TWI589229B - Mycotoxin adsorbent - Google Patents

Mycotoxin adsorbent Download PDF

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TWI589229B
TWI589229B TW102136395A TW102136395A TWI589229B TW I589229 B TWI589229 B TW I589229B TW 102136395 A TW102136395 A TW 102136395A TW 102136395 A TW102136395 A TW 102136395A TW I589229 B TWI589229 B TW I589229B
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mycotoxin adsorbent
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TW201422162A (en
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坂尾一則
高橋範行
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水澤化學工業股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area

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Description

黴菌毒素吸附劑 Mycotoxin adsorbent

本發明,係關於從屬於蒙脫石(montmorillonite)系黏土之膨潤土(bentonite)獲得之黴菌毒素吸附劑。 The present invention relates to a mycotoxin adsorbent obtained from bentonite belonging to montmorillonite clay.

膨潤土係屬於以蒙脫石作為主成分之蒙脫石系黏土之代表性的黏土,對於水的親和性高,具有陽離子交換能力等之離子交換性,而且係為在日本國內出產之低廉的物質,因此使用在以吸附劑為首之各種用途。 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.

尤其最近,有人提議將膨潤土等黏土作為黴菌毒素之吸附劑而摻合於家畜的飼料進行使用(參照專利文獻1~3)。膨潤土係日本國內也出產之低廉的天然礦石,因此由如此之天然礦石構成之黴菌毒素吸附劑,於工業上係極為有用。 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.

【先前技術文獻】 [Previous Technical Literature]

【專利文獻】 [Patent Literature]

【專利文獻1】日本特表平6-501388號公報 [Patent Document 1] Japanese Patent Publication No. 6-501388

【專利文獻2】日本特開2001-299237號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-299237

【專利文獻3】日本特開平8-228693號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 8-228693

黴菌毒素係在黴菌產出之二次代謝物中會損害人或家畜健康之有毒物質,亦被稱為真菌毒素(mycotoxin)。有很多因家畜攝取被污染之穀物等,或因為人攝取此畜產物,而導致損害其健康的事例,又,從被污染之穀物等去除黴菌毒素極為困難。因此,會將吸附如此之黴菌毒素之吸附劑摻合至家畜飼料並在家畜的消化道內吸附黴菌毒素並使其排泄,藉此迴避對生物體等之影響。 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.

關於黴菌毒素有很多種類,其數目超過300,在其主要者,有黃麴毒素或玉米赤黴烯酮(zearalenone)。有人報告該等的毒性強,容易使玉蜀黍等之穀物產生污染。 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.

前述之膨潤土等之天然礦石系之黴菌毒素吸附劑,尤其對於毒性強之黃麴毒素B1(以下亦略稱為AfB1)展現優良吸附特性,然而對於玉米赤黴烯酮(以下亦略稱為ZEN)之吸附性的報告不多。 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.

在前述專利文獻3中,稍微有報告關於酸活化蒙脫石對於玉米赤黴烯酮之吸附性的實驗結果,然而相較於對於黃麴毒素之吸附性遜色許多。 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.

因此,本發明目的係提供不僅對於黃麴毒素,對於玉米赤黴烯酮也展現優良吸附性之黴菌毒素吸附劑。 Accordingly, the object of the present invention is to provide a mycotoxin adsorbent which exhibits excellent adsorptivity to zearalenone not only for safrole toxin.

本發明之其他目的,係提供不需要酸處理等之伴隨著排液處理的藥劑處理,而可從低廉的天然膨潤土獲得之黴菌毒素吸附劑。 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.

本發明人等針對天然出產之膨潤土對於黴菌毒素之吸附性能實施很多的實驗進行探討的結果,發現藉由將滿足指定之物性之Ca型膨潤土作為黴菌毒素吸附劑使用,不僅對於黃麴毒素,也對於玉米赤黴烯酮展現優良吸附性之新穎之見解,而完成本發明。 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.

