JPH07328390A - Enzymatic decomposition treatment of ungula/horn of animal - Google Patents

Abstract

PURPOSE:To obtain an oligopeptide fraction having a predetermined mol.wt. and usable for a desired purpose such as a foaming agent by successively treating an enzyme decomposition product of ungula/horns using a UF membrane and an RO membrane and to recycle RO membrane transmitted matter to enzyme reaction to use the same. CONSTITUTION:An enzyme decomposition product can be treated in a closed system generating no environmental pollution. The enzyme decomposition product is successively treated using a UF membrane and an RO membrane to obtain an oligopeptide fraction devided into desired molecular fractions. This fraction can be used as a foaming compsn. or a cosmetics material. Since Fe<2+> is used in the production of the foaming compsn., the foaming compsn. excellent in foamability and the holding power of an air bubble is obtained. The oligopeptide compsn. with a low mol.wt. transmitted through the RO membrane has a light color and can be used as a cosmetics material as it is. RO membrane transmitted matter is recycled to enzyme reaction to be reutilized and the enzyme decomposition product is effectively treated without bringing about environmental pollution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is to hydrolyze hoof horns of animals such as cows and buffaloes by enzymes without causing pollution such as foul odors and organic pollution, and to effectively use the decomposed products. And a method for producing a foaming agent composition from the decomposed product; and a method for producing an oligopeptide composition that can be used as a moisturizing agent and the like from the decomposed product. The present invention further relates to the foaming agent and oligopeptide composition produced by the above method.

[0002]

Background Art [0002] Animal hoof horns (hereinafter, hoof horns are referred to as horns and / or hoofs in the present specification), and particularly hoof horns of cattle and buffalo have a high content of keratin and their decomposition products. Has a high foaming property, and since the generated bubbles are relatively stable, it is used as a fire extinguishing agent or a foaming agent (foaming agent) for obtaining a lightweight concrete member.

[0003] The hoof horns of the above-mentioned animals are used as a raw material of the above-mentioned foaming agents because they are wastes of livestock and can be supplied inexpensively in large quantities. For example, in order to obtain a foaming agent from buffalo horn, first, the buffalo horn is subjected to heat treatment and then crushed, and a slaked lime water suspension is added to the crushed product as an alkaline solution, followed by heating to carry out alkali decomposition. As a result, keratin is hydrolyzed and mainly exists in the form of oligopeptide dissolved in the reaction solution. The reaction solution is collected by filtration, ammonium bicarbonate is added as a neutralizing agent to adjust the pH to 7 to 7.5, and then filtered and concentrated. This can be used as a foaming agent as it is, and normally, additives such as a stabilizer and a preservative are further added to obtain a product.

In the above-mentioned conventional method, since the buffalo horns are decomposed by using alkali, ammonia is produced as a by-product. In addition, ammonium bicarbonate is used to neutralize the alkali (usually slaked lime). It is neutralized to calcium carbonate, but ammonia is also produced as a by-product in this step. The generated ammonia is removed by further passing through a deodorizing device, but since it cannot be completely removed, the working environment in the factory deteriorates. In addition, the living environment in the area around the factory may be compromised, causing a pollution problem.

Further, the above method requires a considerable amount of energy and time for decomposing keratin, and thus the working efficiency is poor.

On the other hand, the present inventors have developed a method for producing a foaming agent by heat-treating hoof horns of animals such as cows and buffaloes, and then crushing and enzymatically hydrolyzing them. -1
54627 publication). According to this method, enzymatic decomposition is possible, resulting in low energy cost and no odor due to ammonia.

Furthermore, the present inventors have developed a method for producing a foaming agent by adding Ca ²⁺ to the above-mentioned enzymatic hydrolyzate and then heating and concentrating it (JP-A-5-279652). According to this method, a foaming agent with improved cell retention can be obtained.

As described above, a method has been developed in which hoof horns of animals such as cows and buffaloes are enzymatically decomposed and used effectively as a foaming agent. Furthermore, an enzymatic decomposition treatment method is desired in which this enzymatic decomposition and the subsequent treatment can be carried out in a closed system and does not affect the surrounding environment. It is also desired to use the enzymatic degradation product for applications other than the above foaming agent.

