HU181210B - Process for preparing chemically homogenous mineral feed additives - Google Patents

Abstract

Mineral fodder additives are prepared by a process wherein: a) (1) zinc and/or copper are separated as (basic) carbonates from a zinc ammine complex and/or copper ammine complex solution by heat treatment and (2) the manganese is precipitated as manganese carbonate on the obtained carbonate (mixture) from a manganese sulfate solution by the introduction of carbon dioxide and ammonia, or steps (1) and (2) are carried out in reversed sequence, and optionally before or between the precipitations a carrier is added, then the solid phase is separated and added to an aqueous solution containing iron (II) ions, or b) (3) from an aqueous solution containing iron (II) ions iron carbonate is precipitated by adding ammonium carbonate, optionally in the presence of a carrier, zinc and/or copper carbonate and manganese carbonate, respectively, are precipitated on the iron carbonate according to steps (1) and (2) or (2) and (1), hereupon the carbonates are optionally dissolved in the suspensions obtained according to variants a) or b) by adding sulphuric acid, optionally selenite and iodide are added and the mixture is dried. As starting substances by-products and wastes of the metallurgical industry can be used.

Description

The present invention relates to a process for the preparation of a homogeneous mineral feed supplement. These feed supplements are primarily intended to provide the necessary amount of trace elements in animal feed. According to the invention, the feed supplements are prepared by processing waste materials, first of all metallurgical waste materials,

It is known that feeds and compound feeds used in animal husbandry contain certain or inadequate amounts of biologically important minerals (trace elements) and trace elements should therefore be added. The incorporation and homogenisation of small amounts of the desired mineral are important technological steps and maintaining the homogeneity achieved is not an easy task.

Until now, these mineral admixtures have generally been prepared by mechanical mixing of salts of different chemical compositions. Some micronutrients (Mn, Cu, Zn, Co, Se, Mo, J, Fe, etc.) can be laboriously mixed only after successive dosing and after each addition by separate homogenization. Often there is a risk of subsequent separation because of the different grain size and species weight of the different metal salts. This problem applies not only to mineral mixtures used as feed supplements but also to micronutrient mixtures used in other applications (eg fertilizers). 30

No. 845,313. According to a process known from French patent no., homogeneous salts are formed from trace elements by the addition of phosphoric acid and ground limestone in one step. However, this process has the disadvantage of starting from relatively pure materials; so e.g. the starting materials must not contain harmful heavy metals (Pb, Sn, As, etc.). It is also a disadvantage that the use of metal phosphates is relatively poor in monogastric animals.

It is an object of the present invention to provide a process for the production of a completely homogeneous mineral feed supplement for animal feed which is not homogeneous subsequently. It is another object of the present invention to utilize metallurgy by-products and wastes as well as low-value manganese ores for the production of feed supplements.

Accordingly, the present invention relates to a process for the preparation of a homogeneous mineral feed supplement comprising:

(a) (1) precipitating the zinc and / or copper from a solution of zinc-amine and / or copper-amine complexes obtained by extraction with zinc and / or copper waste with ammonia and carbon dioxide in the form of basic carbonate and (2) the carbonate or carbonate mixture obtained is liberated from manganese sulfate solution containing 20-110 g / l, preferably 80-100 g / l manganese, by introducing carbon dioxide and ammonia, or (1) and

-1181210 (2) is carried out in an inverted order, optionally before or during the precipitation, a carrier, preferably limestone powder, is added and the solid phase is separated from the solution and 50-150 g / l, preferably 80-100 g / l iron II) -ion containing an aqueous solution, or

b) (3) separating iron carbonate from an aqueous solution containing iron (II) ions, optionally in the presence of a carrier, preferably limestone flour, to the resulting carbonate or carbonate compound of (1) and (2) or (2) and (2); The zinc and / or copper carbonate and manganese carbonate are precipitated according to steps 1) and the carbonates are optionally dissolved in sulfuric acid in the carbonate suspensions obtained in a) or b), optionally selenium is added to the resulting mixture or solution. and iodide is added and the product is dried to a moisture content of up to 10%, preferably 1%.

