TWI589229B - Mycotoxin adsorbent - Google Patents

Description

Mycotoxin adsorbent

The present invention relates to a mycotoxin adsorbent obtained from bentonite belonging to montmorillonite clay.

The bentonite is a representative clay of montmorillonite clay containing montmorillonite as a main component, and has high affinity for water, ion exchangeability such as cation exchange capacity, and low-cost substance produced in Japan. Therefore, it is used in various applications including adsorbents.

In particular, it has been proposed to use a clay such as bentonite as a mycotoxin adsorbent for blending into livestock feed (see Patent Documents 1 to 3). Bentonite is a low-cost natural ore produced in Japan, so the mycotoxin adsorbent composed of such natural ore is extremely useful industrially.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 6-501388

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-299237

[Patent Document 3] Japanese Patent Laid-Open No. Hei 8-228693

Mycotoxins are toxic substances that damage human or livestock health in the secondary metabolites produced by mold, also known as mycotoxins. There are many cases in which livestock are infested with contaminated grains, or because humans ingest this animal product, which causes damage to their health, and it is extremely difficult to remove mycotoxins from contaminated grains and the like. Therefore, the adsorbent which adsorbs such a mycotoxin is blended into the livestock feed, and the mycotoxin is adsorbed and excreted in the digestive tract of the livestock, thereby avoiding the influence on the living body or the like.

There are many types of mycotoxins, the number of which exceeds 300, and in its main part, there are sacrotoxin or zearalenone. It has been reported that such toxicity is strong and it is easy to cause pollution of grains such as maize.

The mycotoxin adsorbent of the natural ore type such as bentonite described above exhibits excellent adsorption characteristics especially for the highly virulent xanthotoxin B1 (hereinafter also abbreviated as AfB1), but for zearalenone (hereinafter also referred to as ZEN) There are not many reports of adsorption.

In the aforementioned Patent Document 3, the experimental results regarding the adsorption of acid-activated montmorillonite to zearalenone are slightly reported, but the adsorption property against xanthine is much inferior.

Accordingly, the object of the present invention is to provide a mycotoxin adsorbent which exhibits excellent adsorptivity to zearalenone not only for safrole toxin.

Another object of the present invention is to provide a mycotoxin adsorbent which can be obtained from inexpensive natural bentonite by providing a chemical treatment which does not require an acid treatment or the like, and which is accompanied by a liquid discharge treatment.

The present inventors have conducted a number of experiments on the adsorption performance of naturally occurring bentonite for mycotoxin, and found that Ca-type bentonite which satisfies the specified physical properties is used as a mycotoxin adsorbent, not only for safrole toxin. The present invention has been completed for the novel insight that zearalenone exhibits excellent adsorptivity.

According to the present invention, there is provided a mycotoxin adsorbent which is characterized by a Si-O stretching vibration measured by infrared spectrophotometry in a range of 1041 to 1090 cm ^-1 and a median diameter of a volume reference measured by a laser diffraction scattering method. the value (D ₅₀ (W)) when used as a solvent of water and ethanol as the value (D ₅₀ (E)) of the ratio _{(D 50 (W) / D} 50 (E)) when the vehicle based on 60 to 110% The range of Ca-type bentonite is composed.

The mycotoxin adsorbent of the present invention is generally preferably as follows: (1) a calcined material of Ca type bentonite, (2) a methylene blue adsorption amount of 10 to 45 mmol/100 g, and (3) an X-ray. In the diffraction measurement, the relative area intensity ratio of the X-ray diffraction peak from the (06) plane of the montmorillonite observed at the interplanar spacing of 0.148 to 0.153 nm is 40% or more, and (4) the specific surface area is 80~. 200 m ² /g, (5) The ignition less is in the range of 2 to 10% by mass.

The mycotoxin adsorbent of the present invention is used as a feed blend to adsorb and remove safrole toxin or zearalenone in the digestive tract of livestock, to prevent subsequent contamination, and to prevent health hazards to the living body.

The mycotoxin adsorbent of the present invention exhibits high adsorptivity to xanthine toxin B1 which is particularly toxic to safrole toxin, and exhibits excellent adsorptivity to zearalenone as shown in the experimental examples described later.