[0009]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned conventional problems.
An object of the present invention is to provide an enzymatic decomposition treatment method capable of enzymatically decomposing the hoof horns of animals such as cows and buffaloes without affecting the surrounding environment and treating them with a closed system. Another object of the present invention is a method for producing a foaming agent composition utilizing the above treatment method,
Another object of the present invention is to provide a foaming agent composition having improved foaming power and cell retention power obtained thereby. Still another object of the present invention is to provide a method for producing an oligopeptide composition which has a relatively low molecular weight and can be used in various applications, and an oligopeptide composition obtained by using the above-mentioned treatment method. It is in.

[0010]

Means for Solving the Problems If the enzymatic decomposition products of hoof horn are sequentially treated with a UF membrane and an RO membrane, the inventors have a predetermined molecular weight and use them for a desired purpose such as a foaming agent. A possible oligopeptide fraction, and RO
They have found that the membrane permeate can be recycled for use in an enzymatic reaction, and have completed the present invention.

The method for enzymatically decomposing animal hoof horns according to the present invention comprises: A) a step of enzymatically decomposing animal hoof horns; B) subjecting the enzymatic decomposition product to a UF membrane, and UF permeating the UF membrane; A step of obtaining a membrane permeate and a UF membrane concentrate concentrated on the UF membrane, C) subjecting the UF membrane permeate to an RO membrane, and concentrating the RO membrane permeate permeating the RO membrane and the RO membrane And a step of D) recycling the RO membrane permeate to a new animal hoof horn enzymatic degradation step.

The method for producing the foaming agent composition of the present invention comprises the step of enzymatically decomposing an animal hoof horn, and subjecting the enzymatic decomposition product to a UF membrane to obtain a UF membrane concentrate concentrated in the UF membrane. And a step of adding Fe ²⁺ to the UF membrane concentrate and performing heat concentration.

The method for producing the foaming agent composition of the present invention comprises the step of adding Fe ²⁺ to the UF membrane concentrate obtained in step B of the above-mentioned hoof horn treatment method, and the Fe ²⁺ addition concentrate. Further, the step of concentrating by heating is included.

In a preferred embodiment, the Fe ²⁺ added to the UF membrane concentrate is the TOC of the UF membrane concentrate.
The concentration is 0.0035 g or more per 1 g.

The present invention includes a blowing agent composition made by any of the above methods.

The method for producing the oligopeptide composition of the present invention comprises the step of enzymatically decomposing an animal hoof horn, the step of subjecting the enzymatic decomposition product to a UF membrane, and obtaining a UF membrane permeate that has permeated the UF membrane. Subjecting the UF membrane permeate to an RO membrane to obtain an RO membrane concentrate concentrated with the RO membrane, and drying the RO membrane concentrate.

The method for producing the oligopeptide composition of the present invention includes a step of drying the RO membrane concentrate obtained in the above step C.

The present invention includes the oligopeptide composition produced by the above method.

As the hoof horns of animals used as a substrate in the method of the present invention, hoof horns of cattle, buffaloes, etc. containing proteins mainly composed of keratin are used. Buffalo horn, which has been conventionally used as a raw material for a foaming agent or the like, can be particularly preferably used. It is also possible to use a mixture of two or more substrates.

Examples of proteolytic enzymes used for enzymatic degradation include microorganisms (Bacillus genus, Aspergillus genus, etc.)
Examples include enzymes derived from or derived from animal tissues. Commercial products of such enzymes include savinase (Bacillus sub
derived from tilis, Alcalase (Bacillus licheniformis)
Origin), Esperase (from Bacillus genus bacteria), (all from NOVO), protease (Aspergillus mell
Us origin; Amano Pharmaceutical Co., Ltd.), PTN (porcine spleen origin, main component trypsin; NOVO). Savinase is particularly preferable.

The outline of the enzymatic decomposition treatment method of the present invention is shown in FIG. First, the hoof horns of animals such as cows and buffaloes are enzymatically decomposed.
In order to facilitate enzymatic degradation, the hoof horn is usually heat treated,
Perform crushing process. For example, the hoof horn of an animal can be obtained by
As described in Japanese Patent No. 79652, 130 to 200
2.7 to 15.9 under conditions of ℃, preferably 175 ℃.
The heat treatment is performed under a pressure of kg / cm ² , preferably about 5 to 12 kg / cm ² , more preferably about 6 to 8 kg / cm ² , and most preferably about 8 kg / cm ² .
The processing time is usually 1.5 hours. When the heat treatment is performed in this manner, a part of the keratin protein forming the horns and hoofs is changed from the α-helix to the β-helix structure, so that the enzymatic decomposition described later can be easily performed.
The heat-treated hoof horn is then crushed to obtain a crushed product having a particle size suitable for enzyme reaction. The particle size of the pulverized product is preferably 1.0 mm or less, and particularly preferably 0.71 to 0.05 mm.

