赤峰和美嘉科技有限公司
 
新浪微博
欢迎访问天地圣农旗下网站 设为首页 加入收藏 联系我们 天地圣农博客 天地圣农微博
矿石
矿石
矿石
爽身宝
霉毒痢净
肠清宝——(养殖专供)
钻井泥浆用膨润土
冶金球团用膨润土
铸造型砂粘结剂
猫砂

关于我们

更多

公司简介
 

技术中心

饲料脱霉吸附用蒙脱石的采购与评价浅谈

来源: 赤峰和美嘉科技有限公司  点击:27次 发布时间:2016-2-24

饲料脱霉吸附用蒙脱石的采购与评价

      ★                 


蒙脱石采购和使用中,用户会发现以下几个方面:


(1)不是所有的蒙脱石效果都一样。
我们知道,蒙脱石的吸附性能与其层间电荷密切相关,根据蒙脱石层间电荷高低可以将蒙脱石划分为:怀俄明型(Wyoming)(低层电荷蒙脱石,能产生0.20~0.35单位半晶胞的层间负电荷)、切托型(Cheto)(高层电荷蒙脱石,能产生0.45~0.60单位半晶胞的层间负电荷)和过度型(介于上述二者之间)三种类型,而这三种类型电荷差异可以达到3倍之多,可见电荷差异会对其效果会产生多大差异。另外,蒙脱石的成因、晶体形状及杂质种类等都会影响蒙脱石的吸附、分散等众多性能。


事实上,蒙脱石科技研发人员早在2007年就对不同产地不同电荷属性的蒙脱石样品进行了毒素吸附和最低抑菌浓度实验,(见表:不同省份蒙脱石对AFB1的具体吸附脱毒效果)


结果表明:各种产地类型的蒙脱石对毒素和细菌的作用效果差异十分显著,且并非蒙脱石层间电荷越高吸附效果就越好,吸附不同的物质需要选用不同属性的蒙脱石,才能达到最佳效果。


(2)普通蒙脱石和提纯改性蒙脱石的区别很大。
蒙脱石产品核心技术除了蒙脱石提纯技术,更重要的就是蒙脱石的改性技术。为什么要对蒙脱石进行提纯和改性处理呢?由于蒙脱石的成因不同、膨润土中的蒙脱石含量不同、杂质种类和数量不同、有害成分不同,为了获得纯度更高、品质更佳的蒙脱石,需要对膨润土进行提纯。也正是因为各种膨润土性能及杂质种类的差异,使得其提纯技术具有独特性和不可复制性,也就是说,不同膨润土矿只有用不同的提纯工艺和方法才可能达到最佳的品质。另外,我们知道蒙脱石对细菌、毒素都具有一定的吸附效果,但对不同的物质其效果差异也十分明显。例如,2009年有研究报道指出,纯蒙脱石对黄曲霉毒素吸附效果较好但不稳定易解吸附,对玉米赤霉烯酮毒素几乎没有吸附作用,通过改性处理后可以同时增加蒙脱石对黄曲霉毒素和玉米赤霉烯酮毒素的吸附量和吸附的稳定性。但由于改性的方法有数十种,每一种方法所得到的效果都不一样,因此市场上才会出现众多种类改性蒙脱石。



(3)吸附力、比表面积和蒙脱石含量不能说明使用效果。
在蒙脱石产品的实际应用中,常常听到一些客户提出“吸附力多少?比表面积多少?蒙脱石含量多少?是不是越高越好?”等问题。吸附力就是蒙脱石吸附硫酸士的宁的能力,与其吸附次甲基蓝一样,其高低只能说明其对这种物质的吸附效果,不能作为其替代吸附黄曲霉毒素、玉米赤霉烯酮以及各种细菌毒素的评价方法。同样,对于不同的应用领域其比表面积与使用效果也不成比列关系。对于未经改性的蒙脱石,其含量越高效果越好。但对于改性蒙脱石情况发生变化,通过改性过后蒙脱石的组成或吸附次甲基蓝的能力发生变化,而蒙脱石的含量是用吸附次甲基蓝的量来计算的,因此通常还会出现改性蒙脱石使用效果提高,但含量却下降的现象。


(4)蒙脱石产品的安全性非常重要。
在饲料和食品安全越来越被重视的今天,蒙脱石产品作为一种重要的饲料添加剂,产品本身的安全性也尤为重要。二恶英的危害众所周知,2005年有研究报告指出,美国特殊营养公司生产的饲料添加剂霉可脱(改性蒙脱石)中二恶英含量高达88.003ps/g,严重危害养殖动物和人体健康被禁止使用。