The mycotoxin adsorbent of the present invention is composed of Ca-type bentonite, and has a range of Si-O stretching vibration system of 1041 to 1090 cm ^-1 in infrared spectrophotometry, and a volume basis measured by a laser diffraction scattering method. Among the median diameters, the ratio of the value when water is used as a solvent to the value when ethanol is used as a solvent (D ₅₀ (W) / D ₅₀ (E)) is in the range of 60 to 110% (hereinafter, This ratio is described as the median diameter ratio).

Hereinafter, the above-described constituent elements will be described. As the bentonite, Na-type bentonite is known in addition to Ca-type bentonite. Among these, the Ca-type bentonite has a small crystallizer and is easy to obtain particles having a large specific surface area. Therefore, the mycotoxin adsorbent of the present invention can be obtained by, for example, calcination or acid treatment. On the other hand, Na-type bentonite has large crystals and is difficult to obtain a specific surface area. Large particles have a sufficient adsorption performance for mycotoxins, and it is considered that many steps such as calcination are carried out after acid treatment in advance. Therefore, Ca type bentonite is used in the present invention.

Further, the Si-O stretching vibration in the smectite is in the range of 1020 to 1040 cm ^-1 , but in the mycotoxin adsorbent of the present invention, the Si-O stretching vibration of the basic skeleton is in the range of 1041 to 1090 cm ^-1 . Therefore, the vibration energy of the Si-O bond is higher than that of the montmorillonite. From this, it can be inferred that the strength of the Si-O bond is higher than that of montmorillonite, and as a result, the organic affinity is high, and the hydrophobic zearalenone exhibits high adsorptivity.

Further, the mycotoxin adsorbent of the present invention must be a Ca-type bentonite having a median diameter ratio D ₅₀ (W) / D ₅₀ (E) of 60 to 110%. The median diameter ratio takes such a range of values, meaning that the median diameter in the aqueous solvent is close to the median diameter in the ethanol vehicle. That is, compared with the raw material bentonite which is smaller in value than the median diameter ratio, the dispersion property in water is weak and exhibits hydrophobicity, which is presumed to increase the adsorption of hydrophobic zearalenone. Sex.

The ideal conditions of the present invention will be described below. The mycotoxin adsorbent of the present invention preferably has a methylene blue adsorption amount in the range of 10 to 45 mmol/100 g.

That is, the amount of methylene blue adsorbed is an index between the laminated layers of smectite clay by the amount of adsorbed methylene blue, and the more the amount of adsorption, the presence of the interlayer of montmorillonite in the bentonite The more the amount of adsorption, the less the interlayer of montmorillonite is.

Further, the mycotoxin adsorbent of the present invention preferably has a diffraction peak of (06) surface derived from montmorillonite observed at a crystal plane pitch of 0.148 to 0.153 nm in the X-ray diffraction image of 40% or more. Relative area strength ratio.

That is, the relative area intensity ratio of such a diffraction peak is an index of the basic skeleton of the montmorillonite in the bentonite. The greater the intensity ratio, the more the basic skeleton of the montmorillonite is present in the bentonite, and the strength The smaller the ratio, the less the basic skeleton of montmorillonite.

Further, the specific surface area of the mycotoxin adsorbent of the present invention is preferably 80 to 200 m ² /g.

That is, the specific surface area is an index that imparts an influence on the adsorption amount of the mycotoxin. When the value is small, the amount of adsorption becomes small, and as a result, regardless of the affinity such as hydrophilicity or hydrophobicity, the adsorptivity becomes insufficient. By setting this value within the range as described above, it becomes an adsorbent which sufficiently adsorbs mycotoxins.

Further, the mycotoxin adsorbent of the present invention preferably has a heat loss of 2 to 10% by mass.

That is, the amount of heat loss is mainly expressed as the amount of hydroxyl groups (the amount of SiOH) in bentonite. The larger the amount of heat loss means that more SiOH groups are present in the bentonite, and the smaller the amount of heat loss is, the less the SiOH group is.

As can be understood from the foregoing description, when the bentonite has a Si-O stretching vibration, a median diameter ratio, a methylene blue adsorption amount, a (06) surface relative area strength ratio, and a burning reduction amount as described above, it means that the bentonite has a range as described above. Hydrophobicity is exhibited by exhibiting adsorptivity by moderately present a basic structure of montmorillonite which is a main component of bentonite. In other words, the inventors of the present invention presumed that due to such properties, they have both adsorptivity to xanthine toxin B1 and adsorption to zearalenone.