The pulverized product thus obtained is suspended in water or an appropriate buffer as a reaction medium, and the above-mentioned proteolytic enzyme is added to carry out the reaction. As the buffer solution, a phosphate buffer solution, a Tris buffer solution or the like can be used. The pH of the buffer solution is appropriately adjusted according to the type of proteolytic enzyme used. For example, when using savinase, the pH is preferably adjusted to about 8.3. The pulverized product as a substrate is added to the reaction medium at a ratio of about 25% by weight or less. The amount of the decomposing enzyme varies depending on the kind and activity of the enzyme, but when a commercially available enzyme is used, it is generally preferably 2 to 15% by weight based on the pulverized product.

For example, the enzymatic reaction is carried out as shown in FIG. First, a mixture of a buffer solution, the pulverized product, and an enzyme was charged, and the reaction solution 1 was stirred with a stirrer 2 to 40
To 70 ° C. (first step). The reaction time may be long, but is usually about 1 hour. By this reaction, the substrate is hydrolyzed to be an oligopeptide or amino acid. After the reaction, a new substrate is added to the enzyme reaction solution 1 (second step),
After standing for 3 to 10 minutes after stirring (third step), the supernatant 1
1 is drawn out by decantation (4th step), and this is used as an enzymatic degradation product. Water or an RO membrane permeate obtained by the treatment described below is newly added to the remaining precipitate 12 (fifth step), and the reaction is returned to the first step for about 60 minutes (first step). In this way, the above operation is repeated. As shown in Example 1 and FIG. 7, which will be described later, the decomposition rate was maintained at about 65% to about 85% in the batch reaction repeated 4 times, but the decomposition rate was significantly increased when the reaction was repeated 6 times or more. Since it decreased, it is considered that the number of repetitions is preferably up to 5.

The new substrate can be added not in the second step shown in FIG. 2 but in the subsequent decantation liquid obtained in the third step, the fourth step, or the fifth step, but in the second step. An effective enzymatic reaction is carried out by the addition of the enzyme. When the substrate is added in the second step, the enzyme 3 in the reaction solution is adsorbed by the substrate 4 as shown in FIG. As a result, the enzyme is prevented from being removed by decantation. When the adsorbed enzyme is further repeatedly reacted, it is released from the substrate and decomposes the substrate as shown in FIG. The residue generated after enzymatic decomposition of hoof horn can be used as, for example, an organic nitrogen fertilizer.

Then, this enzymatic degradation product was subjected to an ultrafiltration membrane (UF membrane) as shown in the scheme of FIG. 1 to obtain a UF membrane concentrate concentrated by the UF membrane and a UF membrane permeate that passed through the UF membrane. Is obtained. As the UF film, a film made of polyolefin or polyacrylonitrile is used. Usually, the molecular weight cutoff is 10,000 to 100,000, preferably about 2.
10,000 UF membranes are used. For example, when a UF membrane having a cut-off molecular weight of 20,000 is used, the UF membrane concentrate contains oligopeptides having an average molecular weight of about 1,000 or more. The average molecular weight of this oligopeptide is, for example, 2,4,6-trinitrobenzenesulfonic acid (T
It is calculated by measuring the absorbance at 420 nm after performing the reaction using NBS (AFSA HABEEB: De
termination of Free Amino Groups in Proteins by Tr
initrobenzensulfonic Acid. ANALYTICAL BIOCHEMISTRY
14 , 328-336 (1966)). However, the apparent molecular weight of the oligopeptide contained in this UF membrane concentrate depends on its conformation or due to the addition of water molecules.
It is considered that the average molecular weight is higher than the above. The UF membrane concentrate is treated as described below to obtain a foaming agent composition. The use of the UF membrane has the effect of suppressing the consumption of energy required for heating and concentration during the production of the foaming agent.