目前有些厂家以有机膨润土为原料生产制备霉菌毒素吸附剂(有机膨润土是膨润土经季铵盐复合改性得到的改性蒙脱石产品),体外实验表明有机改性蒙脱石有助于提高其对ZEN的吸附,但动物体内应用试验结果却不一致;同时,有机蒙脱石在养殖业中的应用还存在极大的安全隐患,改性用的有机试剂以及有机试剂中残留的合成中间体都可能存在一些毒副作用,如果这类物质被长期大量的使用,最终将危害养殖动物和人体健康。这应引起饲料行业的关注。

另外近年方英石的危害也备受关注,在2013年中国药典中最新实施的蒙脱石原料药标准已经明确限定了有害物质方英石含量,因此有必要考虑对畜牧用蒙脱石产品也进行相关方面指标的考察。

 

为此,关于蒙脱石,笔者有些粗浅的分析要说,通常我们会用以下的一些性能指标来对蒙脱石进行初步评价:
(1)蒙脱石产品的纯度指标
目前,评价蒙脱石纯度的指标主要有吸蓝量、阳离子交换量、吸氨值、砂石量、XRD。
吸蓝量的基本原理:水分散状态下的蒙脱石具有吸附亚甲基蓝的能力,其吸附的量被称为吸蓝量,以100g样吸附的亚甲基蓝毫克当量数或克数表示。亚甲基蓝在水中为一价阳离子,可以与蒙脱石进行层间离子交换,形成蒙脱石有机复合体。按经验公式蒙脱石含量(%)=吸蓝量/0.442计算得出。一般膨润土中的蒙脱石含量越高,吸蓝量越大。因此,吸蓝量可作为粗略评估膨润土中蒙脱石相对含量的主要技术指标之一。
阳离子交换量/吸氨值:膨润土层间有可交换性阳离子,进行膨润土的阳离子交换容量测试,是鉴别膨润土矿的属型和判断蒙脱石含量的重要依据。常规采用氯化铵-50%乙醇法测试。吸氨值来自GB/T21695-2008饲料级沸石粉,基本原理与阳离子交换量测试方法相同,测试结果较阳离子交换高。
砂石量:一般指矿石内没有除去的石英砂,云母片、铁质等粗粒杂质,含量过多会影响产品品质。因此,砂石量是粗略评价膨润土中蒙脱石品质优劣的主要技术指标之一。其测试方法是采用在有分散剂条件下,加水将试样制成均匀分散的悬浮液,由于粗粒级石英、云母片等不受分散剂影响,经一段时间后沉积在容器底部,根据沉积物计算石英砂的百分含量。市场上很多不良商家用膨润土假冒蒙脱石或改性蒙脱石,甚至宣称产品纯度达到95-99%,通过砂石量的方法可以区分类似的假冒伪劣的蒙脱石产品,但是我们应注意的是,有的蒙脱石产品含有粘土、方英石等细粒杂质,砂石量也可能很低。
XRD图谱:一般是指运用X射线衍射仪测出某种蒙脱石样品的XRD衍射图谱后,根据所得的衍射峰位置和强度,对照JCPDS卡片检索,确定蒙脱石种属及含量,并可得到蒙脱石产品杂质的种类和有害物质方英石含量。


(2)蒙脱石产品的粒度
众所周知,蒙脱石产品粒度越细分散性能及吸附性能越好,蒙脱石粒度的评价方式主要有:粉体粒度、堆密度、水分散粒度。
粉体粒度测试:分为干法过筛、显微镜观察、粉体粒度仪和SEM(扫描电子显微镜)图像法。
堆密度的测试:将测试样在105℃烘干至恒重,慢慢倒入干燥的100ml量筒中直至刻度100,倾泻过程中以没有明显粉体上扬为标准,不对量筒进行震敲操作,对满刻度两桶内的粉体进行称重,计算堆密度值,以g/ml表示,产品粒度越细,松堆密度越小。该方法可以迅速简单的比较出不同产品的粒度差异。
水分散粒度:是将蒙脱石产品分散在水中采用激光粒度分布仪进行粒度测试,这种方法比较科学直观,应用较广。


(3)分散悬浮性
膨胀倍和胶质价是评价蒙脱石分散悬浮性的主要技术指标。同时,膨胀倍和胶质价与膨润土的属型和蒙脱石的含量密切相关,同一属型的膨润土,蒙脱石含量越高,膨胀倍和胶质价越高;所以膨胀倍和胶质价也是鉴定膨润土属型和评价膨润土质量的技术指标之一。并且,膨胀倍根据不同的要求又分为酸膨胀倍、药品膨胀倍、5g膨胀倍和2g膨胀倍。


