HU204176B - Method for increasing the specific surface of clay minerals and making premixture and/or fodder mixture or stabilizing solutions particularly liquid fertilizer by using the clay mineral having increased surface - Google Patents

Abstract

A method is proposed to increase the specific surface of clay minerals and to use the treated material to produce animal feed or to stabilise solutions, especially of artificial fertilisers. The raw, wet clay mineral, primarily bentonite, is mechanically broken up and mixed with water in a preparatory unit. The resulting sludge is kneaded in an enclosed, pressurised space and used to prepare a fine emulsion, with 3mm-80 micron bentonite granules, by pressing through filters. The emulsion is mixed with feed additives in a mixer unit . Alternatively, the emulsion is fed to a reactor to produce a stabilised artificial fertiliser solution.

Description

The present invention relates to a process for increasing the specific surface area of clay minerals. The present invention also relates to a process for the preparation of premixes or compound feeds or the stabilization of solutions, such as liquid fertilizers, by using clay minerals with increased surface area.

It is known that animals, e.g. When feeding pigs, clay minerals, which are ground as a carrier and mineral feed supplement, are primarily bentonite, since the composition of the clay minerals is sufficient to meet a significant part of the animal's micronutrient requirements. The carrier should be neutral to the animal body and should not damage it, while at the same time promoting a uniform distribution of minerals and trace elements added to the compound feed or premr'x. The carrier must be a non-hygroscopic, delicate, lint-like material. All these conditions are met by naturally occurring high-mass clay minerals, not only because they are easily milled to form fine-grained excipients, but also because of the macronutrients and trace elements (calcium, phosphorus, magnesium, sodium, potassium, , iron, manganese, copper, zinc, iodine, cobalt, selenium, molybdenum and boron).

The suitability of bentonite to replace iron deficiency in pigs and to supply them with other mineral derivatives, e.g. is disclosed in Hungarian Patent Application No. 182003.

According to Hungarian patent application A168 364, a zeolite-containing mineral additive is added to the compound feed to increase the production of pork.

Another application for ground fine-clay minerals is liquid materials, e.g. stabilization of liquid fertilizers.

As is known, fertilizers are liquid-solid systems: solutions in which the solid phase must be prevented, i.e. the solution must be stabilized. For this purpose, fine-grained clay minerals are well suited.

The higher the specific surface area of the crushed clay mineral, the more effective it can be used either as a premix carrier or as a stabilizer. The finer-grained clay mineral carrier absorbs more of the feed components, and the finer the stabilizer, the more homogeneous the stabilized solution. í

At present, clay minerals, e.g. the bentonite is crushed in a ball mill or on a rolling mill. The mine wet material (containing about 30% moisture) is dried and used as a carrier or stabilizer in this form. A major disadvantage of these methods is that the desired particle fineness cannot be achieved by a grinding operation. Doing double or multiple grinding operations results in an excessively high energy input which, by drying, would otherwise increase the high energy costs to the extent that the final product may become unsaleable. A further disadvantage is that the ground, dried bentonite is usually mixed with water during use. The resulting emulsion is used as a carrier or stabilizer

It is an object of the present invention to provide a process that maximizes the specific surface area of clay minerals with minimum energy input.

The invention is based on the discovery that when forming slurry from crude clay mineral, preferably bentonite, and slurrying the slurry and filtering it by compression, the use of eneigia, as a thixotropic material with a low friction coefficient, ), however, as a result of the hydromechanical kneading-crimping filtration process, which takes place in a single apparatus as a continuous process, maximum granularity can be achieved by multiple filtration operations, and the desired particle size of the final product can be adjusted within wide limits (e.g.

Based on the above recognition, the object of the present invention has been solved by a method of increasing the specific surface area of clay minerals by mechanically grinding the damp clay minerals, if necessary, which comprises adding water from the optionally premixed clay minerals. making a slurry which is kneaded at a pressure above atmospheric pressure and pressed through one or more filters to form an emulsion containing a fine-grained clay mineral phase.