The UF membrane permeate is then passed through the reverse osmosis membrane (R
O membrane) and RO membrane concentrate concentrated on the RO membrane and R
An RO membrane permeate that has permeated the O membrane is obtained. As the RO film, a cellulose acetate-based or synthetic polymer-based film is used. Loose RO membranes, typically NT, that can be operated at low pressure
R-7400 series (manufactured by Nitto Denko Corporation) is used. As a result, the RO membrane concentrate has an average molecular weight of about 500.
Approximately 1,000 oligopeptides are contained. The average molecular weight of the oligopeptide contained in the RO membrane concentrate can be calculated in the same manner as the oligopeptide contained in the UF membrane concentrate. This RO membrane concentrate is treated as described below to give an oligopeptide composition used for creams, cosmetic materials such as hair styling agents, raw materials for artificial hair, and the like.

As shown in the scheme of FIG. 1, the RO membrane permeate is returned to the enzymatic decomposition step and used as make-up water (water for preparing a substrate solution having a predetermined concentration). Although this RO membrane permeate contains components such as oligopeptides and amino acids having small molecular weights, the efficiency of enzymatic degradation is hardly reduced as shown in Example 1 described later.

A foaming agent composition is prepared from the UF membrane concentrate obtained by the above-mentioned enzymatic decomposition treatment method. First, Fe ²⁺ is added to this UF membrane concentrate. Specifically, a water-soluble iron compound that can generate Fe ²⁺ or a solution thereof is added. Examples of such iron compounds include iron sulfate and iron chloride. The amount of the above salt added depends on the total organic carbon content (TOC) of the UF membrane concentrate to be treated as Fe ^2+.
Per gram of about 0.002g or more, preferably about 0.002g
It is about g to 0.026 g. Below this, the desired holding power is not obtained, above which a precipitate forms in the thermal concentrate. The heat concentration is performed at about 100 ° C. until the volume of the UF membrane concentrate becomes about 1/3 to 1/10, preferably about 1/5.

Since the above Fe ²⁺ need only be present at the time of heat concentration, it may be added at any time before the heat concentration or at the time of the heat concentration, but the foaming property and retentivity of the obtained concentrate may be improved. Considering this, it is preferable to add it before heating and concentrating.
When Fe ²⁺ is added during the enzyme reaction, the resulting foaming agent is
Compared to the foaming agent added with Fe ²⁺ after the enzymatic reaction and before heating and concentration, the foamability is not inferior, but the holding power is low. Fe ²⁺
Without adding at all, compared to conventional commercial blowing agents,
Foamability, especially low holding power. By heating and concentrating in the presence of Fe ²⁺ ions, foaming properties and holding power equivalent to those of the foaming agent obtained by alkali decomposition can be obtained.

The obtained concentrate has a high foaming property and a holding power, as is clear from Example 2 and FIG. 3 described later, and further has a preservability as shown in Example 2 and FIG. 4 described below. Is also excellent. To this, if necessary, an additive such as a suitable stabilizer or preservative used for a usual foaming agent is added,
Products such as foam extinguishers and foaming agents for obtaining lightweight concrete members.

The permeate of the UF membrane contains a significant amount of low molecular weight oligopeptides and amino acids. The permeate was further concentrated using an RO membrane and
A membrane concentrate is obtained. The obtained concentrate contains a hydrolyzate containing an oligopeptide having an average molecular weight of 1,000 or less as a main component. By drying the RO membrane concentrate,
An oligopeptide composition is obtained. As a drying method, a usual spray drying method, a freeze drying method or the like can be adopted. This oligopeptide composition has excellent moisturizing properties and can be used as a hairdressing agent, a cosmetic material such as cream, and the like. R
The O-membrane concentrate has a cream color to a light yellow color, and can be used as it is for the above-mentioned cosmetic materials after drying without purification or decolorization by gel filtration or the like.

Thus, a method for decomposing the hoof horn of an animal with an enzyme and treating it effectively has been established. According to this method, the enzymatic degradation product can be treated in a closed system without environmental pollution. By sequentially treating with a UF membrane and an RO membrane, an oligopeptide fraction separated into desired molecular fractions can be obtained, which can be used as a foaming composition or a cosmetic material. In the production of the foaming agent composition,
Since Fe ²⁺ is used, a foaming agent composition excellent in foamability and cell retention can be obtained. The low molecular weight oligopeptide composition that has permeated the RO membrane can be used as a cosmetic material or the like as it is with a light color. Since the RO membrane permeate is recycled for reuse in the enzyme reaction, it can be effectively treated without causing environmental pollution as described above.