根據本發明提供一種黴菌毒素吸附劑,其係由以紅外線分光光度測定之Si-O伸縮振動在1041~1090cm-1之範圍,雷射繞射散射法測定之體積基 準計的中位直徑中,將水作為溶媒時的值(D50(W))與將乙醇作為溶媒時的值(D50(E))的比值(D50(W)/D50(E))係在60~110%之範圍的Ca型膨潤土構成。 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.

本發明之黴菌毒素吸附劑,一般理想如下:(1)係Ca型膨潤土之煅燒物,(2)亞甲藍(methylene blue)吸附量係10~45mmol/100g之範圍,(3)在X射線繞射測定中,於晶面間距0.148~0.153nm觀測之來自於蒙脫石之(06)面之X射線繞射峰部的相對面積強度比為40%以上,(4)比表面積係80~200m2/g,(5)灼熱減量(ignition less)係2~10質量%之範圍。 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.

本發明之黴菌毒素吸附劑係作為飼料摻合物而使用,在家畜的消化道內吸附去除黃麴毒素或玉米赤黴烯酮,防止其後之污染,且防止對生物體的健康危害。 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.

本發明之黴菌毒素吸附劑,如後述實驗例所示,不但對於在黃麴毒素中毒性特別強之黃麴毒素B1展現高吸附性,且對於玉米赤黴烯酮也展現優良之吸附性。 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.

本發明之黴菌毒素吸附劑,由Ca型膨潤土所構成,在紅外線分光光度測定中其Si-O伸縮振動係1041~1090cm-1之範圍,同時在以雷射繞射散射法測定之體積基準的中位直徑中,將水作為溶媒時的值與將乙醇作為溶媒時的值的比值(D50(W)/D50(E))在60~110%的範圍係為必要(以下,亦將該比值記載為中位直徑比)。 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).

以下,針對前述之構成要件進行說明。作為膨潤土,除了Ca型膨潤土以外已知有Na型膨潤土。此等之中Ca型膨潤土的結晶子較小,容易獲得比表面積大的粒子,故例如藉由實施煅燒或酸處理,可獲得本發明之黴菌毒素吸附劑。另一方面,Na型膨潤土的結晶子較大,不易獲得比表面積很 大的粒子,為使其對於黴菌毒素擁有足夠的吸附性能,據認為例如須預先進行酸處理後實施煅燒等很多步驟。故在本發明使用Ca型膨潤土。 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.

又,蒙脫石中之Si-O伸縮振動係在1020~1040cm-1的範圍,但在本發明之黴菌毒素吸附劑中,基本骨架的Si-O伸縮振動在1041~1090cm-1的範圍,故較蒙脫石的Si-O鍵結的振動能量高。由此可推測:啟示Si-O鍵結的強度較蒙脫石高,作為就其結果而言,有機親和性高,對於疏水性之玉米赤黴烯酮展現高吸附性。 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.

又,本發明之黴菌毒素吸附劑,必須為中位直徑比D50(W)/D50(E)係60~110%之範圍的Ca型膨潤土。中位直徑比採取如此之範圍的值,意謂在水溶媒中的中位直徑接近在乙醇溶媒中之中位直徑。亦即,其與該中位直徑比之值較小之後述之原料膨潤土相比,在水中進行分散之性質弱,呈現疏水性,推測因該此提高對於疏水性之玉米赤黴烯酮之吸附性。 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.

以下針對本發明之理想的條件進行說明。本發明之黴菌毒素吸附劑,其亞甲藍吸附量理想係在10~45mmol/100g的範圍。 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.

亦即,亞甲藍吸附量,係為利用吸附亞甲藍的量而定量蒙脫石系黏土之疊層層間的一個指標,此吸附量越多,表示膨潤土中之蒙脫石疊層層間存在越多,此吸附量越少,表示蒙脫石之疊層層間越少。 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.

又,本發明之黴菌毒素吸附劑理想為具有在其X射線繞射像中於晶面間距0.148~0.153nm觀測之來自於蒙脫石的(06)面之繞射峰部為40%以上之相對面積強度比。 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.

