HU175588B - Process for preparing stable cu/ii/sulphate-monohydrate as a micronutrient additive for feeds - Google Patents

Description

Procedure for the preparation of stable copper / H / sulphate monohydrate as feed trace element> 1

FIELD OF THE INVENTION The present invention relates to a process for the preparation of copper (II) sulfur mxmohydrate which can be used as a trace element in animal feeds, which is essentially trem hygroscopic, easy to grind and finely ground. neutralized with ammonium hydroxide, carbonate, or bicarbonate, and the crystalline water of the molecule is removed by drying at -0 ° C to 150 ° C for at least one minute.

It is known that the importance of micronutrients in animal husbandry and animal nutrition is growing, since the animal body needs these in addition to the nutrients that provide the energy for the smooth functioning of food and tissues.

Such essential micronutrients include, but are not limited to, copper, which is primarily involved in the formation of 'hemoglobin' in the animal body, but plays an important role in the function of certain 'enzymes such as uricase, ctechromoxidase and polyphylaxis oxidase. in the development of nerve tissue, in the coloring of hair and fleece, and in the protection of the wall of the large veins.

The animal behavior of animals depends on many factors, such as the direction of production, the animal's species, age, health and genetic characteristics, and moreover the protein and energy content of the feed. Copper compounds are not marketed with the same efficiency in the animal body; copper sulphate has proven to be the most favorable in this respect.

Copper sulfate is the most important copper salt for industrial purposes. Simple technology for large-scale industrial applications is known only for the production of copper sulphate pentahydrate, but this salt is not preferably used for the trace element addition of feed. The reason for this is that it has a relatively high water content of crystalline water and also contains free sulfuric acid, which damages certain components of the feed, such as unsaturated vegetable and animal oils and fats, and vitamins.

Copper (II) sulfate monohydrate is prepared from saturated copper sulfate solutions or dehydration of solid pentahydrate by methods known in the art for the preparation of copper sulfate monohydrate. The most common procedures are:

(a) The process of Grün and Bockisch (Bér. 41, 3465 (1908)) is the process of thermally decomposing diglycol copper sulfate [CuSO ₄ · 2C ₂ H ₄ (OH) ₂ · 2H ₂ O] into copper sulfate monohydrate at 125 ° C.

b) According to Gmelin's manual (Gmelin's Handbuch Dairy Anorganischen Chemie, Band 60, Teil B, Lief. 1, 1958, p. 576), copper sulfate monohydrate can be prepared by treating saturated copper sulfate solutions with concentrated sulfuric acid or oleum. Depending on the concentration of sulfuric acid in the ternary system, copper sulfate pentahydrate, copper sulfate trihydrate, copper sulfate monohydrate, and anhydrous copper sulfate may be formed as solid products. The disadvantage of this method is that the desulphurization of the monohydrate obtained can be carried out only with absolute methanol or ethanol to a sufficient extent, which significantly increases the cost of production.

c) According to another method, the saturated copper sulfate solution is boiled and the temperature of the thickening and subsequently solidifying mass is gradually raised to 120 ° C (Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. I, 1953, p. 24), as a result of which the substance is gradually converted to the monohydrate. The composition of the solid product thus formed corresponds to the stoichiometric formula of CuSO / ·, H2O. The disadvantage of this method is that the solid product is difficult to remove from the evaporator. Therefore, in more modern plants, the saturated copper sulphate solution is converted to the monohydrate by spraying with air at 120 ° C. The product thus obtained is extremely finely divided, but the process is very expensive.

d) According to Liptay (Atlas of Thermoanalytical Curves, Vol. 4, Akadémiai Kiadó, Budapest, 1954, pp. 474-7), when copper sulfate pentahydrate is heated, partial dehydration of the pentahydrate begins at 90 ° C and for a longer time at 120 ° C. below 150 ° C, 4 moles of crystalline water are discharged in less time. Fifth water breaking starts only at temperatures around 200 ° C and ends at 230-250 ° C. Both tray and tumble drier as well as fluidized-air dryer (120 ° C) are suitable for this purpose. The copper sulphate solution always contains free sulfuric acid; the disadvantage of this process is that the water-copper sulphate-sulfuric acid system formed during drying is extremely corrosive, which requires the drying equipment to be made of expensive materials which are resistant to corrosion. A further disadvantage of the method is that the resulting product is hygroscopic.

e) Flame and Stattler's method [Z. phys. Chem. A., 179, 427 (1937)] comprises treating anhydrous copper sulfate with 1.2 to 1.4 moles of water per mole and converting the various hydrates thus formed to a monohydrate at 117-118 ° C. The process is not suitable for large-scale commercialization because the production of the starting material entails significant additional costs.

f) Elicur [Zsurn. Prikl. male. 14, 682 (1941)] used calcium hydride (CaH2) to dehydrate copper sulphate pentahydrate in the presence of absolute ethanol at 196 ° C. In the process, monohydrate is formed during the evolution of hydrogen gas. The process is of theoretical importance only and is unsuitable for industrial implementation.

