WO2019158756A1

WO2019158756A1 - Pulverous composition containing clay mineral

Info

Publication number: WO2019158756A1
Application number: PCT/EP2019/053981
Authority: WO
Inventors: Christian Koepsel; Dietrich Rein
Original assignee: Basf Se
Priority date: 2018-02-19
Filing date: 2019-02-18
Publication date: 2019-08-22

Abstract

The invention relates to pulverous compositions, the powder particles of which contain at least one clay mineral and at least one water-soluble organic binder. The invention further relates to a method for producing compositions of this type and to the use of the compositions in foods, in particular in pulverous foods, for example in cereal flours. In the pulverous compositions according to the invention, the powder particles contain at least one clay mineral and at least one water-soluble organic binder, at least 80 vol% of the powder particles contained in the composition having a particle diameter in the range of 70 to 350 µm, and the clay mineral in the powder particles being in the form of agglomerated primary particles, the particle size distribution of which is characterized by a D[v, 09] value below 80 µm, the particle diameter indicated here and the D[v, 09] value being the values determined by static laser light scattering according to ISO 13320:2009.

Description

Powdered composition containing clay mineral

The present invention relates to pulverulent compositions whose powder particles contain at least one clay mineral and at least one water-soluble, organic binder. The invention also relates to a process for the preparation of such compositions and to the use of the compositions in foodstuffs, in particular in powdered foodstuffs, such as in cereal flours.

The contamination of food and feed with mycotoxins, in particular aflatoxins, is a serious problem, especially in emerging countries. Aflatoxins are known to be potent carcinogens and mutagens. They are stable in food and feed, even under processing conditions. Exposure to aflatoxins in food is the cause of severe human disease such as aflatoxicosis and hepatocellular carcinoma. Especially in children, aflatoxins can cause growth disturbances and mental retardation even at low levels of exposure - see, eg. See, for example, P. Wang et al., Food Additives and Contaminants, 25 (5) (2008) 622-634 for further references. The harmful effects of aflatoxins on domestic and farm animals, especially poultry and small pets such as dogs or cats, have also been known for a long time.

There have been various reports of the use of clay minerals in food to reduce exposure to aflatoxins caused by food or feed. For an overview, see for example T.D. Phillips et al., Food Additives and Contaminants, 25 (2) (2008), 134-145. The effect of the clay minerals is essentially due to adsorption of the aflatoxins to the clay minerals. This reduces the uptake of aflatoxins in the gastrointestinal tract of exposed organisms and, consequently, their bioavailability and thus their toxicity to the organism - see T.D. Phillips et al., Poultry Science, 67 (1988) 243-247; T. D. Phillips et al., Toxicological Sciences 52 (1999) 118-126; as well as T.D. Phillips et al., Advances in Experimental Medicine and Biology 504 (2002) 157-171. The property of clay minerals to adsorb mycotoxins such as aflatoxins and thus significantly reduce their bioavailability is also referred to in the literature as the deactivation of mycotoxins.

US Pat. No. 5,165,946 describes additives for feedstuffs which essentially consist of a particulate phyllosilicate whose particle is coated with a water-soluble sequestering agent or complexing agent. By the sequestering agent should improve the adsorption of mycotoxins on the layered silicate particles. In this context, phosphate-containing granules and powders are described.

WO 92/05706 describes the use of certain montmorillonite-based clay minerals as an aflatoxin-binding additive in feeds for animal nutrition and proposes a method of identifying clay minerals which bind aflatoxins to a particular degree.

WO 2007/011825 describes the use of acid-treated clay minerals as a food and feed additive for deactivating aflatoxins and for reducing the growth of mycotoxin-producing microorganisms. Preference is given to using clay minerals with a particle size below 80 μm.

US 2012/0328672 describes a process for the fractionation of finely divided, cadmium-containing clay minerals into a coarse fraction having an average particle size above 100 μm and a finely divided fraction having an average particle size below 100 μm, in particular in the range from 20 to 60 μm. The finely divided fraction should be characterized by a lower heavy metal content and an increased binding capacity for aflatoxins.

Although clay minerals in the form of finely divided dusts adsorb mycotoxins such as aflatoxins particularly well and thus reduce their bioavailability, these dusts are difficult to handle. In particular, these dusts can be incorporated only poorly or less reliably in powdered foods such as flours. The problem here is that the finely divided powder particles can separate from the flour due to their higher density and fineness, resulting in an uneven distribution in the flour. By contrast, coarse fractions of clay minerals have the above-mentioned disadvantages of a lower binding capacity for mycotoxins and optionally a higher heavy metal content. In addition, they cause an unpleasant, sandy mouthfeel on consumption of a foodstuff made from a flour produced therewith due to their particle size and hardness, as is also the case when processing the additized flour, for example in the production of baked goods such as bread or other foods such as porridge Particle size is maintained.

JPS-63312105 describes granules of alumina powder prepared by mixing alumina powder with an aqueous solution of a binder such as polyvinyl alcohol in a granulating drum having a plurality of rotary mixing elements. In this case, relatively coarse-particle granules are obtained which have a mean Have diameters in the range of 170 to 840 pm and a high proportion of coarse particles. The granules are proposed for use in plant protection products and fertilizers. For use in powdery foods they are unsuitable.