(4)重金属及毒害成分
蒙脱石重金属主要包括铅、镉、汞和砷等,这类物质可以通过原子吸收分光光度法进行评价,而目前对于医药用蒙脱石重金属的测试方法主要采用比色法。毒害成分主要包括方石英和二恶英。


(5)吸附性
评价蒙脱石吸附性能的指标主要有:吸附力和吸附霉菌毒素的能力;但吸附力的大小不能代表其吸附霉菌毒素的能力。
吸附力:是每1g蒙脱石应吸附硫酸士的宁的量,一般为0.30~0.50g。该指标仅能反应蒙脱石对硫酸士的宁的吸附效果以及蒙脱石的含量,蒙脱石中镁含量增加会导致吸附力增加。
而评价吸附霉菌毒素的能力主要分为体外缓冲液体系、饲料体系、人工模拟动物胃肠液和动物体内测试四个方面。
评价蒙脱石产品的性能指标众多,应用范围各不相同。事实上,不同用途的蒙脱石产品要运用不同评价指标和体系来评价,最佳的评价方法就是动物养殖试验。

 

三鼎科技研发团队早在2006年就同华中农业大学动物医学院合作进行纳米蒙脱石用于仔猪止泻试验,2007年与华南农业大学动物科学院合作进行纳米蒙脱石替代氧化锌对断奶仔猪生产性能的影响的试验,以及后来进行过数十次养殖试验来不断评价和改进产品性能和效果,并在《饲料工业》、《精细与专用化学品》、《湖北畜牧兽医》、《山东畜牧兽医》、《广东饲料》、《兽医导刊》、《吉林畜牧兽医》、《兽药与饲料添加剂》、《农村养殖技术》、《动物保健》、《今日畜牧兽医》、《中兽医医药杂志》、《湖南饲料》、《矿产保护与利用》、《浙江畜牧兽医》《养猪》、《非金属》、《南方饲料》等几十个公开期刊上发表了100多篇相关应用研究的文章,这些试验成果如今已被众多的膨润土及某些蒙脱石厂家广泛采用,为蒙脱石行业做出了贡献。

 

不同的蒙脱石原料,不同的改性加工技术、不同的厂家是不可能会有一样的效果的。



The English version

Feed off mold adsorption with montmorillonite sourcing and evaluation

Procurement and use of the montmorillonite, users will find the following several aspects:


(1) not all effect of montmorillonite.

We know that the adsorption properties of the montmorillonite interlayer charge with closely related, according to the montmorillonite interlayer charge and montmorillonite can be divided into: Wyoming type (Wyoming) (lower charge montmorillonite, can produce 0.20 ~ 0.35 unit negative half cell layers), cutting type (Cheto) (top charge montmorillonite, can produce 0.45 ~ 0.60 unit negative half cell layers) and type (between) between the three types, and the differences between three types of charge can be three times as much, visible difference to charge the effect will be to make much difference. In addition, the cause of the montmorillonite, crystal shape and types of impurities will affect the adsorption of montmorillonite, dispersion, and many other performance.


Montmorillonite technology research and development personnel, in fact, as early as 2007 with different origin of different charge properties of the toxin montmorillonite samples adsorption experiments, and the minimum bacteriostasis concentration (see table: different provinces montmorillonite the specific adsorption of AFB1 detoxification effect)


The results show that the various types of origin of the montmorillonite on the effects of toxin and bacteria is very significant difference, not montmorillonite interlayer charge and the higher the better adsorption effect, the adsorption of different substances need to choose different properties of montmorillonite, to achieve the best effect.


(2) common montmorillonite and purification of modified montmorillonite is a big difference.

Montmorillonite product core technology in addition to the montmorillonite purification technology, more important is that montmorillonite modification technology. Why to purification and modification of the montmorillonite? Differ as a result the causes of montmorillonite, the montmorillonite content in bentonite different, the amount and type of impurities and harmful components, in order to get higher purity, better quality of montmorillonite, bentonite have to be purified. Also because of various kinds of bentonite properties and impurity, making its purification technology has the unique and unrepeatable, that is, different bentonite ore is only possible with different methods of purification technology and best quality. In addition, we know that montmorillonite on bacteria and toxins have certain adsorption effect, but the effect for different substances difference is also very obvious. In 2009, for example, a study reported that pure montmorillonite on aflatoxin adsorption effect is good but not stable and easy desorption, for corn gibberellic ketene toxins, almost no adsorption after modification can increase at the same time montmorillonite on aflatoxin and corn gibberellic ketene toxin stability of adsorption capacity and adsorption. But because there are dozens of ways to modify, each kind of method of effect is different, so will appear on the market of many kinds of modified montmorillonite.