亦即,如此之繞射峰部的相對面積強度比,係定量膨潤土中之蒙脫石基本骨架的一個指標,此強度比越大,表示在膨潤土中存在越多蒙脫石基本骨架,此強度比越小,表示蒙脫石基本骨架越少。 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.

又,本發明之黴菌毒素吸附劑之比表面積,理想係80~200m2/g。 Further, the specific surface area of the mycotoxin adsorbent of the present invention is preferably 80 to 200 m 2 /g.

亦即,比表面積係在對於黴菌毒素之吸附性中賦予影響其吸附量之指標。此值小的情形時,吸附量變小,結果與親水性或疏水性等之親和性無關,吸附性變為不足。藉由使此值在如前述之範圍內,能成為充分吸附黴菌毒素的吸附劑。 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.

又,本發明之黴菌毒素吸附劑,其灼熱減量理想係在2~10質量%之範圍。 Further, the mycotoxin adsorbent of the present invention preferably has a heat loss of 2 to 10% by mass.

亦即,灼熱減量,主要係表示膨潤土中之羥基量(SiOH量)者,此灼熱減量越大係意謂膨潤土中存在越多SiOH基,灼熱減量越小,意謂SiOH基越少。 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.

如從前述之說明所能理解般,當膨潤土具有如前述之範圍的Si-O伸縮振動、中位直徑比、亞甲藍吸附量、(06)面之相對面積強度比及灼熱減量,意謂因藉由適度地存在作為膨潤土之主成分之蒙脫石基本結構,而於展現吸附性的同時也展現疏水性。亦即,本發明人等,推測由於如此之性質,而兼具對於黃麴毒素B1之吸附性與對於玉米赤黴烯酮之吸附性者。 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.

針對此點進行說明,即該膨潤土適度存在蒙脫石基本結構,故能夠保持成為對於黃麴毒素B1的吸附性的要素亦即(後述說明)疊層層間,也維持某程度的比表面積或細孔。因此,確保了對於黃麴毒素之吸附性。 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.

黃麴毒素係親水性,而相對於此,玉米赤黴烯酮係疏水性。通常,膨潤土等之蒙脫石系黏土係親水性,推測如此之性質成為降低對於玉米赤黴烯酮之吸附性之要素。然而,推測符合本發明規定之參數之膨潤土係在邊適度地維持疊層層間或多孔質的表面結構的狀態,變質為疏水性者,結果對於玉米赤黴烯酮也展示良好之吸附性。 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.

本發明之黴菌毒素吸附劑,符合上述各物性之Ca型膨潤土即可,作為製造方法可考量:將原料Ca型膨潤土煅燒之方法,或實施酸處理之方法等各種之方法,並不限定於何者。理想為利用煅燒之方法,此情形時,尤其不須要進行酸處理等之藥劑處理,在製造時不發生特別的排液處理,可最大限度地發揮天然產礦物的低廉之優點。 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.

本發明之黴菌毒素吸附劑,作為家畜用之飼料摻合物使用,可在家畜的消化道內(例如腸內)將強毒性的黃麴毒素或玉米赤黴烯酮吸附去除有效地抑制生物體的健康受害。 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.

圖1顯示在實驗例1獲得的原料膨潤土及本發明之黴菌毒素吸附劑的紅外線分光光譜圖。 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.

圖2顯示在實驗例1-5獲得的本發明之黴菌毒素吸附劑的X射線繞射圖(實線),及在實驗例H-2獲得的Na型膨潤土之煅燒物的X射線繞射圖(點線)。 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).

本發明之黴菌毒素吸附劑,能夠以Ca型膨潤土作為原料,視須要實施適當地處理而獲得。 The mycotoxin adsorbent of the present invention can be obtained by using Ca-type bentonite as a raw material and performing appropriate treatment.