The present invention also relates to a process for the preparation of a premix and / or compound feed for animal feed and for stabilizing solutions, preferably liquid fertilizers, characterized in that slurry is prepared from clay or / and clay-containing rock, preferably bentonite, by adding water to the slurry. The resulting emulsion is mixed with feed additive or feed ingredients or / or the emulsion is added to a solution, preferably a liquid fertilizer, of 0.5 or more, and then pressed through one or up to four filters. It is added in an amount of -3.0% by weight to stabilize the solution.

Preferably, clay minerals or clay-containing rocks with a montmorillonite content of more than 50% are used as starting materials. Bentonite is most suitable for the purpose of the present invention, but zeolite, lyllite or other clay minerals may also be used. Theoretical formula for montmorillonite:

Al ₄ Si ₈ O ₂₀ x (OH) ₄ x XH ₂ O (Al is partially replaced by Mg)

The dominant cation distinguishes between Na-, K-, Ca- and Mg-montmorillonil. From the technological point of view, the most preferred are the Na-bentonyls which

They may also be used in their natural state. The Ca-bentonites do not swell in their natural state and therefore require activation, which means that they are mixed with soda (NA ₂ CO ₃ ) to replace the exchangeable Ca ions with Na ions.

The most characteristic properties of bentonite, both as a premix carrier and as a feed, are: swelling, high viscosity, good peptisation, dispersion stability, high and scalable specificity, good film formation, high crude bonding capacity, high cation exchange. It is important from a nutritional point of view that bentonite usually contains no or only minimal amounts of toxic heavy metals

In view of the fact that clay minerals alone have a very wide range of micronutrient contents, the bentonite emulsion of the present invention not only functions as a carrier during the preparation of the premix, but is also considered as a general micronutrient supplement. It is known that the micro-nutrient content of the vegetation used for animal nutrition differs in different areas, mainly due to the composition of the soil. After this determination, the bentonite or other clay mineral emulsion acting as a carrier should be supplemented only with the macronutrients and micronutrients that are absent in the particular landscape. Accordingly, the ratio of emulsion to mineral containing the nrichroic macronutrients may vary within wide limits, for example, the emulsion to mineral ratio may be from 5: 1-2: 1, preferably 4: 1.

The invention will now be described in more detail on the basis of the accompanying drawing, which illustrates the technological process of compounding the feed and stabilizing the fertilizer. Figure 1 is a block diagram of a compound feed preparation; Figure 2 is a block diagram of a fertilizer stabilizer.

According to Figure 1, the minced wet bentonite is fed into the preparation unit 1 according to the arrow α, where it is first subjected to coarse mechanical grinding (pre-grinding) and then mixed with water, and the slurry resulting from this operation is further treated according to the invention. the emulsion leaving the preparation unit 1 according to b or arrow contains bentonite of the desired particle size. In this operation, the slurry is moved forward under pressure above atmospheric pressure, for example by means of a conveyor screw, by which the material is kneaded and pressed through filters which reduce the aperture size in the direction of the slurry progression. The particle size of the bentonite component of the emulsion leaving the preparation unit 1 is e.g. It can range from 3mm to 80 microns.

When sodium bentonite is used as starting material, the emulsion is fed into the mixing unit 3 according to the arrow. If the starting material is Ca-bentonite, its activation, known per se, is carried out in the preparation unit 1 during the emulsion formation step, however, the emulsion must be treated in the settling unit 2 before being fed into the mixing unit 3 according to arrow c. Evacuation is also required if the starting clay or clay mineral is, for example, Na-bentonite + zeolite + quartz. In this case, the settling unit may consist of a flow-through trough settling system, which operates on the principle of gravity; It can be up to 1 m / min, and the system is called a. has a lower quartz trimmer which makes the emulsion quartz free. Depending on the degree of contamination, the settling time is 4-6 hours, preferably about 5 hours.

In the mixing unit 3, feed supplement components are fed according to the direction of arrow c, e.g. It is mixed with a bentonite emulsion having a moisture content of 30-50% to a homogeneous pulp. The mixture - premix - is removed from the mixing unit 3 according to arrow e and can be used either in this wet state or, if desired, dried, e.g. We can be marketed.