[0033]

【Example】

(Example 1) (1) Enzymatic decomposition of hoof horn After heat treating buffalo horn at 6 to 8 kg / cm ² at 175 ° C. for 1.5 hours, an analytical crusher R-8 (manufactured by Nippon Rikagaku Kikai Co., Ltd.) Crushing was carried out to obtain a hoof horn crushed product. CHN of this crushed product
The analytical values were C content 48.63%, H content 6.77%, and N content 15.1%. As an enzyme, Bacillus subtil
Using an alkaline proteolytic enzyme derived from is Savinase (NOVO), an enzymatic reaction was performed as follows.

A jar fermenter (MBF, EYELA) was charged with 125 g of hoof horn crushed product (substrate) and 2 liters of tap water. While stirring at 500 rpm, the temperature was controlled at 50 ° C. and pH was 8.3, and the enzyme was adjusted to 3.1 g / liter 6.2.
g was added, and the reaction was carried out by stirring for 60 minutes. During the reaction, the reaction solution was sampled with stirring with time, cooled and centrifuged (8000 rpm, 20 minutes, 4 ° C.), and the enzyme activity in the supernatant was measured. FIG. 5 shows the relationship between the reaction time and the enzyme activity of the supernatant.

As can be seen from FIG. 5, the activity of the supernatant immediately after addition of the enzyme dropped to about 300 U / ml, but it was found that the activity returned to the original level 60 minutes after the reaction. This is presumably because, as shown in FIG. 6, when an insoluble substrate such as keratin is hydrolyzed enzymatically, the enzyme first attaches to the substrate and the solubilization proceeds after the decomposition occurs. After stirring for 60 minutes, 125 g of a new substrate was added, the mixture was allowed to stand for 10 minutes, the supernatant was drawn off by decantation, and then tap water was added so that the actual volume became 2 liters. And reacted for 60 minutes. Thus, the enzyme reaction was repeated 4, 6, and 8 times to measure the decomposition rate of the substrate. Savinase is only 6.2 g added in the first reaction. The decomposition rate of the substrate was calculated from the TOC concentration in the reaction solution using the following formula unless otherwise specified.

[0036]

[Equation 1]

The total organic carbon meter (TOC-
500, manufactured by Shimadzu Corp.) was used. Centrifuge (cooling centrifuge, Kubota 6700,
RA-300; 8000 rpm, 20 minutes) 1 supernatant
It was diluted from 00 to 5000 times and used for the measurement. 0.39 g / liter in the above formula is the TOC concentration when the substrate is 100% decomposed, and the C content of the substrate is 48.63%.
Was calculated.

The change in the decomposition rate of the substrate is shown in FIG. In this figure, the vertical axis represents the number of reactions and the horizontal axis represents the decomposition rate. Therefore, the repeated operation of FIG. 2 is repeated 4 times for ○ and 6 for △.
Times, and □ indicates that it was performed 8 times, and changes in the decomposition rate of each substrate are shown. In a 4 batch reaction,
The total decomposition rate (percentage of the total weight of the decomposed substrate with respect to the total weight of the added substrate) was 83.2%, but the decomposition rate was rapidly reduced after reacting 6 times and 8 times. It is considered that the batch reaction is preferably repeated up to 5 times in practice.

(2) Recycling of RO membrane permeation into enzyme reaction The supernatant liquid extracted by decantation from the above enzyme reaction solution was approximately 5 times as thick as a UF membrane (NTU-3250, manufactured by Nitto Denko Corporation). After concentrating, the permeate was converted to an RO membrane (NTR-7410).
(Fraction molecular weight 1,000, manufactured by Nitto Denko Corporation)) and further concentrated about 8 times to obtain a permeate.