<原料膨潤土> <raw material bentonite>

膨潤土,係指屬於蒙脫石系黏土,以雙八面型式膨潤石(smectite)的一種之蒙脫石作為主成分之黏土。次於蒙脫石而含有多量之蛋白石(opal)者,也亦特別地被稱為酸性白土。 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.

該蒙脫石具有由SiO4四面體層-AlO6八面體層-SiO4四面體層所構成之層狀結構,並具有該等八面體層的一部份的Al被Mg或Fe(II)所取代,四面體層的一部份的Si被Al所取代之以較低原子價的異種金屬元素進行同形 取代之基本骨架。在此基本骨架的同形取代部份產生負電荷,但在該等疊層層間存在與其相稱之量的陽離子與水,電荷性係中和。亦即,由基本骨架與疊層層間構成之蒙脫石基本結構,展現因應如此之同形取代元素或層間離子的種類或量之陽離子交換能力。在如此之蒙脫石基本結構中,展現Si-O-Si鍵結的連結層面的有機親和性,與來自同形取代部位的極性的親水性之特性。再者,蒙脫石中之Si-O伸縮振動係在1020~1040cm-1的範圍,蛋白石則係在1100cm-1附近。 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.

作為原料膨潤土,已知有Na型膨潤土或Ca型膨潤土(亦包含一般稱為酸性白土之黏土)。 As the raw material bentonite, Na type bentonite or Ca type bentonite (including a clay generally called acid clay) is known.

Na型膨潤土,疊層層間的Na含量多,使其分散於水時之分散液的pH高,例如在5質量%懸浮液為9.5以上之高,對於水之膨潤力也高,例如為15mL/2g以上之高。再者,Na型膨潤土,具有供予多量的水則凝膠化,將其乾燥則固結之性質。 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.

另一方面,Ca型膨潤土,疊層層間之Ca含量或質子量多,使其分散至水時的分散液的pH低,例如在5質量%懸浮液為4.5~9.5之低,對於水之膨潤力低,為3~10mL/2g左右之低。又,在供予多量的水的情形時,也不會產生凝膠化。 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.

其中,Na型膨潤土的結晶子大,僅實施煅燒無法獲得比表面積大的粒子,故對於黴菌毒素的吸附性不及Ca型膨潤土(參照實驗例H-2)。又,若經過預先實施酸處理增大比表面積後並實施煅燒之二階段之步驟,據認為能夠對於黴菌毒素展現良好之吸附性,但此情形時也無法避免的會增加成本。另一方面,Ca型膨潤土,結晶子小,能夠獲得大的比表面積的粒子,故例如僅以煅燒或酸處理的一階段的處理,就能夠獲得由針對黴菌毒素吸附性高的粒子構成的吸附劑。因此,在本發明中以Ca型膨潤土作為原料使用。 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.

在本發明中,做為原料膨潤土使用之Ca型膨潤土之以氧化物換算的化學組成,一般係如下述。另,括號內係Na型膨潤土的組成例。 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.

SiO2:50~75質量%(Na型:61.7) SiO 2 : 50 to 75% by mass (Na type: 61.7)

Al2O3:12~25質量%(Na型:22.2) Al 2 O 3 : 12 to 25% by mass (Na type: 22.2)

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

Fe2O3:0.5~10質量%(Na型:2.2) Fe 2 O 3 : 0.5 to 10% by mass (Na type: 2.2)

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

Na2O:0~3質量%(Na型:3.6) Na 2 O: 0 to 3 mass% (Na type: 3.6)

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

其他之金屬氧化物:2.5質量%以下(Na型:0.3) Other metal oxides: 2.5% by mass or less (Na type: 0.3)

灼熱減量:5~15質量%(Na型:6.3) Searing loss: 5~15% by mass (Na type: 6.3)

又,Ca型膨潤土之膨潤力較Na型膨潤土低。例如,實驗例H-1的膨潤力為60mL/2g,而相對於此實驗例1-1的膨潤力為6mL/2g。 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.