AU 548773 describes feed formulations for ruminants containing a layer silicate from the montmorillonite group. The feeds can be produced in the form of granules or pellets. They are unsuitable for use in powdery foods.

It is therefore an object of the invention to provide compositions based on clay minerals which are easy to handle, which can be incorporated easily and uniformly into powdery food or feed and which do not separate and which do not lead to disadvantageous sensory properties. The compositions should be easy and reproducible. In addition, the compositions should not or not appreciably impair the property of the clay minerals to bind mycotoxins, in particular aflatoxins such as aflatoxin B1.

It has surprisingly been found that these and further objects are achieved by the powdered, clay mineral-containing compositions whose powder particles have a particle diameter in the range of 70 to 350 pm, in particular in the range of 70 to 250 pm, wherein the clay mineral in the powder particles in the form of agglomerated primary particles whose particle size distribution is characterized by a D [v, 09] value below 80 μm, in particular below 70 μm, and wherein the clay minerals contain at least one water-soluble organic binder which is mono-, di-, or di- and polysaccharides which preferably have at least one glucose unit.

Accordingly, the present invention relates to pulverulent compositions whose powder particles contain at least one clay mineral and at least one water-soluble organic binder selected from mono-, di- and polysaccharides, which preferably have at least one glucose unit, wherein at least 80 vol .-% of the powder particles contained in the composition have a particle diameter in the range of 70 to 350 pm, in particular 70 to 250 pm or 80 to 250 pm and wherein the clay mineral is present in the powder particles in the form of agglomerated primary particles whose particle size distribution by a D [v, 09] value is characterized below 80 pm, in particular below 70 pm, wherein the particle diameter specified here and the D [v, 09] value are the values determined by static laser light scattering in accordance with ISO 13320: 2009.

The invention also relates to a process for preparing such compositions which comprises agglomerating a clay mineral dust using an aqueous solution of the water-soluble organic binder, wherein the particle size distribution of the clay mineral dust by a D [v, 09] value below 80 gm , in particular below 70 gm, determined by static laser light scattering according to ISO 13320: 2009.

The invention also relates to the use of a composition according to the invention as an additive in foodstuffs and feedstuffs, in particular in powdery foods and feedstuffs, such as, for example, in flours intended for human nutrition. The invention also relates to the use of a composition according to the invention for binding mycotoxins in such food and feed.

The invention has a number of advantages. Because of their particle size, the compositions according to the invention are easier to handle than the clay dust normally used and are easier and more uniformly incorporated into pulverulent food and feed. In these powdered food and feed they show a lower tendency to settle or to separate. In contrast to clay mineral powders of comparable particle size, they do not lead to disadvantageous sensory properties. In addition, the compositions do not or do not appreciably affect the property of the clay minerals contained therein to bind mycotoxins, in particular aflatoxins such as aflatoxin B1. Despite their comparatively large particle size they do not lead to a sensory impairment. In addition, the compositions according to the invention can be produced in a simple and easy manner and on a large scale by conventional agglomeration processes of commercially available clay mineral dusts using commercially available, water-soluble binders.

Clay minerals in the context of the invention are sheet silicates and minerals with a high proportion of sheet silicates of preferably at least 50% by weight, in particular at least 60% by weight, based on the clay mineral. Preference is given to clay minerals with a high proportion of aluminum-containing sheet silicates, so-called aluminum phyllosilicates, of preferably at least 50% by weight, in particular at least 55% by weight, based on the clay mineral, and especially with a high content Proportion of hydrated calcium-containing aluminum phyllosilicates of preferably white at least 50% by weight, in particular at least 55% by weight, based on the clay mineral.

Foods according to the invention are nutrient-containing compositions for human nutrition. The term foodstuffs includes food raw materials that are processed into ready-to-consume foods, as well as ready-to-eat foods made from these food commodities.

Feed for the purposes of the invention are nutrient-containing compositions for animal nutrition, in particular for the nutrition of domestic animals, such as dogs or cats, and poultry.

Here and below are the expression wt .-% for weight percent and the expression Vol .-% for volume percent.