Preferred starting materials for the process according to the invention are by-products and wastes from metallurgy and manganese ores. Extraction of zinc and copper scrap with aqueous solution containing carbon dioxide and ammonia yields high purity amine complex solutions. The required manganese sulfate solution can be obtained by the digestion of low-grade manganese ores with sulfuric acid and used as a solution containing iron (II) ions in the pickling of iron plates.

The individual components are precipitated homogeneously. When working according to variant (a), in each case according to the order of steps (1) and (2), the basic copper carbonate and / or zinc carbonate for manganese carbonate, or in the presence of a carrier, or vice versa let's beat it. Ground limestone is the most suitable for each substrate. however, other mineral carriers or organic carriers, e.g. bran may also be used. The solid phase of the resulting slurry is separated from the solution using a suitable apparatus (e.g., a filter). The filter cake is then suspended in a solution containing ferric ions.

When working according to variant b), the iron carbonate is first precipitated, optionally in the presence of a solid support. Thereafter, steps (1) and (2) are carried out in any order, i.e., zinc and / or copper carbonate and manganese carbonate are precipitated onto the iron carbonate in the presence of a support.

In variants a) and b), the resulting suspension is optionally mixed with selenite and iodide as further trace elements. The selenite is preferably aqueous sodium selenite and the iodide is also used in the form of its water-soluble salts

If the aim is to produce a homogeneous soluble salt mixture, no carrier is added and the carbonates formed during precipitation are dissolved in sulfuric acid. In this case, the acidity of the brine solution containing iron (II) ions should be utilized. When suspended in the brine solution, the carbonates are generally dissolved, and at most the brine solution must be concentrated by adding a little sulfuric acid. The resulting solution is then dried at a temperature of up to 250 ° C in a spray dryer. In the resulting salt mixture, the sulfates are present as monohydrates.

If the carbonates do not have to be dissolved [according to variant (a) (1) and (2)), the solution containing iron (II) ions may be used, but the sulfuric acid content must be suitably neutralized beforehand by addition of iron shavings. The mixture containing insoluble carbonates is dried by spray drying rather than by spray drying. The carbonates can be separated by filtration before drying; however, when soluble selenite and iodide compounds are added to the suspension, the whole slurry is dried together.

The main advantages of the process according to the invention are as follows:

Unlike prior art mineral feed supplements, the product obtained by the process of the present invention is not prone to separation. thus its composition remains constant;

- the process is suitable for the processing of waste from the metallurgical and chemical industries and the heavy metals (Pb, Sn, etc.) which are harmful to the living organism remain undissolved. The purified solutions prepared may be used directly in the preparation of the product;

- the trace elements (Zn, Cu, Mn, Fe, etc.) can be applied to the inert support in carbonate or sulfate form. This facilitates the utilization of the animal digestive process;

- according to the invention, the proportion of trace elements can be arbitrarily adjusted and thus adapted to the particular requirements,

The following examples illustrate the process of the present invention in more detail.

Example 1 Direct steam was added to a solution of copper amine complex containing 110 g / l copper (Cu) until 3.4 g of copper (Cu) corresponding to copper (Cu) were precipitated from the solution, and the basic copper carbonate was then filtered off. 687 ml of zinc-amine complex solution containing 120 g / l of zinc (Zn) were added directly to the solid solution while stirring until 41 g of zinc carbonate (ZnCO3) was precipitated. The precipitate containing copper and zinc carbonate was filtered off. The filter cake was placed in a solution of 512.5 ml of manganese sulphate containing 80 g / l manganese (Mn), while stirring, ammonia and carbon dioxide were added to a solution containing solids (copper carbonate + zinc carbonate), until 41 g of manganese carbonate corresponding to manganese (Mn) are precipitated. The mixture of carbonates is separated from the solution by filtration. The cake was mixed in a solution of iron sulfate containing 142 g / l iron (Fe), obtained by the final neutralization of acidic pickle with iron shavings, and the slurry was dried at 100 ° C to a moisture content of 1% to give 248 g of Mn: Zn: Fe: Cu - 1: 1: 0.344: 0.0835

A carrier-free salt mixture of -2181210, preferably 40.2% total trace elements, is preferably used for poultry feed.