(3) adsorption force, specific surface area and montmorillonite content cannot explain the using effect.

In the practical application of montmorillonite product, often heard some customers put forward "adsorption?? Surface montmorillonite content? The higher the better?" Wait for a problem. Adsorption is montmorillonite sulfuric acid and better ability of adsorption, adsorption time with methyl blue, its height can only explain the adsorption effect of this kind of material, not as a substitute for the adsorption of aflatoxin, corn gibberellic ketene and evaluation methods of various kinds of bacterial toxins. Also, for different application fields of the specific surface area than out of step with the using effect is also listed. For without the modification of montmorillonite, the content, the higher the better the results. But for the modified montmorillonite, changes by the composition of modified montmorillonite after the adsorption of methylene blue or ability to change, and the content of montmorillonite is the amount of methylene blue adsorption time can be used to calculate, so often there will be the use effect of the modified montmorillonite suspension increased, but the content is falling phenomenon.


(4) montmorillonite product safety is very important.

In the feed and food safety is more and more attention today, montmorillonite as an important feed additive products, the safety of the product itself is also particularly important. The harm of dioxin is well known, a 2005 study, points out that the special nutrition company production of feed additives mildew can take off (modified montmorillonite) of dioxin levels as high as 88.003 ps/g, serious damage to the breeding of animals and human health are prohibited from use.

There are some manufacturers with organic bentonite as raw material to produce mycotoxins adsorbent preparation (organic bentonite bentonite modified by quaternary ammonium salt compound modified montmorillonite with the products), in vitro experiments show that organic modified montmorillonite is helpful to improve its adsorption of ZEN, but animals application test results are inconsistent; At the same time, the application of the organic montmorillonite in aquaculture has great potential safety hazard, modified with organic reagents and residual intermediates in organic reagents are there may be some side effects, if this kind of material is the use of a large amount for a long time, will damage to the breeding animals and human health. The feed industry should pay attention to.

In addition also has attracted much attention in recent years, the harm of cristobalite, in 2013 China pharmacopoeia of montmorillonite on the implementation of the latest API standards have clear limits the cristobalite content of harmful substances, so it is necessary to consider using montmorillonite on livestock products also on relevant indicators.


For this, of montmorillonite, the author to say some superficial analysis, usually we will use the following some performance index to preliminary evaluation of montmorillonite:

(1) montmorillonite purity of the products

At present, the evaluation index of montmorillonite purity are mainly blue uptake, cation exchange capacity, amount of ammonia absorption value, sandstone, and XRD.

Blue uptake: the basic principle of water under the decentralized state of montmorillonite has the ability of adsorption of methylene blue, its adsorption amount was known as the blue uptake, with 100 g sample adsorption of methylene blue mg equivalent number or g said. Methylene blue for monovalent cations in water, can with montmorillonite interlayer ion exchange, the formation of organic montmorillonite is complex. According to the empirical formula of montmorillonite content (%) = blue uptake / 0.442 calculated. Generally the higher the montmorillonite content in bentonite, the greater the blue uptake. Blue uptake, therefore, can be used as a rough evaluation of montmorillonite of a bentonite relative content of one of the main technical indicators.

Cation exchange capacity/ammonia absorption value: between the layers of bentonite has exchangeability cation, cation exchange capacity of bentonite tests, is to identify bentonite ore type and judge the important basis of montmorillonite content. Conventional ammonium chloride - 50% ethanol method is used to test. Ammonia absorption value from GB/T21695-2008 feed grade zeolite powder, basic principle is the same as the test method of cation exchange capacity, high cation exchange test results.

Sand: generally refers to the mineral inside without removal of quartz sand, mica sheet, iron and other coarse impurities, content is too much will affect the product quality. Therefore, sand volume is a rough evaluation of montmorillonite of a bentonite one of the main technical indicators of quality. The test method is to use under the condition of a dispersant, water will be made uniformly dispersed suspension sample, such as coarse grained quartz, mica sheet is not affected by dispersing agent, after a period of time deposit in the bottom of the container, according to the percentage content of sediment calculation of quartz sand. On the market a lot of fake montmorillonite or undesirable businessman with bentonite modified montmorillonite, even claimed product purity 95-99%, by the amount of sand and gravel method can distinguish between similar montmorillonite of fake and shoddy products, but we should pay attention to is that some of the montmorillonite product contains fine impurities, such as clay, christobalite sand quantity can be lower.