In view of the above, the bentonite has a basic structure of montmorillonite, and therefore, it is possible to maintain a certain degree of specific surface area or fineness between the laminated layers, which is an element which is adsorbable to the safrole toxin B1 (described later). hole. Therefore, the adsorption to xanthine toxin is ensured.

Xanthine is hydrophilic, whereas zearalenone is hydrophobic. In general, montmorillonite clays such as bentonite are hydrophilic, and it is presumed that such a property is an element for lowering the adsorption property to zearalenone. However, it is presumed that the bentonite which satisfies the parameters specified in the present invention is in a state in which the surface structure of the laminated layer or the porous surface is moderately maintained, and is deteriorated to be hydrophobic, and as a result, good adsorbability is exhibited for zearalenone.

The mycotoxin adsorbent of the present invention may be a Ca-type bentonite satisfying the above physical properties, and various methods such as a method of calcining a raw material Ca-type bentonite or a method of performing an acid treatment may be considered as a production method, and are not limited thereto. . It is desirable to use a method of calcination. In this case, in particular, it is not necessary to carry out an acid treatment such as acid treatment, and no special liquid discharge treatment occurs at the time of production, and the advantages of natural mineral production can be maximized.

The mycotoxin adsorbent of the present invention is used as a feed blend for livestock, and can effectively remove the highly toxic xanthine toxin or zearalenone in the digestive tract of livestock (for example, intestine) Health damage.

Fig. 1 shows an infrared spectroscopy spectrum of the raw material bentonite obtained in Experimental Example 1 and the mycotoxin adsorbent of the present invention.

2 shows an X-ray diffraction pattern (solid line) of the mycotoxin adsorbent of the present invention obtained in Experimental Example 1-5, and an X-ray diffraction pattern of the calcined material of Na type bentonite obtained in Experimental Example H-2. (Dotted line).

The mycotoxin adsorbent of the present invention can be obtained by using Ca-type bentonite as a raw material and performing appropriate treatment.

<raw material bentonite>

Bentonite refers to a clay belonging to the smectite clay and having a montmorillonite as a main component of a double octahedral type smectite. Subsequent to montmorillonite, which contains a large amount of opal, it is also known as acid clay.

The smectite has a layered structure composed of a SiO ₄ tetrahedral layer-AlO ₆ octahedral layer-SiO ₄ tetrahedral layer, and a part of the octahedral layer is replaced by Mg or Fe(II). A part of Si in the tetrahedral layer is replaced by Al, and the basic skeleton which is isomorphously substituted with a lower valence dissimilar metal element. The isomorphous substitution of the basic skeleton produces a negative charge, but there is a cation and water commensurate with the amount of cation and water neutralized between the laminate layers. That is, the basic structure of the smectite composed of the basic skeleton and the laminated layer exhibits a cation exchange ability in response to such a homomorphic substitution element or a type or amount of interlayer ions. In such a basic structure of montmorillonite, the organic affinity of the bonding layer of the Si-O-Si bond is exhibited, and the hydrophilicity of the polarity from the homomorphic substitution site. Further, Si-O stretching vibration in the range-based montmorillonite 1020 ~ 1040cm ^-1, and opal are based around 1100cm ^-1.

As the raw material bentonite, Na type bentonite or Ca type bentonite (including a clay generally called acid clay) is known.

The Na type bentonite has a high content of Na between the laminated layers, and the pH of the dispersion liquid when it is dispersed in water is high, for example, the 5% by mass suspension is 9.5 or higher, and the swelling power to water is also high, for example, 15 mL / 2 g. The above is high. Further, the Na type bentonite has a property of being gelled by supplying a large amount of water, and drying it to be solidified.

On the other hand, in the Ca-type bentonite, the Ca content or the amount of protons between the laminated layers is large, and the pH of the dispersion liquid when it is dispersed in water is low, for example, the 5% swelling of the suspension is 4.5 to 9.5, and the swelling of the water is performed. The force is low, which is about 3~10mL/2g. Further, in the case where a large amount of water is supplied, gelation does not occur.