Example 2

The salt mixture was prepared as described in Example 1 except that the filter cake containing copper and zinc carbonate was combined with 750 g of calcium carbonate in 1025 ml of 40 g / l manganese (Mn) manganese sulfate solution and until then ammonia and carbon dioxide were introduced into a solution containing solids (copper carbonate + + zinc carbonate + calcium carbonate). until 41 g of manganese carbonate equivalent to manganese (Mn) are produced. The carbonate mixture was separated from the solution by filtration. The filter cake was stirred in 142 ml of iron sulfate solution containing 100 g of iron (Fe), and the slurry was dried in a fluidization apparatus at 100 ° C to 1% moisture. 998 g of a salt mixture containing Mn: Zn: Fe: Cu = 1: 1: 0.344: 0.0835, preferably 10% of total trace elements and containing calcium carbonate, are preferably used in poultry feed.

Example 3

Direct steam was introduced into 378 ml of a 110 g / l copper-amine complex solution until 18.9 g of copper (Cu) -basic copper carbonate Cu (OH) ₂ CuCO _{3 was} exchanged, followed by the basic copper -carbonate was isolated by filtration. The filter cake was placed in a solution containing zinc amminkomplex 955 ml 120 g of zinc (Zn), and direct steam is introduced into a solution containing 57.3 g of zinc precipitate is a suitable zinc carbonate (ZnC0 ₃₎ with stirring to precipitate. Copper and zinc carbonate were separated from the solution by filtration. The filter cake was placed in 300 ml of manganese sulphate solution containing 80 g / l manganese (Mn) and with stirring was introduced into a solution containing ammonia and carbon dioxide solids (copper carbonate + zinc carbonate) until 24 g of manganese corresponding to manganese carbonate (MnC0 ₃₎ causes. The carbonate mixture was separated from the solution by filtration and dried at 100 ° C to a moisture content of 1%. Thus, 193 g of Mn: Zn: Cu = 1: 2.413: 0.796, carrier-free, preferably for pig feed. 52.1% total salt mixtures containing trace elements were obtained.

Example 4

The preparation of the salt mixture is as described in Example 1, except that the filter cake containing copper and zinc carbonate is introduced into 808 g of calcium carbonate in a solution of manganese native wood containing 1188 ml of 20 g / l manganese (Mn) and stirring. ammonia was added to a solution of carbon dioxide in solids (copper, zinc, calcium carbonate) until 23.7 g of manganese carbonate corresponding to manganese were precipitated. The carbonate mixture was separated from the solution by filtration. The filter cake was dried at 100 ° C to 1% moisture. This gave a salt mixture of 1005 g of Mn: Zn: Cu = 1: 2.413: 0.796, preferably containing 10% total trace elements and calcium carbonate in pig feed.

EXAMPLE 5 Direct steam was introduced into a solution of copper amine complex containing 110 g / l of copper (Cu) until 0.6 g of basic copper carbonate Cu (OH) ₂ CuCO _{3 was} precipitated from the solution. The basic copper carbonate was then separated from the solution by filtration. The filter cake was placed in a solution containing zinc amminkomplex 500 ml 120 g of zinc (Zn), and steam is directly introduced with stirring to a solution of the solid in a suitable 30 g zinc as zinc carbonate (ZnC0 ₃₎ precipitate. The precipitate containing copper and zinc carbonate was separated from the solution by filtration. The filter cake was placed in 750 ml of 80 g / l manganese (Mn) manganese sulphate solution and, while stirring, was introduced into a solution containing ammonia and carbon dioxide (60 g of manganese corresponding to manganese). carbonate. The carbonate mixture was separated from the solution by filtration. The filter cake was stirred in 96 ml of iron sulfate solution containing 100 g of iron (Fe) and the slurry was dried at 10 ° C to 1% moisture. thus obtained a salt mixture having a ratio of Mn: Zn: Fe: Cu = 1: 0.5: 0.16: 0.01, preferably 40.8% of the total trace element used in cattle feed,

Example 6

The salt mixture was prepared as in Example 5, except that the filter cake containing copper and zinc carbonate was combined with 750 g of calcium carbonate in 1497 ml of a 40 g / l manganese (Mn) solution of manganese sulfate and stirring. ammonia and carbon dioxide were introduced into solutions containing solids (copper, zinc, and calcium carbonate) until 60 g of manganese carbonate equivalent to manganese were released. The carbonate mixture was separated from the solution by filtration. The filter cake was mixed with 96 ml of iron sulfate solution containing 100 g of iron (Fe) and dried at 100 ° C to 1% humidity. A salt mixture of 995 g, Mn: Zn: Fe: Cu = 1 = 0.5: 0.16: 0.01, preferably 10% total trace elements and calcium carbonate carrier, is used for bovine tc steering.