XRD spectrum: generally refers to using X ray diffraction to measure some montmorillonite samples of XRD diffraction pattern, according to the diffraction peak position and intensity, contrast JCPDS card retrieval, determine the species and content of montmorillonite is available and montmorillonite product kinds of impurity and cristobalite content of harmful substances.


(2) the granularity of the montmorillonite products

As is known to all, the granularity of montmorillonite product fine dispersion performance and the better the performance of adsorption, and montmorillonite granularity of evaluation methods mainly include: powder particle size, bulk density, water dispersed particle size.

Powder particle size test: divided into dry sieving, microscopy, powder particle size instrument and SEM (scanning electronic microscope) images.

Will heap of density test: test samples at 105 ℃ drying to constant weight, slowly pour in 100 ml measuring cylinder drying scale until 100, in the process of the landslide is a standard with no apparent rose powder, no shock on measuring cylinder for operation, the full scale two barrels of powder in weighing, calculation of bulk density value, expressed in g/ml, the granularity of product fine, the smaller the bulk density. This method can rapid simple comparison of the differences of granularity of different products.

Water dispersed particle size, is spread montmorillonite products in water using laser particle size distribution of particle size test, this method is scientific and intuitive, widely used.


(3) the dispersion suspended

Expansion times and montmorillonite dispersion colloid valence is suspended, the main technical indicators. At the same time, the expansion times and glial price and type of bentonite and montmorillonite content is closely related to the same type of the bentonite, the higher the content of montmorillonite, expansion times and glial price is higher; So the expansion times and glial price appraisal is a type of bentonite and evaluate the quality of bentonite is one of the technical indicators. And times according to different requirements, inflation is divided into acid expansion times, drug times, 5 g and 2 g expansion times.


(4) of heavy metals and toxic ingredients

Montmorillonite heavy metals including lead, cadmium, mercury and arsenic, etc, this kind of material can undertake assessment by atomic absorption spectrophotometry, and the current for pharmaceutical montmorillonite main test method of heavy metals by colorimetric method. Toxic ingredients including stones and dioxins.


(5) adsorption

Evaluation of montmorillonite adsorption performance indicators mainly include: adsorption capacity and adsorption ability of mycotoxin; But the size of the adsorption force can't represent its ability to adsorb mycotoxins.

Adsorption: montmorillonite is per 1 g should be the amount of adsorption of sulfuric acid and ning, general is 0.30 ~ 0.50 g. The index can only reaction of sulfuric acid and montmorillonite better adsorption effect and the content of montmorillonite, the montmorillonite stone magnesium content leads to adsorption force increases.

In vitro and evaluate the adsorption ability of mycotoxin consists of buffer system, feed system, artificial simulation animal gastric intestinal juice and animal test four aspects.

Montmorillonite product performance evaluation index is numerous, the application scope of each are not identical. In fact, different USES of montmorillonite product to use different evaluation index system to evaluate and the best evaluation method is animal breeding test.


SanDing technology research and development team as early as 2006 animals with huazhong agricultural university medical school cooperation on nanometer montmorillonite used in piglets test of diarrhoea, cooperation with south China agricultural university animal academy of sciences in 2007 nanometer montmorillonite instead of zinc oxide affect the performance of weaned piglets production test, and later, and with dozens of breeding to continually evaluate and improve product performance and effect, and in the feed industry, fine and specialty chemicals, animal husbandry and veterinary in hubei, shandong animal husbandry and veterinary, "feed of guangdong", "the veterinarian guide," jilin veterinary ", "veterinary drugs and feed additives", "rural breeding technology", "animal health", "animal husbandry and veterinary today", journal of medicine that the win has been have another year, hunan feed, protect and utilize mineral, animal husbandry and veterinary in zhejiang "pig", "non-metallic", "southern feed" and so on dozens of public journals published more than 100 article related application research, the results of this test is now a multitude of bentonite and some montmorillonite factory widely adopted, contributing to the montmorillonite industry.


Different montmorillonite material, different modification processing technology, different manufacturers is not possible to have the same effect.

打印本页】 ||【 关闭窗口
友情链接:
返回首页 | 产品中心 | 组织结构 | 企业文化 | 联系我们
CopyRight @ 2015 赤峰和美嘉科技有限公司(Chifeng hemeijia Science and Technology Ltd.) ALL Rights Reserved
地址:内蒙古赤峰市宁城县 客服电话:400-919-6553 总部电话:0476-5666356
京ICP备20004470号-1

津公网安备 12010102000302号