According to the invention, at least 80% by volume of the powder particles contained in the composition have a particle diameter in the range from 70 to 350 μm or in the range from 80 to 350 μm, in particular in the range from 70 to 300 μm or in the range from 80 to 300 pm and especially in the range of 70 to 250 pm or in the range of 80 to 250 pm. Accordingly, the D [v, 01] value of the particle size distribution of the composition according to the invention is generally at least 70 .mu.m and in particular at least 80 .mu.m, for example in the range from 70 to 150 .mu.m or in the range from 80 to 135 .mu.m or below Range from 80 to 125 pm. The D [v, 09] value of the particle size distribution of the composition according to the invention is generally at most 350 .mu.m, in particular at most 300 .mu.m and especially at most 250 .mu.m and especially at most 200 .mu.m, and is for example in the range from 130 to 350 pm or in the range of 150 to 300 pm or in the range of 180 to 250 pm. The D [v, 05] value of the particle size distribution of the compositions according to the invention is generally in the range from 80 to 240 μm, in particular in the range from 85 to 200 μm and especially in the range from 90 to 190 μm. In another group of embodiments, the D [v, 05] value of the particle size distribution is in the range from 80 to 180 μm, in particular in the range from 85 to 175 μm and especially in the range from 90 to 170 μm. In another group of embodiments, the D [v, 05] value of the particle size distribution is in the range from 1 10 to 240 μm, in particular in the range from 115 to 200 μm and especially in the range from 120 to 190 μm. The compositions according to the invention preferably have a particle size distribution whose volume-weighted average D [4,3] is in the range from 90 to 250 μm, in particular in the range from 95 to 220 μm and especially in the range from 100 to 200 μm. The surface weighted mean D [3,2] of Particle size distribution of the compositions according to the invention is generally in the range from 75 to 200 gm, in particular in the range from 80 to 180 gm and especially in the range from 85 to 160 gm. Here and in the following, all information relates to particle sizes, particle diameters and particle size distributions , including the values D [v, 01], D [v, 05], D [v, 09], D [4,3] and D [3,2] to those by static laser light scattering according to ISO

13320: 2009 determined on samples of the powdered compositions or the clay mineral dusts particle size distributions. For the term "static laser light scattering according to ISO 13320: 2009", the abbreviation SLS is used below. In this context, the value D [v, 01] means that 10% by volume of the particles of the measured sample have a particle diameter below the value indicated as D [v, 01]. Accordingly, the value D [v, 05] means that 50% by volume of the particles of the measured sample have a particle diameter below the value indicated as D [v, 05]; and the value D [v, 09] means that 90% by volume of the particles of the measured sample have a particle diameter below the value stated as D [v, 09]. The value D [4, 3] stands for the volume-weighted average determined by means of SLS, which is also referred to as De Brouckere mean value and which corresponds to the weight average in the particles according to the invention. The value D [3, 2] stands for the surface-weighted average determined by means of SLS, which is also referred to as Sauter diameter.

In the compositions according to the invention, the particle size distribution of the powder particles can also be determined by sieve analysis according to DIN 66165-1: 2016-08. In particular, the inventive compositions contain less than 20 wt .-%, in particular less than 15 wt .-%, especially less than 10 wt .-% powder particles having a particle size below 63 pm. In particular, the inventive compositions contain less than 15 wt .-%, preferably less than 10 wt .-% powder particles having a particle size above 250 pm. Most preferably, the compositions of the invention contain at least 70

Wt .-%, especially at least 80 wt .-% powder particles having a particle size in the range of 63 to 250 pm and especially in the range of 63 to 212 pm. The weight-average particle diameter, hereinafter also D50, of the powder particles, as results from the particle size distribution determined by sieve analysis, is generally in the range from 70 to 200 μm, in particular in the range from 80 to 180 μm and especially in the range from 90 to 170 pm.

In the powder particles of the compositions according to the invention, the clay minerals are present in the form of primary particles which are separated by the water-soluble organic binder. demittel be held together to form larger powder particles. It is assumed that the powder particles of the compositions according to the invention decompose upon contact with aqueous liquids, for example water, but also saliva, and thus release the primary particles. The water-soluble binder may also cause the primary particles to stabilize against reagglomeration. In any case, therefore, the ability of the clay mineral particles to bind mycotoxins, especially aflatoxins, is not or not appreciably reduced.

The particle size distribution of the primary particles is characterized by a D [v, 09] value of not more than 80 μm, in particular not more than 75 gm and especially not more than 70 μm, and is typically in the range from 20 to 80 μm, in particular in the range from 30 to 75 pm and especially in the range of 40 to 70 pm. In one group of embodiments, the particle size distribution of the primary particles has a D [v, 09] value in the range from 40 to 80 μm, in particular in the range from 45 to 75 μm and especially in the range from 50 to 70 μm. For the suitability of the compositions according to the invention, the D [v, 05] and D [v, 01] values are only of minor importance. Typically, the D [v, 05] value of the particle size distribution of the primary particles is in the range of 10 to 50 μm, especially in the range of 15 to 45 μm. The D [v, 01] value will typically not fall below a value of 1 pm, in particular 2 pm, and is generally in the range from 1 to 15 pm, especially 2 to 10 pm.

Suitable clay minerals contained in the compositions according to the invention are naturally those which are capable of sufficiently adsorbing mycotoxins, in particular aflatoxins. By determining adsorption isotherms for mycotoxins, especially for aflatoxin Bi, the person skilled in the art can select clay minerals which are suitable as primary particles for the compositions according to the invention in a manner known per se. Methods for this purpose are known from the cited prior art, for. From WO 2007/01 1825 and from A. Marroquin-Cardona et al., Food Addit. Contam. Part A, 2009 26: 733-743 and T.D. Phillips in Toxicol.

1999: 52: 118-126.

In particular, suitable primary particles are those clay minerals whose suspension in water at pH 6.5 and 22 ° C. has a _Qmax - Ne t for aflatoxin Bi of at least 0.1 mol / kg, especially at least 0.15 mol / kg and especially at least 0.2 mol / kg. The Q _max - \ Ne t corresponds to the maximum possible loading of the clay minerals with aflatoxin B1 under the conditions mentioned and is calculated by extrapolation of the adsorption isotherms (Langmuir application) to high concentrations of the aflatoxin.

