a conventional extraction method.

Thereafter, the above-mentioned various fine porous materials prepared separately are immersed in this liquid organic acid compound to impregnate the organic acid compound into the structure of the fine porous materials. In this case, conventionally the above-mentioned dipping operation was performed under normal pressure. Thereafter, it was dried and the fine porous material containing this organic acid compound was pulverized to obtain a low-molecular gas adsorption catalyst material. They were then processed according to their intended use.

[Problem to be solved by the invention]

Although the above-mentioned conventional technology is an excellent technique for producing a low-molecular gas adsorbent in which an organic acid compound is impregnated into a fine porous material, the present inventors Improving the gas adsorbent itself, that is, improving its freshness retention function, antibacterial function, deodorizing function, dehumidification function, etc., and improving this manufacturing method,
In other words, after trying to establish a manufacturing method to improve productivity and stabilize quality, it was discovered that there was a problem with the method.

That is, to obtain raw materials for extracting liquid organic acid compounds, it is necessary to obtain soil containing diatoms and dry it to a moisture content of 25 to 35%. The final drying stage also relied on natural drying. Therefore, based on 1 raw material for extracting organic acid compounds, approximately 3 to 4
It took a week.

For this reason, productivity was extremely poor, and improvements in efficiency were desired.

In addition, in order to improve the freshness preservation function and deodorization function of this low molecular gas adsorption catalyst material, the more polysaccharides are included in the final product, the better the freshness preservation effect will be. However, in the past, the raw material was simply dried naturally without adding any additives to the soil containing diatoms, so there was a certain limit to the polysaccharide content, and even more completely. It was a desirable place.

Furthermore, in the case of the prior art, the process of immersing a fine porous material in the extracted liquid organic acid compound and impregnating the liquid organic acid compound into the fine porous material is carried out under normal pressure, so As a result of the experiment, it was found that it is difficult for liquid organic acid compounds to penetrate into every corner of the microporous material's structure. More specifically, since the fine porous material itself has an open cell structure and has a large specific surface area, in order to effectively use it, it is necessary to impregnate the inside of the fine pores with a liquid organic acid mixture. It was confirmed that the liquid organic acid compound adhered to the outermost surface of the microporous material and was less likely to penetrate into the microporous material because it was conventionally operated under normal pressure.

Therefore, there is a limit to increasing the amount of liquid organic acid compound relative to the amount of porous material, and it takes a certain amount of effort to improve the freshness retention function, deodorization function, dehumidification function, etc. of the final product's low molecular gas adsorption catalyst material. There was a limit.

〔the purpose〕

Therefore, an object of the present invention is to produce a low-molecular gas adsorption catalyst material made of a fine porous material impregnated with an organic acid compound, and in particular to obtain a raw material for extracting an organic acid compound, We have improved the drying process of the drying process to further shorten the drying time and increase mass productivity, and at the same time, we have added as much polysaccharide as possible to the low molecular gas adsorption catalyst material of the final product in order to better demonstrate its effectiveness. In addition, we have improved the process of impregnating a liquid organic acid compound into a fine porous material, and we have also improved the process of impregnating a liquid organic acid compound into a fine porous material. It is an object of the present invention to provide a manufacturing method for better permeation, maximizing the amount of impregnated organic acid compound relative to the amount of fine porous material, and better exhibiting effects such as maintaining freshness.

[Means for Solving the Problem] [Operation] In order to achieve the above object, the present invention has the following technical means.

First, the process of drying and pulverizing soil containing diatoms to obtain a raw material for extracting organic acid compounds is as follows.

That is, soil containing diatoms that exhibits a moisture content of around 80% at the stage of collection is left in a warehouse or the like, and is brought to a moisture content of about 55 to 65% over about 6 months. Such soil is produced, for example, in Moriyama-cho, Kita-Takagi-gun, Nagasaki Prefecture, Japan. It is said that diatoms were formed through low-temperature fermentation over many years.