The RO membrane permeate and tap water were converted into their TOC.
As a result of comparing the concentration, conductivity, chromaticity, and pH, it was found that the RO membrane permeate was almost the same as tap water except that the TOC concentration was high. The TOC concentration of the RO membrane permeate is 0.16 g / liter, and the TOC concentration of tap water is 0.5 × 10 ⁻³ g / liter. This RO membrane permeate was recycled and used as make-up water for enzyme reaction. The reaction was repeated 4 times basically in the same manner as the above batch reaction. The result is shown in FIG.
In this figure, ○ indicates tap water and Δ indicates the results when RO membrane permeate was used as make-up water, respectively. The total decomposition rate using the RO membrane permeate in the 4 times reaction was 77.5%. The total decomposition rate is 72.9% when tap water is used.
Thus, a higher decomposition rate was obtained when the RO membrane permeate was used.

Example 2 Production of Foaming Agent from UF Membrane Concentrate In Example 1, the enzymatic degradation product obtained by decantation was treated with UF membrane (NTU-2120 (fraction molecular weight: 20,
000, manufactured by Nitto Denko Corporation))
This was a membrane concentrate. The TOC concentration of this UF membrane concentrate is 65.
g / liter. Here, with ferrous sulfate as Fe ²⁺ , the TOC concentration of the membrane concentrate was 7.9 g / liter,
Each of them was added so as to be 0, 0.028, 0.084, 0.14, 0.21 and 0.28 g / liter, and each was heated and concentrated about 3 times under boiling to obtain a foaming agent. . The following foaming test was conducted for each foaming agent.

Foaming test: 10 ml of a sample diluted to a TOC concentration of 7.9 g / ml was placed in a 50 ml colorimetric tube shown in FIG. 9 and shaken 60 times at a constant speed. The foam volume was calculated by measuring the sum of the height with the liquid portion. The total height h of the bubbles and the liquid portion of the sample was measured with time to calculate the volume.

The results of the foaming test are shown in FIG. In FIG. 3, per TOC concentration of the membrane concentrate of 7.9 g / liter, ○ is Fe ²⁺ 0.28 g / liter, and Δ is Fe ²⁺ 0.2.
1 g / liter, □ is Fe ²⁺ 0.14 g / liter, ●
Is Fe ²⁺ 0.084 g / liter, ▲ is Fe ²⁺ 0.028
g / liter, and ▪ indicate the foamability of a concentrate concentrated by heating after adding Fe ²⁺ 0 g / liter.

Fe ²⁺ 0.14 g / liter, 0.21 g
The samples added at a ratio of 0.12 g / liter or 0.28 g / liter were excellent in both foaming ability and holding ability. Among these, 0.22 g / liter and 0.28 g / liter of Fe ²⁺ were added.
A precipitate formed in the sample added at the rate of 1 liter.
The sample added at a rate of 0.14 g / liter was excellent in both foaming power and holding power, and no precipitate was formed.

The foaming agent to which 0.14 g / liter of Fe ²⁺ was added was stored at 4 ° C. for 60 days and then subjected to a foaming test. The result is shown in FIG. 10, 20, 30,
Both the foaming power and the holding power were maintained both after and after storage for 60 days. Thus, it can be seen that this foaming agent has excellent storage stability.

Example 3 Production of Oligopeptide Composition from RO Membrane Concentrate The UF membrane permeate obtained in Example 2 was used as an RO membrane (NTR-74).
10 (fraction molecular weight 1,000, manufactured by Nitto Denko KK) was used and concentrated at a working pressure of 30 kg / cm ² to obtain an RO membrane concentrate. The RO membrane concentrate was freeze-dried to obtain an oligopeptide composition. The oligopeptide composition after lyophilization may be added with water as necessary, and may be made into, for example, a cream and used as a cosmetic cream, a hair dressing, or the like.

The RO membrane permeate was subjected to gel filtration to examine changes in chromaticity before and after gel filtration. The following platinum / cobalt method was used to measure the chromaticity. First,
2.49 g of potassium chloroplatinate (K ₂ PtCl ₆ ) and 2.02 g of cobalt chloride (CoCl ₂ · 6H ₂ O) were placed in a 1-liter volumetric flask and dissolved in 200 ml of hydrochloric acid.
A standard stock solution was prepared by adding purified water to a total volume of 1 liter. Then, this was diluted to prepare standard solutions with chromaticity of 0, 200, and 500, and the absorbance at 380 nm was measured. The chromaticity of the RO membrane permeation without gel filtration was 46.9, whereas that of gel filtered had a chromaticity of 37.7. Since the chromaticity is almost unchanged, it can be seen that the oligopeptide composition produced from the RO membrane concentrate can be directly used for various applications.