Aflatoxin Bi

The method for determining the O _max value is described by A. Marroquin-Cardona et al., Food Addit. Contam. Part A, 2009 26: 733-743 and by TD Phillips in Toxicol. 1999: 52: 118-126. for aflatoxin B1 and in WO 2007/01 1825.

Suitable clay minerals are in particular phyllosilicates based on aluminum-containing silicates, especially based on calcium- or magnesium-containing aluminum silicates, especially those which contain water of hydration and which are referred to as hydrated aluminum silicates. Here and below, the term "based on" means that said specific clay mineral constitutes at least 50% by weight, in particular at least 55% by weight, of the total mass of the clay mineral. Examples of such clay minerals are those based on clay minerals of the Strunz classes 9. EC.05 (talc group), 9. EC.40 (montmorillonite group), 9.EC.45 (saponite group) and 9 EC.50 (vermiculite group). Of these, those based on calcium-containing montmorillonites and those based on magnesium-containing montmorillonites are particularly preferred.

The clay minerals used as primary particles are typically treated fractions of naturally occurring clay minerals. These usually contain other mineral constituents, which need not necessarily be clay minerals, but can act. Accordingly, the content of the here referred to as preferred clay minerals in the primary particles, based on the total mass of the primary particles, at least 50 wt .-%, in particular at least 55 wt .-%. The clay minerals used can accordingly contain further mineral constituents, which, however, preferably constitute not more than 45% by weight of the particular clay mineral. Such constituents are, for example, quartz, mica, feldspar, pyrites and calcites as well as clay minerals which differ from the respective main or base sistone mineral.

Preferably, the clay minerals contain no or only small amounts of heavy metals which are toxic to the human or animal organism when ingested, such as cadmium, lead, arsenic, nickel or chromium. The proportion of toxic heavy metals is typically below the limit values provided for this purpose. By contrast, higher iron contents are harmless.

Particularly preferred are clay minerals which have a content of hydrated aluminum silicates of at least 50% by weight, especially at least 55% by weight. Particularly preferred in this case, the hydrated aluminum silicates are selected from hydrati cal calcium aluminum silicates and hydrated magnesium aluminum silicates. In particular, clay minerals are preferred which have a content of layer silicates from the group of montmorillonites of at least 50% by weight, especially at least 55% by weight. Specifically, it concerns clay minerals, which have a content of phyllosilicates from the group of calcium-containing montmorillonite of at least 50 wt .-%, especially at least 55 wt .-%. Such a clay mineral based on a calcium-containing montmorillonite is the commercially available product NovaSil Plus® from BASF SE, which is a bentonite containing calcium montmorillonite. Also suitable are finely divided clay minerals described in US 2012/0328672, in particular clay minerals, which have a content of phyllosilicates from the group of the calcium-containing montmorillonites of at least 50% by weight, especially at least 55% by weight, and whose particle size Sizes below 63 μm (mesh 250) and especially below 44 μm (mesh 325), e.g. B. sieve fractions in which at least 95% of the particles have a size in the range of 5 to 60 pm and especially 5 to 44 pm.

In addition to the primary particles of clay mineral, the compositions according to the invention comprise at least one water-soluble organic binder which holds or glues together the primary particles to form an agglomerate. In general, therefore, the powder particles of the compositions according to the invention have an irregular structure, which is often referred to as blackberry structure.

With regard to the water-soluble binders, the term water-soluble means that the binder has a solubility of at least 10 g / l, in particular at least 20 g / l, at 20 ° C. in deionized water. The water-soluble binders are preferably suitable for use in foods or animal feeds and are especially approved for this purpose.

Suitable binders according to the invention are selected from food-grade mono-, di- and polysaccharides, especially those mono-, di- and polysaccharides based on glucose and / or fructose. In particular, the binders are selected from glucose, fructose, sucrose, maltose, starch degradation products with a DE value in the range from 2 to 50, in particular in the range from 2 to 30, lipophilic starch derivatives and cold water-soluble starches.

The binders according to the invention not only have the advantage that the affinity of the clay minerals is substantially or completely retained and good compatibility with foodstuffs is ensured. In addition, the formation of coarse-particle granules is less pronounced, in particular in comparison with other binders, and it is possible to set narrower particle size distributions. In this way, higher yields can be achieved.

Examples of starch degradation products with a DE value in the range from 2 to 50, in particular with a DE value in the range from 2 to 30, are above all starch hydrolysates and especially maltodextrins with a DE value in the range from 2 to 50, in particular with a DE value in the range of 2 to 30.

Examples of lipophilic starch derivatives are starches and starch hydrolysates modified with lipophilic groups, eg. For example, with alkylsuccinic acid groups and / or alkenylsuccinic acid-modified starches or their salts, in particular their sodium salts, wherein the alkyl or alkenyl radical is usually unbranched and preferably 6 to 20 and especially 8 to 18 C Carries atoms. Examples of lipophilic starch derivatives are starches and starch hydrolysates which are modified with Cs-C-is fatty acids. Preferred lipophilic starch derivatives are starches and starch hydrolysates which have been modified with octenylsuccinic acid and their salts, in particular their sodium salts.