Among them, the Na-type bentonite has a large crystal form, and it is not possible to obtain particles having a large specific surface area by calcination, so that the adsorption property to mycotoxins is inferior to that of Ca-type bentonite (see Experimental Example H-2). Further, it is considered that the step of performing the second surface of the calcination after the acid treatment is carried out by the acid treatment is carried out, and it is considered that the mycotoxin can exhibit good adsorptivity, but in this case, the cost is unavoidable. On the other hand, since Ca-type bentonite has small crystals and can obtain particles having a large specific surface area, for example, adsorption by particles having high adsorption to mycotoxin can be obtained by only one-stage treatment by calcination or acid treatment. Agent. Therefore, in the present invention, Ca-type bentonite is used as a raw material.

In the present invention, the oxide-converted chemical composition of the Ca-type bentonite used as the raw material bentonite is generally as follows. In addition, the composition of Na type bentonite is shown in parentheses.

SiO ₂ : 50 to 75% by mass (Na type: 61.7)

Al ₂ O ₃ : 12 to 25% by mass (Na type: 22.2)

MgO: 1 to 8 mass% (Na type: 3.3)

Fe ₂ O ₃ : 0.5 to 10% by mass (Na type: 2.2)

CaO: 1 to 5 mass% (Na type: 0.6)

Na ₂ O: 0 to 3 mass% (Na type: 3.6)

K2O: 0~1.5% by mass (Na type: 0.1)

Other metal oxides: 2.5% by mass or less (Na type: 0.3)

Searing loss: 5~15% by mass (Na type: 6.3)

Moreover, the swelling power of Ca-type bentonite is lower than that of Na-type bentonite. For example, the swelling strength of Experimental Example H-1 was 60 mL/2 g, and the swelling force with respect to Experimental Example 1-1 was 6 mL/2 g.

However, the cation exchange ability and hydrophilicity exhibited by isomorphous substitution of Si or Al in the basic skeleton of montmorillonite are elements which exhibit adsorptivity to xanthine toxin, and hydrophilicity is a hindrance to The element of the adsorption of zearalenone. Therefore, in many cases, depending on the nature of the raw material bentonite which varies depending on the place of production, it is necessary to carry out appropriate treatment to increase the adsorption property to zearalenone.

<Processing method>

The mycotoxin adsorbent of the present invention must be a Ca-type bentonite which conforms to a predetermined physical property. In order to obtain such a mycotoxin adsorbent, when the raw material bentonite does not conform to the physical property, appropriate treatment is required. The method is not particularly limited, and examples thereof include a method of calcining a raw material bentonite, a method of performing an acid treatment, or a method of ion exchange. Among them, the method of calcination is ideal from the viewpoint that the liquid discharge treatment is not required and the economy is excellent.

<calcination>

The raw material bentonite is coarsely pulverized, subjected to hydrometallography or air elutriation to remove inclusions, and then calcined, whereby a bentonite calcined product which can be a mycotoxin adsorbent of the present invention can be obtained.

The calcination is not carried out to the extent that complete sintering is carried out, and the temperature of the basic structure of the montmorillonite can be maintained to some extent, specifically 200 to 800 ° C, preferably 300 to 600 ° C, more preferably 400 to 600. The calcination time is 0.5 hours or more, preferably about 0.5 to 4 hours.

That is, in the calcination, the higher the temperature, the dehydration condensation of the SiOH group, the Si-O stretching vibration energy of the basic skeleton of the montmorillonite is increased, and the laminated layers tend to disappear, so the basic structure of the montmorillonite is reduced, and the result is The Si-O stretching vibration moves to the high wavenumber region, the amount of methylene blue adsorbed is small, and the amount of ignition loss becomes small. Further, the temperature is low and the treatment time is shorter, the amount of methylene blue adsorbed is large, and the amount of ignition loss is maintained large. Therefore, the calcination temperature and time can be set to obtain the intended Si-O stretching vibration, methylene blue adsorption amount or ignition loss.

The mycotoxin adsorbent of the present invention is not limited as long as it can adsorb and remove a predetermined mycotoxin, and is generally used as a blend of livestock feed, for example, preferably 100 parts by weight per feed. ~1.0 parts by weight of the appropriate amount to the feed for use. Thereby, AfB1 or ZEN which is harmful to the living body and which is harmful to the living body can be effectively adsorbed and removed in the digestive tract of the livestock, and the health damage caused by the mycotoxins can be effectively prevented.

<Mycotoxin adsorbent>

The principle that the mycotoxin adsorbent of the present invention exerts high adsorptivity to zearalenone has not been clearly explained, but the inventors' hypothesis is explained below from the viewpoint of deterioration caused by the calcination treatment of bentonite. However, this speculation does not impose any limitation on the present invention.