(g) Svesnikov and Koleva [Zavodskaya Laboratory. 9, 357 (1940)] used calcium acetylide (CaC2) to partially dehydrate copper sulphate pentahydrate. In the process, acetylene gas is evolved and a mixture of mono- and trihydrate is formed.

h) Rakusin and Brodski [Z. Angew. Chem. 40, 110 (1927)] utilizes absolute ethanol to dehydrate copper sulphate pentahydrate. The process is not industrially feasible due to expensive ethanol. A further disadvantage is that ethanol can only dehydrate until it is diluted to 96%.

i) Tate and Warren (Trans Faraday Soc. 35, 1192 (1939)) convert copper sulfate pentahydrate to a monohydrate with organic solvents such as benzene, cyclohexanone and light gasoline. For benzene, pentahydrate is distilled at 80 'C for 3 hours and for cyclohexanone at 80 ° C for 5 hours.

j) Bidwell and Sterling, Ind. Eng. Chem. 17, 147 (1925)] converts pentahydrate to monohydrate by distillation with hot toluene and xylene.

k) The conversion of pentahydrate into monohydrate by the method of Bergmann (German Patent No. 595,128) can also be accomplished by the use of acetals, ketals, and ethylene glycol ether and its homologs boiling above 100 ° C.

Based on a review of the state of the art, none of the known processes is suitable for the low-cost large-scale production of copper sulfate monohydrate.

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the drawbacks of the prior art by providing a process for the preparation of copper sulfate monohydrate as a trace element additive in animal feed, even in a large scale commercial application.

The invention is based on the discovery that when copper (II) sulfate pentahydrate is melted in its crystalline water, it is treated not only with the amount of alkaline material required to neutralize its free sulfuric acid but also with at least 3% more copper (II) sulfate pentahydrate and the resulting mixture is dried to give copper (II) sulfate monohydrate, which is substantially non-hygroscopic, even when finely ground, and is thus useful as a trace element in animal feeds. This finding is surprising because, in the prior art, it was not expected that increasing the amount of alkaline component used to neutralize the free sulfuric acid content would lead to a stabilized product.

Accordingly, the present invention provides a process for the preparation of Thesilyl Sulfate Monohydrate, which is practically non-hygroscopic, easy to grind and finely ground as a trace element additive in animal feed, wherein the free sulfuric acid content of copper (II) sulfate pentahydrate is sodium, neutralized with ammonium hydroxide, carbonate or bicarbonate (hereinafter referred to as "alkaline component") and the crystalline water of 4 molecules is removed by drying at 80 to 150 for at least 30 minutes. According to the present invention, the copper (II) sulfate pentahydrate is melted in its crystalline water, in excess of the stoichiometric amount required to neutralize the free sulfuric acid content, calculated as sodium carbonate and, relative to the copper (II) sulfate pentahydrate, It is treated with an alkaline component in an amount of 20% by weight, preferably 5-8% by weight.

In accordance with the present invention, it is convenient to add the copper sulphate pentahydrate to be converted into the monohydrate into a rotary dryer and to add 5 to 7% by weight of calcined soda in addition to the amount required to neutralize its free sulfuric acid content. After briefly stirring, the temperature of the salt mixture is gradually raised to 110-118 ° C and maintained at this temperature for approximately two hours. After cooling, the granular material thus obtained is ground in a hammer mill to the desired fineness.

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

(a) It allows the direct industrial production of stabilized copper sulphate monohydrate from copper (II) sulphate pentahydrate, a cheap raw material. The product obtained is easy to grind and is stable in finely ground condition.

b) The production reaction and drying are extremely fast.

c) As a large-scale technology it can be implemented easily and cheaply.

(d) The product obtained, without any further transformation or purification, is best used as a trace salt for feed additives because it is physically stable, does not lump and is thus easily incorporated into the feed.

In order to carry out the process of the invention, the following embodiments are provided.

Example 1

950 kg of copper sulfate pentahydrate with a free sulfuric acid content of 0.24% is added to a rotary drum with a roller cylinder. Neutralization of the latter requires 2.5 kg of sodium carbonate. In addition, the alkaline component is used in an amount of 8% by weight, based on copper copper, which corresponds to 76 kg of sodium carbonate. Thus, a total of 78.5 kg of calcined soda is added.

After stirring for 1 minute, the temperature of the salt mixture is gradually raised to 110-118 ° C and maintained at this temperature for 80 minutes. The salt mixture melts for 20-30 minutes and then granulates as the water content decreases. After cooling, the resulting granular material is ground in a hammer mill to the desired fineness.

The resulting 607 kg (97%) stabilized copper sulfate monohydrate has a copper content of 32-33% and no free acid content.