Cold-water-soluble starches are starches which are completely soluble or swellable in water at 20 ° C. These are typically starches with a high amylose content of preferably> 50% by weight. The cold-water-soluble starches may be starches which naturally have a high amylose content, eg. As waxy starches, as well as starch fractions with high amylose content.

Among the abovementioned binders, particular preference is given to di- and oligosaccharides which have the at least one glucose unit, in particular lactose and starch degradation products, in particular maltodextrins, with one having a DE value in the range from 2 to 50, in particular with a DE value Range from 2 to 30. A particularly preferred group of embodiments relates to compositions in which the binder is selected from starch degradation products, in particular maltodextrins, with one having a DE in the range from 10 to 50.

Another particularly preferred group of embodiments relates to compositions in which the binder is selected from lactose.

In order to achieve the necessary stability of the powder particles contained in the compositions according to the invention, the proportion of binder, based on the total mass of the clay mineral and the binder, is generally at least 1% by weight, in particular at least 5% by weight especially at least 10% by weight. In general, the proportion of binder, based on the total mass of Tonmine- rals and the binder, 50 wt .-%, especially 40 wt .-% and especially 35% by weight does not exceed.

Accordingly, the powders according to the invention generally contain at least 50% by weight, in particular at least 60% by weight and especially at least 65% by weight, e.g. From 50 to 99% by weight, in particular from 60 to 95% by weight and especially from 65 to 90% by weight, of the clay mineral, the details in% by weight being based on the total mass of the clay mineral and the binder.

In addition to the clay mineral and the binder, the powder may also contain small amounts of water due to the production. The water content will generally not exceed 10 wt .-%, based on the total mass of the powder and is often in the range of 1 to 10 wt .-%, based on the total mass of the powder.

The compositions according to the invention can be prepared analogously to agglomeration processes which are known per se and are suitable for the production of powders, for example by spray drying processes and fluidized bed agglomeration processes. Such methods are generally known to the skilled person, z. From H. Mollet and A. Grubenmann, "Formulation Technology", 1st Edition, Wiley VCH Verlag GmbH, Weinheim 2001, Chapters 6.2.7 and 6.2.8 and the literature cited therein and R.H. Perry et al. (Ed.) "Perry's Chemical Engineers' Handbook," 7th Edition, McGraw Hill, New York 1997, 20-77-20-79 and the literature cited therein.

Such a process typically comprises the agglomeration of a clay mineral dust whose particle size distribution typically corresponds to the particle size distribution of the primary particles in the powder particles of the composition according to the invention. Accordingly, the particle size distribution of the set clay mineral dust by a D [v, 09] value, determined by static laser light scattering according to ISO 13320: 2009, below 80 gm, in particular at most 75 gm and especially at most 70 gm characterized and is typically in the range of 20 to 80 gm, in particular in the range from 30 to 75 gm and especially in the range from 40 to 70 gm. With regard to the D [v, 01] and D [v, 05] values of the particle size distribution of the clay mineral dust, the statements made above for the particle size distribution of the primary particles apply analogously ,

The binder required for the agglomeration of the particles of the clay mineral dust is used here in the form of an aqueous solution of the water-soluble organic binder. Such an aqueous solution usually contains the water-soluble organic binder in a concentration of 1 to 30% by weight, in particular in a concentration of 2 to 25% by weight or 5 to 25% by weight and especially 10 to 25 wt .-%.

In addition to the binder, the solution may also contain other constituents other than water. These other ingredients may be volatile or non-volatile. These include, for example, impurities or aids, eg. As stabilizers that may be contained in the commercially available binders, but also additives that cause stabilization of the powdered composition on storage. A significant advantage of the invention is to be seen in the fact that such additional stabilizing agents are generally not required. The aqueous solution preferably contains not more than 20% by weight, in particular not more than 10% by weight, based on the binder contained in the aqueous solution, of constituents which are different from the binder.

The type of treatment of the clay mineral dust with the aqueous solution of the water-soluble, organic binder is determined in a manner known per se according to the type of agglomeration process and is usually carried out by spraying the aqueous solution of the binder on a moving Tonmine- ralstaub or by spraying together the aqueous solution of the binder with the clay mineral dust.

The preparation of the compositions according to the invention is preferably carried out by a fluidized-bed agglomeration process. For this purpose, a fluidized bed of the clay mineral dust is produced and the aqueous solution of the water-soluble organic binder is sprayed onto the clay mineral dust present in the fluidized bed. In general, one will generate the fluidized bed in a device suitable for this purpose by means of a gas stream, that is, a gas stream through the clay mineral lei th and thereby produce a fluidized bed of the clay mineral. Optionally, one will provide rotating elements to aid formation of the fluidized bed. Preferably, the device is operated such that the flow rate V of the gas flow in the device is at least 1.2 times, in particular at least 1.5 times, the flow rate of the gas stream required to produce the fluidized bed, which is also hereafter is referred to as V _min . Preferably, the flow velocity V will not exceed 10 times the value, in particular 5 times the value of V _m in.