但,藉由對於蒙脫石基本骨架中的Si或Al進行同形取代等而展現之陽離子交換能力及親水性,係成為對於黃麴毒素展現吸附性之要素,又,親水性,係成為妨礙對於玉米赤黴烯酮之吸附性之要素。因此在很多時候,因應因產地等而變動之原料膨潤土的性質,有實施適當的處理,增大對於玉米赤黴烯酮的吸附性之必要。 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.

<處理方法> <Processing method>

本發明之黴菌毒素吸附劑,必須為符合既定之物性之Ca型膨潤土。為獲得如此之黴菌毒素吸附劑,當原料膨潤土不符合該物性的情形時,須要實施適當的處理。不特別限定此方法,可舉例如:將原料膨潤土煅燒之方法,實施酸處理之方法或藉由離子交換之方法。在此之中,由不須要排液處理且經濟性優秀之觀點來看,藉由煅燒之方法係為理想。 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.

<煅燒> <calcination>

將原料膨潤土進行粗粉碎,實施水力淘析或空氣淘析去除夾雜物後,實施煅燒,藉此,可獲得能成為本發明之黴菌毒素吸附劑之膨潤土煅燒物。 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.

該煅燒不實施至產生完全燒結的程度,於可某程度維持蒙脫石基本結構之溫度進行,具體而言於200~800℃,較佳為300~600℃,更佳400~600 ℃實施,煅燒時間為0.5小時以上,較佳為0.5~4小時左右。 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.

亦即,在前述煅燒中,其溫度越高,則SiOH基進行脫水縮合,蒙脫石基本骨架的Si-O伸縮振動能量提高,疊層層間趨向消失,故蒙脫石基本結構減少,結果為Si-O伸縮振動移向高波數區,亞甲藍吸附量少,灼熱減量變小。又,其溫度低且處理時間越短,亞甲藍吸附量多,且灼熱減量維持為大。因此,設定煅燒溫度及時間以獲得目的之Si-O伸縮振動、亞甲藍吸附量或灼熱減量即可。 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.

本發明之黴菌毒素吸附劑,只要可吸附去除既定之黴菌毒素,其使用態樣則不受任何限制,一般作為家畜飼料的摻合物進行使用,例如理想係為每飼料100重量份摻合0.1~1.0重量份般的恰當的量至飼料進行使用。藉此,可在家畜的消化道內有效的進行吸附去除污染玉蜀黍等飼料且對生物體極為有害之AfB1或ZEN,而有效地防止該等黴菌毒素導致之健康損害。 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.

<黴菌毒素吸附劑> <Mycotoxin adsorbent>

本發明之黴菌毒素吸附劑對於玉米赤黴烯酮發揮高吸附性之原理尚未明確解明,但在以下從由膨潤土之煅燒處理導致之變質之觀點說明本發明人的推測。然而,此推測並不對本發明做任何限制。 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.

本發明之一種實施態樣亦即膨潤土煅燒物,以維持某程度蒙脫石基本骨架之溫度實施煅燒,故例如在其X射線繞射像,於晶面間距0.148~0.153nm來自於蒙脫石之(06)面之繞射峰部一定會被觀測到。由本發明之膨潤土煅燒物中之此繞射峰部的面積強度,將作為標準物質之Kunipia F(KUNIMINE工業製Na型膨潤土)之繞射峰部的面積強度作為100而算出之相對面積強度比(%),可作為表示蒙脫石基本骨架的含量之指標,理想係40%以上。在ICDD:13-135則賦予指數於(0010)與(300),但在此方便上集中表示為(06)。 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).

來自於蒙脫石之(001)面之繞射峰部,有不被觀測到的情形。原因在於煅燒導致疊層層間收縮之故。 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.

在本實施態樣之膨潤土煅燒物中,基本骨架之Si-O伸縮振動在1041~1090cm-1之範圍,故較未煅燒之蒙脫石基本骨架之Si-O鍵結的振動能量高。據推測此係啟示蒙脫石基本骨架之Si-O鍵結距離短,共價鍵性較通常高,結果增加了Si-O-Si鍵結的連接層面之有機親和性且提高對於疏水性之玉米赤黴烯酮之吸附性。 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.