The counterexample to Example 1

All were carried out as in Example 1, but only the free sulfuric acid content of the cupric acid was neutralized with 2.5 kg of calcined soda. During drying, the salt mixture does not granulate, but gradually decomposes into a fine powder. As a result, the drying efficiency is greatly reduced, the dust loss is greatly increased, resulting in economic, technological and occupational health problems. In addition, the product is highly hygroscopic and thus precludes the preparation of a precise feed premix.

Tray dryers can be used to reduce dust loss, which, in turn, requires a lot of live work and thus further reduces the economics of the process.

Example 2

In the drying apparatus of Example 1, 950 kg of copper sulfur having a free sulfuric acid content of 0.245% was added. To neutralize this acid content, 3.3 kg of potassium carbonate are required. In addition, the alkaline component is used in an amount of 10% by weight relative to copper copper, equivalent to 95 kg of sodium carbonate. The latter is equivalent to 124 kg of potassium carbonate. Thus, a total of 127.3 kg of potassium carbonate is added to the copper gauze.

The salt mixture was heated to 130-138 ° C for 45 minutes as described in Example 1 and then ground to the desired particle size. The resultant 731 kg (95%) of stabilized copper sulfate monohydrate has a copper content of 30-31% and no free acid content.

Example 3

In the drying apparatus of Example 1, 950 kg of copper phosphorus with a free sulfuric acid content of 0.65% was added. Neutralization of the latter requires 5.3 kg of sodium bicarbonate. In addition, the alkaline component is used in an amount of 5% by weight, i.e. 47.5 kg of sodium carbonate. The latter is equivalent to 37.6 kg of sodium bicarbonate. Thus, a total of 42.9 sodium bicarbonate is added to the copper gallium. The salt mixture was granulated and ground as described in Example 1. The resultant 675 kg (97%) of the stabilized copper sulphate monohydrate has a copper content of 33.5 to 34.5% and no free acid content.

Example 4

In the drying apparatus of Example 1, 950 kg of copper sulfur having a free sulfuric acid content of 0.245% was added. To neutralize this acid content, a solution of 6.7 kg by weight of ammonium hydroxide is required. In addition, the alkaline component is used in an amount of 18% by weight, corresponding to 171 kg of sodium carbonate, with respect to copper mica. The latter is equivalent to 452 kg of a 25% w / w solution of ammonium hydroxide. Thus, a total of 458.7 kg of a 25% w / w solution of ammonium hydroxide is added to the copper algae.

λ. *

The salt mixture was heated to 110-118 ° C for 2 hours as described in Example 1 and then ground to the desired particle size. The thus obtained 668 kg (96%) of stabilized copper sulphate monohydrate had a copper content of 33.5 to 34.5% by weight and had no free acid content.

Example 5

In the drying apparatus of Example 1, 950 kg of copper sulfur having a free sulfuric acid content of 0.65% was added. To neutralize this acid content, 12.6 kg of 40% w / w sodium hydroxide solution is required. In addition, the alkaline component is used in an amount of 3.5% by weight, based on copper copper, equivalent to 33.3 kg of sodium carbonate. 62.8 kg of 40% w / w sodium hydroxide solution is equivalent to the latter, so a total of 75.4 kg of 40% w / w sodium hydroxide solution is added to the copper gauze.

The salt mixture was granulated and ground as described in Example 1. The resultant 679 kg (97%) of stabilized copper sulphate monohydrate had a copper content of 33.5 to 34.5% and no free acid content.

Example 6

In the drying apparatus of Example 1, 950 kg of copper gypsum having a free sulfuric acid content of 1.2% was added. To neutralize this acid content, 13.3 kg of ammonium carbonate monohydrate are required. In addition, the alkaline component is used in an amount of 7% by weight relative to copper copper, corresponding to 66.5 kg of sodium carbonate. The latter is equivalent to 72 kg of ammonium carbonate monohydrate. so in total

85.3 kg of ammonium carbonate monohydrate are added to the copper gallium.

The salt mixture was granulated and ground as described in Example 1. The resulting 699 kg (97%) stabilized copper sulphate monohydrate has a copper content of 32.5-33.5% today and has no free acid content.

Claims (1)

A process for the preparation of copper (II) sulfate monohydrate as a trace element additive in animal feed, which is non-hygroscopic, easily ground and finely ground. 20, the free sulfuric acid content of copper (II) sulfate pentahydrate, sodium, potassium or ammonium hydroxide, carbonate or bicarbonate (hereinafter referred to as "alkaline component") is neutralized and at least 4 molecules of crystalline water are neutralized. It is removed by drying for 30 minutes at 80 ° C to 150 ° C, characterized in that the copper (II) sulfate pentahydrate is melted in its own crystalline water, in excess of the stoichiometric amount needed to neutralize its free sulfuric acid content and copper With respect to (II) sulfate pentahydrate, it is treated with an alkaline component in an amount of from 3 to 20% by weight, preferably from 5 to 8% by weight.