The spraying can be carried out from below and thus in cocurrent with the gas stream (bottom spray method) or from above and thus in countercurrent to the gas stream (top spray method) or tangentially to a fluidized bed (tangential spray method). Procedure). Preferred is the top spray method.

Preferably, the fluidized bed process is carried out at temperatures above 20 ° C and below the boiling point of the aqueous solution of the binder. Decisive here is the temperature in the fluidized bed, which corresponds approximately to the exhaust air temperature. Preferably, the process will be carried out so that the temperature in the fluidized bed is in the range of 30 to 80 ° C. Higher temperatures are also possible. Here, one can control the temperature in the fluidized bed in a simple manner on the temperature of the gas stream, the rate of addition of the aqueous solution of the binder and the flow rate of the gas stream. Preferably, the temperature of the gas stream will be chosen to be in the range of from 40 to 150 ° C. Depending on the size and capacity of the plant then the temperature difference between incoming and exiting air flow is at least 10 K, z. B. 10 to 100 K.

The fluidized bed process makes it possible to adjust the particle size of the powder particles of the inventive composition, for. On the concentration and viscosity of the aqueous solution of the binder, on the droplet size during spraying, on the temperature and the velocity of the gas stream. The connections are known in principle, z. From RH Perry et al. (Ed.) "Perry's Chemical Engineers'Handbook," 7th Edition, McGraw Hill, New York 1997, 20-79, Tables 20-46. The exact parameters can be determined by the skilled person via routine tests. As already mentioned, the compositions according to the invention are particularly suitable as an additive in powdered foodstuffs and feedstuffs, since they are easy to incorporate, do not segregate and, moreover, are not undesirable in the ready-to-consume products prepared from the powdered foodstuffs. cause sensory effects.

Suitable powdered foodstuffs and feedstuffs are, above all, those foods in which there is the danger of mold being attacked or which may already contain mycotoxins, especially aflatoxins, as a result of the preparation.

These are, in particular, powdery foods and feedstuffs, in particular flours, especially flours of cereals or pseudo cereals such as wheat, rye, barley, oats, emmer, spelled, einkorn, millet, triticale, amaranth, rice or maize, but also to flours of nuts, nuts and oilseeds, z. For example, peanut, walnut, Brazil nut, sesame, sunflower, pumpkin seed, apricot kernel, pea, soybean or lentil flour, flours from starchy fruits such as cassava and potato. Also suitable are beverage powder, for. As milk powder and dried fruit juice or tea extracts.

In principle, it is also possible to incorporate the compositions according to the invention in non-powdery, for example liquid or pasty or semi-solid products in which there is a risk of infestation by mold fungi or which may already contain mycotoxins, especially aflatoxins, as a result of the preparation. These include, for example, dairy products such as cheese and butter, as well as nut pastes and peanut butter, as well as food bars and pasta such as bread.

The amount of composition according to the invention required for effective additive formation depends in a manner known per se on the possible contamination of the food or feed by mycotoxins and is generally 0.1 to 2.0% by weight, in particular from 0.5 to 1.5% by weight, calculated as clay mineral and based on the total amount of the foodstuff.

The following examples serve to illustrate the invention.

analytics:

The particle size distribution was determined by static laser light scattering of the resulting agglomerates by means of a Mastersizer 2000 from Malvern Instruments Ltd. (Sample application was carried out as a powder). Alternatively, the particle size distribution of the powder compositions according to DIN 66165-1: 2016-08 was determined by means of a vibratory sieving machine VS 1000 from Retsch (Haan, Germany), which was equipped with 6 test sieves of the following mesh size 250 gm, 212 gm , 180 gm, 125 gm, 106 gm and 63 gm.

The determination of the Q _max - \ Ne te of the clay mineral starting material and the agglomerates According to the invention available for aflatoxin B1 was carried out by calculation from the adsorption isotherms of a suspension of the clay mineral in water at pH 6.5 and 22 ° C after the A. Marroquin -Cardona et al., Food Addit. Contam. Part A,

2009 26: 733-743, which is that of T.D. Phillips in Toxicol. 1999: 52: 118-126.

The determination of the residual moisture content of the powder is based on DIN EN

12880: 2000 by drying a sample of the powder at temperatures in the range of 105 ± 5 ° C at ambient pressure to constant weight. The binder content in the powders is determined from the ratio of feeds, i. submitted clay mineral and amount of sprayed binder solution, taking into account the binder concentration of the solution and the residual moisture of the powder calculated.

Starting Materials:

In the following examples, the clay mineral used was a commercial calcium bentonite having a montmorillonite content of at least 60% by weight and screened to a particle size of <63 gm (230 mesh). The starting material had the following particle size distribution:

D (v, 01) = 6.6 gm

D (v, 05) = 24.3 gm

D (v, 09) = 57.7 gm

D [4, 3] = 28.8 gm

The Q _max - \ Ne i of the clay mineral for aflatoxin B1, calculated from the adsorption isotherms of a suspension of the clay mineral in water at pH 6.5 and 22 ° C, was about 0.40 mol / kg.