If not only a premix, but for example a feed to be fed directly to the feed using a premix, are to be prepared, the coarse feed components are fed into the wet mill unit 4 according to arrow n and the bentonite emulsion from feed mixer 3 is fed into the wet mill unit 4. wherein these components are thoroughly mixed. This mixture is then used either directly for feeding (arrow o) or fed to the centrifugal filter and grinding unit 5 according to arrow h before being fed (arrow z). It is intended to indicate with the arrow m leaving the preparation unit 1 and the arrow m 'leaving the settler 2 that the bentonite processed into the fine emulsion by the process according to the invention can be used alone, i.e. without mixing with feed supplement components. In dried form, e.g. very suitable for borderline applications or as carriers for premixes or compound feeds.

Figure 2 is a block diagram of a liquid fertilizer stabilization process according to the invention. In the preparation unit 1 and, if necessary, in the settling unit 2, the bentonite emulsion is prepared in the same manner as described in Figure 1, which in this case is fed into the reactor 6 containing liquid fertilizer according to arrows k and j respectively, where the components are thoroughly mixed. The material thus stabilized can be removed in the direction of the arrow and transported to its destination. When the bentonite emulsion is removed from the preparation unit 1 and the settling unit 2, respectively, from the settling unit 2 and m 2, it can be used for other purposes (for example, after drying after drying or as a carrier for premixes or compound feeds in dried form).

The invention will now be described in more detail by way of examples.

/. example

A premix for calf feed is prepared by the process of the invention. The starting material used is Ca-bentonite, which has been subjected to rough mechanical crushing

HU 204176 Β of water, and the resulting slurry is stretched and kneaded twice during continuous agitation and filtered twice. Meanwhile, the Ca-bentonite is activated by the addition of soda and the material is sedimented. The emulsion obtained had a moisture content of 40% and a grain size of 80 microns. This emulsion is admixed with 20% by weight of the mineral content of the emulsion based on the dry matter content of the emulsion, taking into account the mineral requirement of the calves. The mineral content of the finished calf feed expressed as a percentage is 10:

ca 0.7% P 0.5% So 0.15% K 0.5% mg 0.15% Co 0.1 ppm Cu 10 ppm Fe 35 ppm S 0.2 ppm Mn 50 ppm Neither 0.1 ppm Zn 50 ppm

The resulting premix, in its liquid state, is added to the other components of the 25 feed and the mixture is fed to the calves.

Example 2

The bentonite emulsion 30 was prepared as in Example 1, from which the water was removed by centrifugation and drying, and the 80 micron fine bentonite powder was mixed with the mineral mixture of Example 1 and the final product was marketed in bags. 35

Example 3

A pig feed premix is prepared by the process of the invention. The starting material used is sodium bentonyl, which after mechanical pre-grinding is mixed with water, the slurry obtained is kneaded and kneaded under high pressure and filtered through sieves several times. The resulting emulsion has a bentonite particle size of 80 microns. To the 45% water emulsion is added 20% by weight of the mineral mixture based on its dry matter content, expressed as a percentage of the total dry matter content of the feed:

ca 11.36% P 4.57% Reed 8.0% Zn 6.652 ppm Mn 1.326 ppm Fe 2.652 ppm

The premix prepared as described above is mixed in a wet state pig feed and the mixture is fed to the animals.

Example 4

In all of the same procedure as in Example 3, 60 of the premix were removed by plowing to remove moisture and the following vitamins were added to the flour-like bentonite powder:

408,000 NE at 26 ppm

800 NE 82 ppm 34 ppm

680 ppm

Vitamin Bj Vitamin D Vitamin B ₃ , Vitamin B ₆ Vitamin Tylan

Example 5

For ruminants, a feed supplement is prepared by the process of the invention. In this case, too, the slurry formed from the mechanically pre-milled sodium bentonite by water is kneaded kneading and pressed through filters, but only to the extent that the bentonite particles in the emulsion are 1-2 mm in size. The emulsion, containing 30% water, was mixed with 5% by weight of lacquer lime, 5% by weight of zinc oxide and 10.0% by weight of dry matter and 10% by weight of molasses and lecithin and homogenized by mixing. The homogenized emulsion is mixed with 40-50% by weight of ground cereal carrier (grain meal) and this final product is added to the animal feed. When the emulsion carrier mixture is dried, a urea concentrate with mineral material is obtained, which can be marketed, for example, in sacks.