In one embodiment of the present invention, the bentonite calcined material is calcined to maintain a certain temperature of the basic skeleton of the montmorillonite, so that, for example, in its X-ray diffraction image, the interplanar spacing is 0.148 to 0.153 nm from the montmorillonite. The diffracted peak of the (06) plane must be observed. The area intensity of the diffraction peak of the bentonite calcined product of the present invention, and the relative area intensity ratio calculated by taking the area intensity of the diffraction peak of Kunipia F (KUNIMINE industrial Na type bentonite) as a standard material as 100 ( %) can be used as an index indicating the content of the basic skeleton of montmorillonite, and is ideally 40% or more. In ICDD: 13-135, the indices are given at (0010) and (300), but in this convenience, they are collectively expressed as (06).

There are cases where the diffraction peak from the (001) plane of the montmorillonite is not observed. The reason is that the calcination causes shrinkage between the laminate layers.

In the bentonite calcined product of the present embodiment, the Si-O stretching vibration of the basic skeleton is in the range of 1041 to 1090 cm ^-1 , so the vibration energy of the Si-O bond of the basic skeleton of the uncalcined montmorillonite is higher. It is speculated that this system reveals that the Si-O bond distance of the basic skeleton of montmorillonite is short, and the covalent bond is higher than usual, resulting in an increase in the organic affinity of the Si-O-Si bond junction layer and an increase in hydrophobicity. Adsorption of zearalenone.

Furthermore, in the bentonite calcined product of the present embodiment, the median diameter ratio D ₅₀ (W) / D ₅₀ (E) is in the range of 60 to 110%. In view of this, the main component of Ca-type bentonite, that is, montmorillonite, has a property of dispersing fine particles in an aqueous solvent, but it does not exhibit this property in an ethanol solvent. Therefore, the bentonite remaining in a large amount of montmorillonite has a smaller median diameter in the aqueous solvent than in the ethanol solvent, and thus the median diameter ratio also becomes a small value. On the other hand, in the bentonite calcined product in the present embodiment, the basic structure of the montmorillonite is moderately deteriorated by calcination, so that the property of dispersing the fine particles in the aqueous solvent is lost, and the median diameter is also in the ethanol solvent. It becomes close, so the value of the median diameter ratio becomes large. It is presumed that the hydrophilic montmorillonite is changed to hydrophobicity, and the adsorption to the hydrophobic zearalenone is improved.

Further, as a result of maintaining a certain basic structure of montmorillonite, the amount of methylene blue adsorbed by the bentonite calcined product is preferably in the range of 10 to 45 mmol/100 g. When the residual montmorillonite structure has a value such that the amount of methylene blue adsorbed is such a degree, it is possible to maintain a large adsorption property for AfB1 by calcination.

When the amount of methylene blue adsorbed is larger than the above range, the calcination system is insufficient, and the calcination loss described below also becomes a large value, and as a result of containing a large amount of SiOH, even if the adsorption property to AfB1 can be satisfied, it is not satisfactory for hydrophobicity. Adsorption of ZEN. Further, when the amount of methylene blue adsorbed is less than the above range, the calcination is excessively performed, and the state of sintering or close to it is obtained, the basic structure of the montmorillonite is almost eliminated, and the specific surface area is also greatly lowered, and it becomes impossible to satisfy AfB1 and Adsorption of any of ZEN.

Further, as a result of maintaining a certain degree of the basic structure of the montmorillonite, the burning loss of the bentonite calcined product is preferably in the range of 2 to 10% by mass, more preferably 2 to 8.5% by mass, most preferably 2 to 8 The range of mass %. As described above, in the case where the basic structure of the montmorillonite is retained and the amount of SiOH is reduced so that the amount of ignition loss is such a degree that the hydrophobicity is increased, it is presumed that it is a factor which enhances the adsorption property to the hydrophobic ZEN.

That is, when the amount of heat loss is larger than the above range, the calcination system is insufficient, and when the amount of adsorption of methylene blue is too large, the amount of SiOH is large, and as a result, the adsorption property to AfB1 is good, but it becomes unsatisfactory for ZEN. Adsorption. Further, when the amount of heat loss is smaller than the above range, the calcination is excessively performed. Therefore, similarly to the case where the amount of adsorption of methylene blue is small, the basic structure of montmorillonite disappears and the specific surface area is largely lowered, and it becomes impossible to satisfy either AfB1 or ZEN. Adsorption.