Instead of the clay mineral used in the following examples can also be a US 2012/0328672 by fractionation of a commercial calcium bentonite with a montmorillonite content of at least 60 wt .-% produced clay mineral, which was sieved to a particle size <44 pm (350 mesh).

As binders were used:

Binder 1: Commercial maltodextrin with a DE value of 19

Glucidex 19 from Roquette

Binder 2: Commercial, modified with octenyl succinic anhydride

Starch degradation product in the form of the sodium salt (E 1450)

Capsul HF from the company Ingredion

Binder 3: Commercial maltodextrin with a DE value of 47

Glucidex 47 from Roquette

Binder 4: Lactose monohydrate - food grade

Binder 5: partially saponified polyvinyl alcohol (degree of hydrolysis 87-88 mol%) of which 4% strength by weight aqueous solution had a viscosity at 20 ° C., determined in accordance with DIN 53015 of 5-6 mPas (Kuraray Poval 6-88)

The preparation of the compositions described in the following Examples 1 and 2 was carried out by spray agglomeration. The spray agglomeration was carried out in a fluidized-bed granulator GPCG 3 from Glatt, operated in top-spray mode with a compressed-air two-fluid nozzle.

Example 1 - Spray Agglomeration with Binder 1 The fluidized bed was produced by means of an air flow with a temperature of 60 ° C. and a volume velocity of 77 m ³ lr ¹ . The spray pressure was 2 bar. The exhaust valve was 33% open.

1527 g of clay mineral were placed in the fluidized-bed granulator and transferred to an active layer. On the fluidized bed was from above, d. H. in countercurrent to the air flow, within 67 min. 1402 g of a 4.85% strength by weight solution of binder 1 in water (68 g of binder 1) were sprayed on with a constant spray rate. Then under the same conditions within 88 min. Another 1848 g of a 8.8% strength by weight solution of binder 1 in water (162.6 g of binder 1) and then within 70 min. 1504 g of a 10.1% strength by weight solution of binder 1 in water

(151, 9 g of binder 1) sprayed. The product obtained was a finely divided, flowable, non-hygroscopic powder having a binder content of about 20% by weight. The bulk density was 429 g / l. In contrast to the non-agglomerated clay mineral, the powder did not dust. Microscopic analysis of the powder showed that the particles have an irregular shape of bonded together primary particles (blackberry structure). The particle size distribution, determined by means of light scattering, is given in the following Table 1.

Example 2 - Spray Agglomeration with Binder 2

The powders were prepared under the conditions given for Example 1. In this case, 1558 g of clay mineral were placed in the fluidized-bed granulator and transferred to a fluidized bed. On the fluidized bed was from above, d. H. in countercurrent to the air flow, within 151 min. With constant spray rate 3696 g of a 1 1, 2 wt .-% solution of binder 2 in water sprayed (414 g of binder 2). Then under the same conditions within 25 min. Another 804 g of 1 1, 2 wt .-% solution of binder 2 in water sprayed (90.0 g of binder 2). The product obtained was a finely divided, flowable, non-hygroscopic powder having a binder content of about 24.4% by weight. The bulk density was 303 g / l. Unlike the non-agglomerated clay mineral, the powder did not dust.

Microscopic analysis of the powder showed that the particles have an irregular shape of bonded together primary particles (blackberry structure). The particle size distribution, determined by means of light scattering, is given in the following Table 1.

Table 1 :

EXAMPLES 3 TO 14, COMPARATIVE EXAMPLE C1 The powders were produced by spray agglomeration in a fluidized-bed processor Aeromatic Fielder MP1 from GAE, operated in top-spray mode with a compressed air-operated two-substance nozzle (diameter 0.8 mm) and one Spray pressure of 1, 5 bar. The spray rate was about 10 g / min. The fluidized bed was lr ¹ by means of an air flow at a speed of about 50 m ³ . The supply air temperature was adjusted so that the product during the spraying process had approximately the specified temperature in Table 2.

460.3 g of clay mineral were initially introduced into the fluidized bed processor and transferred to a fluidized bed. On the fluidized bed was from above, d. H. in countercurrent to the air stream, sprayed the desired amount of the binder in the form of an aqueous solution in several portions. Optionally, a final drying of the powder in the fluidized bed of about 20 min. at the specified setpoint temperature. In all cases finely divided, flowable, non-hygroscopic powders were obtained. The experimental conditions, the composition of the powders and the characteristic values of the particle size distributions of the powders obtained are given in Table 2.

In Examples 3 to 6, a 20 wt .-% aqueous solution of the binder 1 was used. In Examples 7 to 10, a 20 wt .-% aqueous solution of the binder 3 was used. In Examples 11 to 14, a 16% strength by weight aqueous solution of binder 4 was used. In the comparative example, a 9.5% strength by weight solution of the binder 5 was used.

Table 2:

1) set temperature

2) weight percent, based on the total mass of the powder

3) Determination by sieve analysis

4) Quantities of the respective fraction, based on the total mass of the fractions

5) With after-drying

6) Comparative Example

The examples and the comparative example show that, in contrast to the binders according to the invention, the binder polyvinyl alcohol leads to very coarse-particle powders even at low use. In addition, spraying caused clogging of the spray nozzle.