更者,在本實施態樣中之膨潤土煅燒物,中位直徑比D50(W)/D50(E)在60~110%之範圍。針對此進行說明:Ca型膨潤土的主成分亦即蒙脫石,具有在水溶媒中分散微粒子化之性質,但在乙醇溶媒中則無發揮此性質。所以,在蒙脫石多量殘留之膨潤土,在水溶媒中的中位直徑與在乙醇溶媒中之其相比變為較小,因此該中位直徑比也變為較小的值。另一方面,在本實施態樣中之膨潤土煅燒物,藉由煅燒而蒙脫石基本結構適度進行變質,故失去在水溶媒中分散微粒子化之性質,中位直徑也與乙醇溶媒中之其變為接近,故中位直徑比的值變大。推測藉此親水性蒙脫石變化為疏水性,提高對於疏水性之玉米赤黴烯酮之吸附性。 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.

又,作為維持某程度蒙脫石基本結構的結果,該膨潤土煅燒物的亞甲藍吸附量,理想為在10~45mmol/100g的範圍。使殘留之蒙脫石結構有使亞甲藍吸附量成為此程度之值之事,係雖實施煅燒仍可維持對於AfB1之吸附性之很大的要素。 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.

此亞甲藍吸附量較前述範圍多時,煅燒係不充分,以下敘述之灼熱減量也成為很大的值,含有很多SiOH量的結果,即便能夠滿足對於AfB1之吸附性,也無法滿足對於疏水性之ZEN之吸附性。又,亞甲藍吸附量較前述範圍少時,係過度實施煅燒,變為燒結或接近其之狀態,蒙脫石基本結構幾乎消失,且比表面積也大大地降低,變為無法滿足對於AfB1及ZEN之任一者之吸附性。 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.

再者,作為維持某程度蒙脫石基本結構的結果,此膨潤土煅燒物之灼熱減量較佳為在2~10質量%之範圍,更佳為2~8.5質量%,最佳為在2~8 質量%之範圍。如先前所述,在殘留蒙脫石基本結構而減少SiOH量使得灼熱減量成為此程度,增大疏水性之事,推測係為提升對於疏水性之ZEN之吸附性之很大的要素。 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.

亦即,當此灼熱減量較前述範圍大時,煅燒係不充分,與亞甲藍吸附量過多時同樣,包含SiOH量很多,結果對於AfB1之吸附性係良好,但變為無法滿足對於ZEN之吸附性。又,灼熱減量較前述範圍小時,係過度地實施煅燒,故與亞甲藍吸附量少時同樣,產生蒙脫石基本結構消失及比表面積大幅降低,變為無法滿足對於AfB1及ZEN任一者之吸附性。 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.

又,此膨潤土煅燒物適度地實施煅燒的結果,展現80~200m2/g,尤其展現90~200m2/g的比表面積,藉此,對於AfB1及ZEN任一者皆發揮優良的吸附性能。 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.

【實施例】 [Examples]

將本發明之優良效果以下述之實驗例進行說明。 The excellent effects of the present invention will be described by way of the following experimental examples.

另,實驗例中之各種測試以下列方法實施。 In addition, various tests in the experimental examples were carried out in the following manner.

(1)紅外線分光光度測定 (1) Infrared spectrophotometry

將試樣以KBr粉末成形為錠劑,將不包含試樣之KBr作為比較,使用日本分光(股)製之FT/IR-6100進行測定。分辨率係4.0cm-1,鏡徑(Aperture)為Auto。在實驗例的表中以IR作為表示。解析對象範圍為1000~1100cm-1The 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)中位直徑(D50) (2) Median diameter (D 50 )