Further, the bentonite calcined product is subjected to calcination in a moderate manner, exhibiting a surface area of 80 to 200 m ² /g, particularly exhibiting a specific surface area of 90 to 200 m ² /g, thereby exhibiting excellent adsorption properties for either AfB1 or ZEN.

[Examples]

The excellent effects of the present invention will be described by way of the following experimental examples.

In addition, various tests in the experimental examples were carried out in the following manner.

(1) Infrared spectrophotometry

The sample was molded into a tablet in KBr powder, and KBr containing no sample was used for comparison, and FT/IR-6100 manufactured by JASCO Corporation was used for measurement. The resolution is 4.0 cm ^-1 and the aperture is Auto. It is represented by IR in the table of the experimental example. The range of resolution objects is 1000~1100cm ^-1 .

(2) Median diameter (D ₅₀ )

The median diameter (D ₅₀ ) on a volume basis was measured by a laser diffraction scattering method using LS 13 320 manufactured by Beckman Coulter Co., Ltd. using a concentration of 100% ethanol and ion-exchanged water as a solvent. In the table of the experimental example, each of D ₅₀ (E), D ₅₀ (W), and the formula: (D ₅₀ (W) / D ₅₀ (E)) × 100 is calculated to calculate the median diameter ratio (%). .

(3) Methylene blue adsorption capacity

According to the Japanese bentonite industry standard test method JBAS-107-77, without adding 0.5N sulfur After the acid was measured, the water content was corrected to calculate the methylene blue adsorption amount (mmol/100 g). It is represented by the MB adsorption amount in the table of the experimental example.

(4) X-ray diffraction (quantitative measurement)

A 10 vol% ethylene glycol/ethanol solution was added to the sample 1 g, and dried at 50 ° C overnight. The dried sample was pulverized in a mortar to obtain a sample treated with ethylene glycol. The content of the (06) surface of the montmorillonite contained in the sample is represented by a matrix-flushing method by X-ray diffraction, and α-Al ₂ O _{3 is} used as a flushing agent. The sample to be tested is added to a certain amount, and the sample to be tested is filled into a cell by a method of "Standard X-ray diffraction powder patterns" (NBS Monograph, 25 (1971)), and is carried out under the following conditions. Determination.

X-ray diffraction device: RINT-UltimaIV made by Rigaku Co., Ltd.

Measurement conditions: X-ray = Cu-Kα line, Scanning range: diffraction angle (2θ) = 42.0~44.5 and 60.5~63.0°

As a standard substance, Kunipia F treated with ethylene glycol was used, and the peak area of the X-ray diffraction pattern was taken as 100%, and the relative area intensity ratio (%) of each sample was shown. Further, it is represented by (06) in the table of the experimental example.

(5) specific surface area

The measurement was carried out using Tri Star 3000 manufactured by Micromeritics. The specific surface area was judged by the BET method from the adsorption branch side nitrogen adsorption isotherm at a specific pressure of 0.05 to 0.25.

(6) Searing loss (Ig-Loss)

The sample was placed in a porcelain crucible (a), and after calcination at 1000 ° C for 1 hour, it was allowed to cool in a desiccators and the weight (b) was measured. Further, the sample was placed in a weighing bottle to measure the weight (c), and after drying at 110 ° C for 2 hours, it was allowed to cool in a desiccator and the weight (d) was measured.

The ignition loss (% by mass) of the 110 ° C drying standard was calculated by the following formula.

Searing loss (% by mass) = (ad-bc) / (ad) × 100

In the formula, a is the weight of the sample before calcination (g)

b is the weight of the sample after calcination (g)

c is the weight of the sample before drying (g)

d is the weight of the sample after drying (g)

Furthermore, a~d means to remove the weight of the container such as the crucible and the weighing bottle, and only the weight of the sample.

(7) Determination of ZEN adsorption rate

After 5 mg of the adsorbent was placed in 5 mL of a 1 ppm ZEN aqueous solution and shaken for 1 hour, centrifugation was carried out, and the supernatant was measured for the residual concentration using HPLC Prominence and Fluorescence Detector RF-20A manufactured by Shimadzu Corporation. The adsorption rate was calculated by 100 × (initial concentration - residual concentration) / initial concentration.