Application examples:

95 parts by weight of the powder from Example 1 were mixed with 5 parts by weight of a powdered vitamin mixture (particle size distribution: d (v, 0.1) = 5 pm, d (v, 0.5) = 48 pm and d (v, 0.9) = 166 pm) , The mixture was shaken 30 minutes ler in a Rütt (Vibramax 100 from. At 900 rpm ^{x 1).} There was no segregation.

0.5 parts by weight of the powder from Example 1 was mixed with 100 parts by weight of white corn flour having a flour specification suitable for Ugali (particle size distribution: d (v, 0.1) = 40 pm, d (v, 0.5) = 370 pm and d (v, 0.9) shaken fat content about 1, 8%) and mixed (in a shaker Vibramax 100 from 900 Umin ^{· 1)} = 717 pm.. There was no segregation.

Production of enriched ugali:

White maize flour with a flour specification suitable for ugali (particle size distribution: d (v, 0.1) = 40 pm, d (v, 0.5) = 370 pm and d (v, 0.9) = 717 pm, fat content about 1.8%) was mixed with the powder of Example 1 in the ratio 99.5: 0.5 and with 250 ppm of the vitamin mixture. 100 g of the additized corn flour thus obtained were allowed to trickle in about 220 ml of boiling water with stirring and stirred for a further 5 min. Then, the mixture was further kneaded while being kneaded with the spoon 5. Then one formed a ball from the ugali.

For comparison purposes, the white maize flour with only 250 ppm of the vitamin mixture were additized in the same way and processed in the manner described to Ugali. Subsequently, the two Ugali samples were examined for their organoleptic properties. The ugali produced with the corn flour additized according to the invention, ie with the powder of Example 1, had no palatable differences to the ugali produced with the reference flour which did not contain the powder.

Whole corn meal (particle size distribution: d (v, 0.1) = 52 pm, d (v, 0.5) = 392 gm and d (v, 0.9) = 719 pm, fat fraction about 1, instead of white maize flour, 8%) was used. Again, no palpable differences could be found between a ugali prepared with wholegrain maize flour additized with the powder of Example 1 according to the invention and a ugali prepared with the reference flour (wholemeal maize flour without inventive powder). be determined.

Claims

claims:

1. A powdery composition whose powder particles contain at least one Tonmine- ral and at least one water-soluble, organic binder selected from water-soluble, suitable for food mono-, di- and polysaccharides, wherein at least 80 vol .-% of in the Powder particles having a particle diameter in the range of 70 to 350 pm and wherein the clay mineral in the powder particles in the form of agglomerated primary particles whose particle size distribution is characterized by a D [v, 09] value below 80 pm, wherein it the particle diameter specified here and the D [v, 09] value are the values determined by the static laser light scattering according to ISO 13320: 2009.

2. Composition according to claim 1, wherein the size distribution of the powder particles is characterized by D [v, 05] value in the range of 80 to 180 pm:

3. Composition according to one of the preceding claims, wherein the water-soluble, organic binder is selected from di- and Oligosac- chariden having at least one glucose unit.

4. Composition according to one of the preceding claims, wherein the water-soluble, organic binder is selected from sucrose, maltose, lactose, starch degradation products having a DE value in the range 2 to 50, lipophilic starch derivatives and cold water-soluble starches and mixtures thereof ,

5. Composition according to one of the preceding claims, wherein the proportion of binder, based on the total mass of the clay mineral and the binder, in the range of 1 to 50 wt .-% is.

6. A composition according to any one of the preceding claims, wherein the

Clay mineral has a Q _max - \ Ne t for aflatoxin B1, calculated from the adsorption isotherms of a suspension of the clay mineral in water at pH 6.5 and 22 ° C of at least 0.1 mol / kg.

7. A composition according to any one of the preceding claims, wherein the

Clay mineral is selected from hydrated aluminum silicates, especially hydrated calcium aluminum silicates and hydrated magnesium aluminum silicates and clay minerals containing these hydrated aluminum silicates. Contain silicates to at least 50 wt .-%.

A composition according to claim 7, wherein the clay mineral has a content of montmorillonite of at least 60% by weight, based on the total mass of the clay minerals in the composition.

9. A composition according to any one of the preceding claims wherein the powder particles have an irregular structure.

10. A process for the preparation of a composition according to any one of the preceding claims, comprising the agglomeration of a clay mineral dust, whose particle size distribution by a D [v, 09] value below 80 pm, determined by static laser light scattering according to ISO 13320: 2009 , characterized by using an aqueous solution of the water-soluble organic binder.

11. The process according to claim 10, wherein a fluidized bed of the clay mineral dust is produced and the aqueous solution of the water-soluble organic binder is sprayed onto the clay mineral dust present in the fluidized bed.

12. The method according to claim 10 or 11, wherein the aqueous solution contains the water-soluble organic binder in a concentration of 1 to 25 wt .-%.

13. Use of a composition according to any one of claims 1 to 9 in food and feed.

14. Use according to claim 13, wherein the food is a flour intended for human nutrition.

15. Use of a composition according to any one of claims 1 to 9 for the binding of mycotoxins in food and in animal feed, especially in meals intended for human nutrition.