[0048]

According to the present invention, there is provided a method for enzymatically decomposing an animal hoof horn and treating it effectively. According to this method, it is possible to perform treatment in a closed system and with a small amount of enzyme, with low energy consumption as compared with the conventional method, without causing pollution such as malodor and organic pollution. From the enzymatic degradation product, a foaming agent composition having a high foaming performance and foam retention that can be used as a foaming agent for fire extinguishers and an oligopeptide composition that can be used as a cosmetic material can be effectively used with stable quality. can get.

[Brief description of drawings]

FIG. 1 is a scheme showing the steps of the enzymatic decomposition treatment method of the present invention.

FIG. 2 is a scheme showing a step of performing enzymatic decomposition in the enzymatic decomposition treatment method of the present invention.

FIG. 3 is a graph showing the results of a foaming test of a foaming agent obtained by adding Fe ²⁺ to a UF membrane concentrate by the method of the present invention and concentrating it by heating.

FIG. 4 is a graph showing changes in foamability of a foaming agent obtained by the method of the present invention when stored at low temperature.

FIG. 5 is a graph showing the reaction time after the addition of the substrate and the enzyme activity when the enzyme reaction is repeatedly carried out in a batch reaction in the method of the present invention.

FIG. 6 is a schematic diagram showing a state of hydrolysis of a substrate by an enzyme in the method of the present invention.

FIG. 7 is a graph showing changes in the rate of decomposition of a substrate for each reaction number when a batch reaction with an enzyme is repeatedly performed at different times.

FIG. 8 shows the number of reactions and the decomposition rate of the substrate when tap water and RO membrane permeate are used as make-up water for the enzyme reaction when the enzyme reaction is repeatedly carried out by the batch reaction in the method of the present invention. It is a graph showing the relationship with change.

FIG. 9 is a schematic diagram showing a method of a foaming test for evaluating the performance of a foaming agent.

[Explanation of symbols]

 1 Enzyme Reaction Solution 2 Stirrer 3 Enzyme 4 Substrate 11 Supernatant 12 Precipitation

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B01D 61/14 500 9538-4D C08H 1/06 NVD // A61K 7/00 K 7/06 7 / 48 35/36 7431-4C

Claims (8)

[Claims] 1. A) a step of enzymatically decomposing a hoof horn of an animal, B) the enzymatic decomposition product is subjected to a UF membrane, and a UF membrane permeate that has permeated the UF membrane and UF concentrated in the UF membrane. Obtaining a membrane concentrate, C) subjecting the UF membrane permeate to an RO membrane to obtain an RO membrane permeate that has permeated the RO membrane and an RO membrane concentrate that has been concentrated in the RO membrane, and D ) A step of recycling the RO membrane permeate to a new animal hoof horn enzymatic decomposition step, the method comprising: 2. A step of enzymatically decomposing a hoof horn of an animal, wherein the enzymatic decomposition product is subjected to a UF membrane, and U concentrated in the UF membrane is used.
A step of obtaining an F membrane concentrate, and a step of adding Fe ²⁺ to the UF membrane concentrate and concentrating by heating,
A method for producing a foaming agent composition, comprising: 3. The UF obtained in the step B of claim 1.
A method for producing a foaming agent composition, comprising a step of adding Fe ²⁺ to a membrane concentrate, and a step of further concentrating the Fe ²⁺ addition concentrate by heating. 4. The Fe ²⁺ added to the UF membrane concentrate.
Is 0.00 per 1 g of TOC concentration in the UF membrane concentrate.
The method for producing a blowing agent composition according to claim 2 or 3, wherein the amount is 35 g or more. 5. A foaming agent composition produced by the production method according to any one of claims 2 to 4. 6. A step of enzymatically decomposing a hoof horn of an animal, wherein the enzymatic decomposition product is subjected to a UF membrane, and UF permeated through the UF membrane.
An oligopeptide comprising the steps of obtaining a membrane permeate, subjecting the UF membrane permeate to an RO membrane to obtain an RO membrane concentrate concentrated on the RO membrane, and drying the RO membrane concentrate. A method for producing a composition. 7. The RO obtained in the step C of claim 1.
Drying the membrane concentrate. 8. An oligopeptide composition produced by the production method according to claim 6 or 7.