To the soil having such properties, 1 part by weight of sugars corresponding to 0.5 to 2% of the soil is added. After 10 to 12 hours have elapsed after adding this, which is preferably equivalent to 1%, lactic acid fermentation is carried out for about 40 to 55 hours while maintaining the temperature at 60 to 80°C. At this time, a small amount of air is continuously blown during this time.For example, when sugars equivalent to 1% by weight are added to soil containing 1.00 Kg of silicon, 0.3 m''/hr
Blow out the air. The lactic acid fermentation converts sugars into lactic acid and generates fermentation heat in the process. That is, fermentation heat is generated in the piled soil, and this fermentation heat evaporates the moisture in the soil, resulting in a moisture content of around 30%.

That is, drying progresses in an extremely short period of time compared to the conventional method, and as a result, the productivity of the entire low molecular gas adsorption catalyst material as a final product is significantly improved. In addition, it was confirmed that the low-molecular gas adsorption catalyst material contained more polysaccharides, and its various effects such as freshness preservation, dehumidification, deodorization, and antibacterial effects increased. Thereafter, this dried raw material is pulverized to a particle size of 15 to 30 mesh in order to increase the contact area required in the next step of organic acid compound extraction step and immersion step into the microporous material. . This produces a raw material for extracting organic acid compounds.

Subsequently, from the above raw material for extracting organic acid compounds, a high degree of
The extraction process for producing a compound containing 0% or more of organic acid is as follows.

That is, ``Add hot water to the raw material for organic acid compound extraction and keep it at a constant temperature.
Stir. To the above hot water, add 8 to 12% by weight of the raw material for extracting organic acid compounds. Using hot water of about f -C, stir for about 30 to 90 minutes while maintaining the temperature (℃).
Filter through a micron-grade filter. This results in 2
~5 micron particles of organic acids and their compounds are obtained.

This organic acid compound contains 90% or more of organic acids, such as carboxylic acid, sulfonic acid, sulfinic acid,
Among them, humic acid, which is a condensate of polyhydric phenol and nitrogen-containing compound, is used. Preferably.

In particular, as a result of the above lactic acid fermentation, it is possible to increase carbohydrates as polysaccharides that are useful for improving various effects such as freshness retention of the final product of the low-molecular gas adsorption catalyst material. The pH of this liquid organic acid compound is adjusted to a range of 2.98 to 3, and the acidity is 4 to 5% in terms of citric acid.

Next, the step of impregnating the liquid organic acid compound thus obtained into the structure of the microporous material is as follows.

That is, as the fine porous material, coral, silica gel, activated alumina, synthetic or natural zeolite, white china clay, perlite obtained from vermiculite, maifan stone, etc. are considered. Particularly desirable is a fine powder of a natural porous material containing sulfuric acid, calcium sulfate, calcium carbonate, and calcium phosphate as main components.

These pores are micron-sized, have an extremely large surface area, and have extremely high contact efficiency with gas.

Now, this microporous material has a particle size of 300 to 400.
Using something similar to a mesh, it is immersed in an amount of organic acid compound equivalent to the weight ratio. At this time, under reduced pressure, that is, 0.
It is characterized by being carried out under a pressure of 8 to 0.98 atmospheres. That is, in the case of the conventional technique performed under normal pressure, the liquid organic acid compound adheres to the outermost surface of the porous material and does not penetrate into the tissue. Therefore, the total surface area of the fine porous material did not contribute effectively to freshness preservation or deodorization. However, when the process was carried out under reduced pressure, the liquid organic acid compound permeated into each pore more effectively. The above decompression step was carried out for 20 to 30 hours, and the subsequent immersion step was carried out for about 40 to 50 hours.
It is preferable to leave it at a constant temperature for a certain period of time, that is, to allow the organic acid compound to impregnate and fix within each structure of the microporous material.