使用Beckman Coulter公司製之LS 13 320,使用濃度100%之乙醇及離子交換水作為溶媒,以雷射繞射散射法測定在體積基準的中位直徑(D50)。在實驗例的表中,顯示各D50(E)、D50(W)、及以次式:(D50(W)/D50(E))×100算出之中位直徑比(%)。 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)亞甲藍吸附量 (3) Methylene blue adsorption capacity

依據日本膨潤土工業會標準測試方法JBAS-107-77,以不添加0.5N硫 酸進行測定後,校正水分而算出亞甲藍吸附量(mmol/100g)。在實驗例的表中以MB吸附量表示。 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射線繞射(定量測定) (4) X-ray diffraction (quantitative measurement)

於試樣1g添加10vol%乙二醇/乙醇溶液,於50℃乾燥一晚。將已乾燥之試樣以乳鉢進行粉碎而獲得經乙二醇處理之試樣。包含於試樣之蒙脫石的(06)面的含量,利用藉由X射線繞射之基體沖洗法(matrix-flushing method),使用α-Al2O3作為沖洗劑(flushing agent),對於被檢試樣添加一定量之比例,以不定配向法(”Standard X-ray diffraction powder patterns”,NBS Monograph,25(1971))將待測試樣填充至容器(cell),以下列之條件實施測定。 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射線繞射裝置:Rigaku(股)製之RINT-UltimaIV X-ray diffraction device: RINT-UltimaIV made by Rigaku Co., Ltd.

測定條件:X射線=Cu-Kα線, 掃描範圍:繞射角(2θ)=42.0~44.5及60.5~63.0° Measurement conditions: X-ray = Cu-Kα line, Scanning range: diffraction angle (2θ) = 42.0~44.5 and 60.5~63.0°

作為標準物質,使用經乙二醇處理之Kunipia F,以X射線繞射圖的峰部面積作為100%,表示各試樣之其之相對面積強度比(%)。又,在實驗例的表中以(06)表示。 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)比表面積 (5) specific surface area

使用Micromeritics公司製之Tri Star 3000實施測定。比表面積,係以BET法從比壓為0.05至0.25的吸附分支側氮吸附等溫線進行判讀。 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)灼熱減量(Ig-Loss) (6) Searing loss (Ig-Loss)

將試樣放入至瓷坩堝(porcelain crucible)測定重量(a)後,以1000℃煅燒1小時後,在乾燥器(desiccators)中放冷並且測定重量(b)。另外,將試樣放入至稱量瓶測定重量(c)後,於110℃乾燥2小時後,在乾燥器中放冷並測定重量(d)。 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.

利用次式算出110℃乾燥基準之灼熱減量(質量%)。 The ignition loss (% by mass) of the 110 ° C drying standard was calculated by the following formula.

灼熱減量(質量%)=(ad-bc)/(ad)×100 Searing loss (% by mass) = (ad-bc) / (ad) × 100

式中, a為煅燒前之試樣的重量(g) In the formula, a is the weight of the sample before calcination (g)

b為煅燒後之試樣的重量(g) b is the weight of the sample after calcination (g)

c為乾燥前之試樣的重量(g) c is the weight of the sample before drying (g)

d為乾燥後之試樣的重量(g) d is the weight of the sample after drying (g)

再者,a~d意為去除坩堝、稱量瓶等容器重量,僅有試樣的重量。 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)測定ZEN吸附率 (7) Determination of ZEN adsorption rate

在1ppmZEN水溶液5mL放入吸附劑25mg並振盪1小時後,實施離心分離並將上清液使用島津製作所(股)製之HPLC Prominence與螢光檢測器RF-20A測定殘留濃度。吸附率以100×(初濃度-殘留濃度)/初濃度而算出。 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)測定AfB1吸附率 (8) Determination of AfB1 adsorption rate

在5ppmAfB1水溶液10mL放入吸附劑25mg,於25℃振盪2小時後,以濾紙及PTFE製之0.20μm濾膜進行過濾,將所獲得之液體使用日本分光(股)製之紫外可視分光光度計JASCO V-570測定殘留濃度。吸附率以100×(初濃度-殘留濃度)/初期濃度而算出。 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)膨潤力(容積法) (9) Swelling force (volume method)

依據日本膨潤土工業會標準測試方法JBAS-104-77進行測定。 The measurement was carried out in accordance with the Japanese Bentonite Industry Association Standard Test Method JBAS-104-77.