Example 6

For ruminants, a zinc replacement premix is prepared by the process of the invention. A bentonite emulsion was prepared as described in Example 5, with the same amount of wet zinc oxide being added to the preparation unit. The combination, as described in previous examples, results in hydromechanical grinding filtration to produce a zinc-substituted premix emulsion. Where such a premix is required at the place of production or in its immediate vicinity, it shall be fed to the animals in the form of such an emulsion; however, if the premix needs to be transported further, the emulsion may be desiccated and transported from the consignment.

Example 7

Liquid nitrogen phosphorus potassium fertilizer is stabilized by the process of the invention. In the same manner as in Example 1, a bentonyl emulsion was prepared from Ca-bentonite as a starting material having a water content of 40% and a solid phase particle size of 80 microns. This emulsion is mixed with 3% by weight of the fertilizer solution to form a liquid fertilizer to stabilize it. The components in the stabilized solution do not settle.

Example 8

Rivers produced in liquid fertilizer production plants are disposed of in the process according to the invention. Liquid fertilizer4

In fact, the production of a solution results in a 7: 10% solution of nilogen-potassium phosphorus in a ratio of 2: 1: 1 which is in a physical state that cannot be replaced in the fertilizer reactor.

When the bentonite emulsion prepared in Example 1 is mixed with such a solution (in a ratio of 0.5 to 3% by weight, depending on the concentration of the solution), a chemical reaction is carried out in which nitrogen, potassium and phosphorus are bound to recyclable.

An advantage of the present invention is that it allows the production of clay minerals with a maximum specific surface area with minimal energy input. Increasing the specific surface area is advantageous in all functional aspects: improved homogeneity of mineral distribution, easier absorption in animals, increased effectiveness of solution stabilization. It is very important from the point of view of energy saving that drying of the emulsion is not necessarily required for the preparation of premixes or compound feeds, but it can also be used as such, especially in livestock farms which are otherwise not too expensive to produce clay mineral emulsions.

Of course, the invention is not limited to the embodiments detailed above, but may be practiced in many ways within the scope of the claims.

Claims (11)

A process for increasing the specific surface area of clay minerals and / or clay minerals, in particular bentonite, characterized in that slurry is made by adding water to the slurry, which is kneaded at a pressure greater than 101 325 Pa and passed through one or more filters, thereby forming an emulsion containing a fine-grained clay mineral phase. Method according to claim 1, characterized in that the slurry is pressed through at least two successive filters of decreasing aperture size in the direction of movement of the slurry. 3. A process according to claim 1 or 2, characterized in that the slurry is prepared by mixing the clay mineral which has been minced in the wet state with water. 4. A method according to any one of claims 1 to 4, characterized in that the slurry is conveyed in a closed space by kneading it by means of a worm shaft. 5. A process according to any one of claims 1 to 4, characterized in that the slurry is made of clay minerals containing more than 50% montmorillonite. 6. A process for stabilizing a premix and / or feed mixture or solution for animal feed, preferably a liquid fertilizer, characterized in that slurry is made from clay or / and rocks containing clay, preferably bentonite, at a pressure greater than and passing through one or up to four filters during transfer, and then containing the resulting emulsion or feed additive or feed additives in an amount of 90-50% by weight, preferably with mineral and / or feed components containing micro- and / or macro-nutrients. or mixed with a solution, preferably a liquid fertilizer, in an amount of 0.53.0% by weight, thereby stabilizing the solution. Method according to claim 6, characterized in that the slurry is pressed through at least two successive filters of decreasing aperture size in the direction of movement of the slurry. A process according to claim 6 or 7, characterized in that the slurry is prepared by mixing the clay minerals previously minced in the wet state with water. 9. A 6-8. A method according to any one of claims 1 to 5, characterized in that the slurry is conveyed in a closed space by kneading it by means of a worm shaft. 10. A 6-9. A process according to any one of the preceding claims, characterized in that the slurry is made of clay minerals containing more than 50% of montmorillonite. 11. A process according to any one of claims 1 to 3, characterized in that the premix or / and feed mixture is prepared by mixing a clay emulsion and a mineral containing micro and / or macro elements in a ratio of 5: 1 to 2: 1, preferably about 4: 1.