Thereafter, it is forcedly dried using hot air at 50 to 70° C. for about 90 to 100 hours to a moisture content of 3 to 7%, and then pulverized to obtain a low-molecular gas adsorption catalyst material.

The low-molecular gas adsorption catalyst material obtained in this way can be broadly defined as a food preservation material, and can be used as a freshness-preserving material, deodorizing material, dehumidifying material, etc.
It can be used as a bacteriostatic material, etc. As for how it is used, it may be used in food packaging or containers, that is, it may be used as an encapsulant, it may be mixed into a film or sheet, or it may be used as a coating material or glue. May be mixed with As a result of its use, it adsorbs and removes the ethylene gas generated from fresh foods such as vegetables, fruits, fish, and livestock meat, and has an excellent freshness-keeping effect, as well as deodorizing, antibacterial, and discoloration prevention effects. Ta.

In particular, the drying time of soil containing diatoms is significantly shortened and mass production is possible, the polysaccharide content is increased by lactic acid fermentation which makes this possible, and each pore structure of the microporous material is increased. Since the organic acid compound penetrates into every corner of the product, various effects such as almost denting were observed compared to the conventional product with the same amount of product as the conventional repair.

〔Example〕

Next, preferred embodiments of the production method of the present invention will be described in detail.

Example 1 1 kg of sugars was added to 100 kg of soil containing diatoms with a moisture content of 55%, and after 12 hours, it was kept at 70°C and
．． Lactic acid fermentation was carried out for 48 hours while continuously supplying air at a rate of 3 m'/hr, and the fermentation heat dried the product to a moisture content of 30%, which was then ground to obtain a raw material for organic acid extraction with a particle size of 30 mesh. Manufactured.

Add warm water (95°C) equivalent to 10% by weight to this, and
The mixture was stirred at 5° C. for 1 hour, subjected to specific gravity separation for 24 hours, and filtered to extract 2 micron-sized organic acid compounds.

The new method tested the organic acid compounds and obtained the results shown in Tables 1-6.

Table 1 Table 2 General property test results Harmful component test results 3 Quantitative analysis of various metals 6 Sugar analysis results Table 4 Table 5 Organic acid composition NOA acid analysis results After this, 300 of the above liquid 411 acid compounds were found in 250 sentences. Mix and stir 100 kg of Meashiyu perlite, and make the whole 0.
．． The pearlite was placed in a vacuum chamber at 98 atmospheres and immersed in the organic acid compound in that state. This immersion was carried out for 24 hours,
After that, it was left for 48 hours and dried at room temperature for 120 hours.
A product low molecular gas adsorbent was obtained.

The chemical properties of the above pearlite were as shown in Table 7 below. Tama 7 A freshness retention ability test was attempted using this pearlite. The results are listed as the freshness retention ability comparison test results in Tables 8 to 14 below. As can be seen from this, it was recognized that the product had a remarkable ability to maintain freshness.

Example 2 300 grams of the same organic acid compound obtained in Example 1 above were
Mix and stir with 300 kg of coral of 50 mesh, 0.9
Corals are placed in an organic acid compound in a chamber with a reduced pressure of 8 atm.
After soaking for 24 hours, the temperature was maintained at a constant temperature for 24 hours.
It was dried for 8 hours to a moisture content of 5% and pulverized to obtain a product.

Using this, a freshness retention ability test was attempted. The results are also shown in Tables 8 to 14 below.

Table 10 Table 11 Table 13 Table 12 Table 14 In Tables 8 to 14 above, Example 1 and Example 2 refer to the low-molecular gas adsorption catalyst materials produced in Examples 1 and 2, respectively, at 0.03 m/m X400 ■/■ Moreover, commercially available polyfilms are those in which samples of each product name were encapsulated in commercially available polyfilms, and changes thereof were observed under the same conditions as above.

Rating is on a 5-point scale from "5" to rlJ, with "5" being the highest and "3" being the best.
is the limit of product value, and is based on the condition of the store in the evening. As can be seen from these facts, the effect of preserving freshness on fresh foods was observed.