Example 7

6.5 kg of calcium carbonate (100-500 μm particle size) were suspended in 10 liters of manganese sulfate solution containing 40 g / l manganese. Until then, ammonia and carbon dioxide were introduced into the suspension,

-3181210 until 400 g of manganese carbonate corresponding to manganese are replaced on the support material. To the suspension were added 350 ml of copper amine complex solution (100 g / l copper content) and 380 ml of zinc amine complex solution (110 g / l zinc content). At 85-90 ° C, 5 vapors were directly introduced until basic copper carbonate for hanging copper and 200 g for zinc carbonate were precipitated. The carbonate mixture was filtered and mixed with 1 liter of an aqueous solution of 102.4 g iron (II) ion (280 g / l 10 FeSO ₄ ), 0.456 g elemental selenium (1 g / l sodium selenite) and 9.24 g elemental iodine. (11.5 g / l ethylene diamine dihydroiodide). The slurry was dried in a fluidized bed dryer to a moisture content of 1%,

Example 8

6.5 kg of calcium carbonate having a particle size of 100-500 μl was suspended in 3 liters of a filtered solution of 50 g / l iron (II) ions. The suspension was adjusted to pH 3 with tartaric acid and the iron precipitated by adding ammonium carbonate to the support as ferric carbonate. To the resulting slurry was added 10 liters of manganese sulfate solution containing 40 g / l manganese. Ammonia and carbon dioxide were added to the resulting suspension with stirring until 400 g of manganese carbonate corresponding to manganese were precipitated. Zinc and copper carbonate were precipitated on the suspended particles as described in Example 7. To the resulting carbonate slurry was added 9.24 g of ethylenediamine dihydroiodide corresponding to elemental iodine and 0.456 g of sodium selenite corresponding to elemental selenium. The slurry was then dried at 80 ° C in a fluidized bed dryer to a moisture content of 1%.

(a) (1) precipitating the zinc and / or copper (basic) carbonates from a solution of zinc-amine and / or copper-amine complexes obtained by extraction of zinc and / or copper waste with ammonia and / or copper amine complex and (2) ) precipitating the manganese as manganese carbonate from the manganese sulfate solution containing 20-110 g / l, preferably 90-100 g / l of manganese, by introducing carbon dioxide and ammonia into the carbonate or carbonate mixture obtained, or (1) and (2) carrying out the operations in an inverted order and optionally adding a carrier, preferably limestone meal, prior to or between the precipitation steps, separating the solid phase from the solution and adding it to an aqueous solution containing 50-150 g / l, preferably 80-100 g / l iron, or (b) precipitating iron carbonate from a solution of (3) iron (II) ions with ammonium carbonate optionally in the presence of a carrier, preferably limestone powder; zinc and copper carbonate or manganese carbonate are precipitated onto the carbonate according to steps (1) and (2) or (2) and (1) respectively, and then the suspension obtained in (a) and (b) is optionally dissolved by addition of sulfuric acid, optionally adding selenite and iodide to the resulting mixture or solution and drying the product to a moisture content of up to 10%, preferably 1%.

2. The process according to claim 1, wherein the solution containing iron (II) ions is sulfuric acid or neutralized marinated solution.

Patent claims: 3. The method of claim 1 or 2, wherein

Claims (1)

The method of claim ^{40 of} claim 1, wherein the manganese sulfate is selected from the group consisting of: A method of preparing homogeneous mineral feed supplement trees by recovering manganese ores from sulfuric acid, characterized in that data is used. Responsible for the release: Director of the Economic Publishing Company 84.4285 - Zrínyi Printing House, Budapest