(8) Determination of AfB1 adsorption rate

Into 10 mL of a 5 ppm AfB1 aqueous solution, 25 mg of an adsorbent was placed, and after shaking at 25 ° C for 2 hours, it was filtered through a filter paper and a 0.20 μm filter made of PTFE, and the obtained liquid was subjected to a UV-visible spectrophotometer JASCO manufactured by JASCO Corporation. V-570 was used to determine the residual concentration. The adsorption rate was calculated by 100 × (initial concentration - residual concentration) / initial concentration.

(9) Swelling force (volume method)

The measurement was carried out in accordance with the Japanese Bentonite Industry Association Standard Test Method JBAS-104-77.

(10) pH

The pH of the prepared 5 mass% aqueous suspension was measured in accordance with JIS K 5101-17-1:2004.

(11) Chemical composition

The analysis of cerium oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), and sodium oxide (Na ₂ O) was carried out in accordance with JIS M 8853:1998. Further, Fe ₂ O ₃ , CaO, MgO, and K ₂ O are atomic absorption methods. Further, the measurement sample was based on a dried product at 110 ° C.

(Experimental Example 1)

Acidic white clay (1-1) produced in Tsuruoka, Yamagata Prefecture, Japan, pH 6.0. Use this thing, in each The temperature was calcined for 2 hours. The physical property measurement was carried out, and the results are shown in Table 1.

(Experimental Example 2)

Acidic clay (2-1) produced in other parts of Tsuruoka City, Yamagata Prefecture, Japan, was calcined at various temperatures for 2 hours. The physical property measurement was carried out, and the results are shown in Table 2.

(Experimental Example 3)

The acid white clay (3-1) produced in other areas of Tsuruoka City, Yamagata Prefecture has a specific surface area of 133 m ² /g and a pH of 5.9. Using this, it was calcined at 500 ° C for 2 hours (3-2). The physical property measurement was carried out, and the results are shown in Table 3.

(Experimental Example 4)

The acid white clay (4-1) produced in Shibata City, Niigata Prefecture was calcined at 400 ° C for 2 hours (4-2). The physical property measurement was carried out, and the results are shown in Table 3.

(Experimental Example 5)

The acid white clay used in Experimental Example 2 was subjected to an acid treatment to obtain an acid-activated smectite (5-1) having a specific surface area of 318 m ^{2 /} g and a pH of 3.6, and calcined at 500 ° C for 2 hours (5-2). The physical property measurement was carried out, and the results are shown in Table 3.

(Experimental Example H-1, 2)

It is Kunipia F (H-1) manufactured by KUNIMINE Industrial Co., Ltd. of Na type bentonite, has a specific surface area of 5 m ² /g, a swelling power of 60 mL / 2 g, and a pH of 10.0. This material was calcined at 500 ° C for 2 hours (H-2). Physical properties and performance evaluations were carried out for this calcined product, and the results are shown in Table 3.

Claims (7)

A mycotoxin adsorbent is a value obtained by using Si-O stretching vibration measured by infrared spectrophotometry in a range of 1041 to 1090 cm ^-1 and water as a solvent in a median diameter of a volume reference measured by a laser diffraction scattering method. (D ₅₀ (W)) is a ratio of the value (D ₅₀ (E)) when the ethanol is used as a solvent (D ₅₀ (W) / D ₅₀ (E)) in the range of 60 to 110% of Ca-type bentonite. . The mycotoxin adsorbent according to claim 1, wherein the Ca-type bentonite is a calcined product. For example, the mycotoxin adsorbent according to claim 1 of the patent scope, wherein the methylene blue adsorption amount is in the range of 10 to 45 mmol/100 g. The mycotoxin adsorbent according to the first aspect of the patent application, wherein in the X-ray diffraction measurement, the X-ray diffraction peak from the (06) plane of the montmorillonite is observed at a plane spacing of 0.148 to 0.153 nm. The relative area strength ratio is 40% or more. The mycotoxin adsorbent according to claim 1, wherein the specific surface area is in the range of 80 to 200 m ² /g. For example, the mycotoxin adsorbent according to the first aspect of the patent application, wherein the ignition loss is in the range of 2 to 10% by mass. A feed blend consisting of a mycotoxin adsorbent as in claim 1 of the patent application.