〔effect〕

As detailed above, according to the present invention, in a broad sense, food preservation is possible, and for each purpose, it is effective to preserve freshness, prevent discoloration, deodorize, and dehumidify. Not only can we provide a method for producing molecular gas adsorption catalyst materials, but we can also carry out the drying stage of soil containing diatoms under lactic acid fermentation in the manufacturing process of raw materials for organic acid extraction, and dry it using the heat of lactic acid fermentation. Raw materials for organic acid extraction can be produced within a short period of time, and the lactic acid fermentation allows the final product to contain an increased amount of polysaccharides, so that various effects such as freshness retention are better exhibited. Furthermore, since the step of impregnating the liquid organic acid compound into the fine porous material is carried out under reduced pressure, each pore of the thin pores and every corner of the tissue is impregnated with the organic acid compound. It is possible to provide a method for producing a low-molecular gas adsorbent that effectively exhibits the following effects.

[Brief explanation of the drawing]

FIG. 1 of the accompanying drawings is a manufacturing process diagram.

Claims (1)

[Claims] (1) A raw material for extracting an organic acid compound containing a high degree of organic acid is produced by drying and pulverizing soil containing diatoms, and then a raw material for extracting the organic acid compound The organic acid compound is extracted from the organic acid compound, and then the extracted organic acid compound is impregnated into a fine porous material, which is then dried,
In the manufacturing method of a low-molecular gas adsorption catalyst material produced by pulverization; the drying process of the soil containing diatoms is performed by adding sugars to the soil containing diatoms, causing lactic acid fermentation, and utilizing the fermentation heat generated at that time. At the same time, the step of impregnating the organic acid compound into the fine porous material is carried out under reduced pressure conditions when the fine porous material is immersed in the organic acid compound. Manufacturing method of catalyst material. (2) The step of adding sugars to the diatom-containing soil, causing lactic acid fermentation, and drying the diatom-containing soil using the fermentation heat generated during the process is carried out from 10 to 30 minutes after adding sugars to the diatom-containing soil. After 14 hours, while supplying air to these and keeping them at a temperature of 60 to 80°C,
The process is carried out for about 5 hours, and the soil containing diatoms with a moisture content of about 65 to 50% is reduced to a moisture content of 25 to 35% by the above fermentation heat.
2. The method for producing a low-molecular gas adsorption catalyst material according to claim 1, wherein the material is dried to a certain degree. (3) The method for producing a low-molecular gas adsorption catalyst material according to claim 2, wherein the sugar added to the diatom-containing soil is equivalent to 1% by weight of the diatom-containing soil. (4) The step of extracting an organic acid compound from the raw material for extracting an organic acid compound is performed by adding warm water to the raw material for extracting an organic acid compound, stirring at a constant temperature, followed by specific gravity separation, and further filtration. Claim 1 characterized by carrying out
A method for producing a low-molecular gas adsorption catalyst material as described in Section 1. (5) The hot water added to the raw material for extraction of the organic acid compound is equivalent to 8 to 12% by weight of the organic acid compound, and the constant temperature stirring step is carried out at 90 to 95°C for 30 minutes to 1.5 hours. 5. The method for producing a low-molecular gas adsorption catalyst material according to claim 4, wherein the specific gravity separation step is carried out for 20 to 24 hours to extract a liquid organic acid compound with a size of 2 to 5 microns. . (8) The step of immersing the fine porous material in the organic acid compound under reduced pressure conditions is performed at 0.8 to 0.98 atm, 20 to 3
2. The method for producing a low-molecular gas adsorption catalyst material according to claim 1, wherein the method is carried out for 0 hours. (7) A claim characterized in that the fine porous material is selected from coral, silica gel, activated alumina, synthetic and natural zeolites, white china clay, perlite obtained from vermiculite, and maifan stone. 6. A method for producing a low-molecular gas adsorption catalyst material according to item 6.