(10)pH (10) pH

依據JIS K 5101-17-1:2004,測製備之5質量%水性懸浮液之pH值。 The pH of the prepared 5 mass% aqueous suspension was measured in accordance with JIS K 5101-17-1:2004.

(11)化學組成 (11) Chemical composition

二氧化矽(SiO2)、氧化鋁(Al2O3)、氧化鈉(Na2O)之分析,係依據JIS M 8853:1998進行測定。又,Fe2O3、CaO、MgO、K2O係使用原子吸光法。再者,測定試樣係將110℃乾燥物作為基準。 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.

(實驗例1) (Experimental Example 1)

日本山形縣鶴岡市生產之酸性白土(1-1),pH為6.0。使用此物,於各 種溫度煅燒2小時。實施物性測定,將結果表示於表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.

(實驗例2) (Experimental Example 2)

使用在日本山形縣鶴岡市之其他的地區生產之酸性白土(2-1),於各種溫度煅燒2小時。實施物性測定,將結果表示於表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.

(實驗例3) (Experimental Example 3)

山形縣鶴岡市之又其他的地區生產之酸性白土(3-1)比表面積為133m2/g,pH為5.9。使用此物,於500℃煅燒2小時(3-2)。實施物性測定,將結果表示於表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.

(實驗例4) (Experimental Example 4)

使用在新潟縣新發田市生產之酸性白土(4-1),於400℃煅燒2小時(4-2)。實施物性測定,將結果表示於表3。 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.

(實驗例5) (Experimental Example 5)

將在實驗例2使用之酸性白土進行酸處理,使成為比表面積318m2/g、pH3.6之酸活化蒙脫石(5-1),於500℃煅燒2小時(5-2)。實施物性測定,將結果表示於表3。 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.

(實驗例H-1,2) (Experimental Example H-1, 2)

係為Na型膨潤土之KUNIMINE工業(股)製之Kunipia F(H-1),比表面積為5m2/g,膨潤力為60mL/2g,pH為10.0。將此物於500℃煅燒2小時(H-2)。針對此煅燒物實施物性測定及性能評價,將結果表示於表3。 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)

一種黴菌毒素吸附劑,係由以紅外線分光光度測定之Si-O伸縮振動在1041~1090cm-1之範圍,雷射繞射散射法測定之體積基準的中位直徑中將水作為溶媒時的值(D50(W))與將乙醇作為溶媒時的值(D50(E))的比值(D50(W)/D50(E))係在60~110%之範圍之Ca型膨潤土構成。 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. . 如申請專利範圍第1項之黴菌毒素吸附劑,其中,該Ca型膨潤土係煅燒物。 The mycotoxin adsorbent according to claim 1, wherein the Ca-type bentonite is a calcined product. 如申請專利範圍第1項之黴菌毒素吸附劑,其中,亞甲藍吸附量係在10~45mmol/100g之範圍。 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. 如申請專利範圍第1項之黴菌毒素吸附劑,其中,在X射線繞射測定中,於晶面間距0.148~0.153nm觀測之來自蒙脫石之(06)面之X射線繞射峰部的相對面積強度比為40%以上。 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. 如申請專利範圍第1項之黴菌毒素吸附劑,其中,比表面積係在80~200m2/g之範圍。 The mycotoxin adsorbent according to claim 1, wherein the specific surface area is in the range of 80 to 200 m 2 /g. 如申請專利範圍第1項之黴菌毒素吸附劑,其中,灼熱減量係在2~10質量%之範圍。 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. 一種飼料摻合物,係由如申請專利範圍第1項之黴菌毒素吸附劑構成。 A feed blend consisting of a mycotoxin adsorbent as in claim 1 of the patent application.
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