CZ301099A3 - Process for preparing pourable additive in feeding stuff for animals based on methionine salt and granulation product obtained in such a manner - Google Patents

Abstract

The method of producing a free-flowing animal feed additive consists of: converting the methionate salt into a granulate. The granulate has a bulk density greater than 650 kg / m3; dust content less than 1%

Description

The present invention relates to a process for the production of a high feed additive for animals based on a salt of methionine and the granulate thus obtained

Technical field

BACKGROUND OF THE INVENTION The present invention relates to a process for the manufacture of a free-flowing, easy-to-handle animal feed additive based on methionine salt, which is prepared starting from a solution of methionine salt obtainable in conventional manner, a granular product as well as obtainable therewith. granulated broom products on i nu.

BACKGROUND OF THE INVENTION

Methionine, as well as aqueous solutions of methionine salts, in particular sodium methioninate (DE 31 05 009 0), but also substitutes such as methionine hydroxy analogues (MRA), are used throughout the world as an additive to oro animal feed, poultry, orasat and other livestock and are mainly beneficial for the production of animal proteins. Given the increasing number of people in the world and the related nutritional problems, the importance of methionine as one of the leading limiting amino acids in the animal growth process and its various forms, and hence its cost-effective production, is particularly important. Depending on the requirements, either solid or liquid forms are used.

The sodium methionine solution to be sold has a concentration of 40% by weight. methionine, and in the oro-2 example of MHA, with respect to its biological value, unknown methiorine, compared on an equimolar basis. Several methods are available for the production of such sodium methioninate solutions:

1. Dissolve isolated methionine in sodium hydroxide,

2. Alkaline hydrolysis of methylmerptoethyl / hydantoin HaOH and / or

3. Alkaline hydrolysis of methioninamic.

Though multiplying 1 provides the purest form of the product, it is more expensive and thus less economical than the production of methionine itself, as a result of the long working step compared to solid production. On the other hand, the processes 2 and 3 are used for earlier production and thus achieve, in terms of lightening capacity, part of the solids of the DL-methanone production.

The preparation of 5- (3-methylmethylammonium) -hytanethane is carried out in a known manner by direct synthesis from the usual starting materials methylmercaptopropionaldehyde (MMP) and hydrocyanic acid in the presence of ammonia and carbon dioxide. Methioninamide is produced in a known manner by the hydrolysis of methionine nitrile, which is again obtained by direct synthesis from the usual starting materials MMP, hydrocyanic acid or ammonium cyanide and ammonia.

Depending on special requirements, it may be expedient to use a solid or liquid form of animal feed additive.

• ·

The decision regarding fornp / administration depends, among other things, on mixing devices that are available or possibly on the user's special reference. In the manufacture of compound feed, various feeds are first submitted. additives as individual components which, depending on the quality, are pre-treated by, for example, grinding, pickling, drying or cleaning. If the individual components are of the necessary quality, the mixing process is carried out in a mixing device which is suitable for this. Methionine is an essential amino acid p ^r i suolementaci jouž'vá be mixed feeds in concentrations of the order of C, C 1 to 1.0% by weight. This amount is added by weighing and dosing systems ^{, from the} mo to the mixed feed.

IDE 31 05 009 discloses that aqueous sodium methioninate and potassium methioninate solutions have the same efficacy of methionine as solid methionine in their use as feed additive.

However, due to the stability of the methionine solutions in the study, which should be guaranteed by the supplier, it has hitherto been possible to supply only solutions containing up to 40 wt. methioninate. Accordingly, up to € 0% by weight of water is included in the product being sold, resulting in up to about 2.5 times the shipping cost compared to solid methionine transport. This has hitherto prevented the market introduction of methionine-based liquid additives.

The use of crystalline Na-methioninate does not occur

9 9 9

-4 due to the hygroscopic behavior of this compound.

However, it is highly desirable to have an animal feed additive that would meet the following requirements:

1. undoubtedly has the nutritional effect of solid, crystalline methionine,

2. It can be converted into the liquid form at the desired concentration by means of the feed mixer itself, without the need for alkali, for example.

j. during transport, it should be transported with as little dead volume as water so that the active substance content of the transported substance would be high,

4. the product can be adapted to special requirements or used as a solid.

In view of these problems, it is the task of the present invention to provide a way to solve these problems. It is also an object of the present invention to provide a novel improved solid methioninate solid product for animal feed.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention provides a process for the manufacture of a free-flowing additive for animal feed with which

4

444 ·

Methionine salt-based starting with an aqueous solution of methionine salt, which can be obtained by a conventional method, consists in converting the methionine salt solution into a granulate in one or more steps.

This process can be carried out continuously or discontinuously.

The solutions are generally 10 to 70% by weight, in particular levers 20 to 60% by weight, preferably 25 to 45% by weight, based on methionine.

In particular, sodium methioninate and / or potassium methioninate solutions are used, wherein the molar ratio of methionine to K or Na ions is preferably about 1.1 1 to 1: 1.1, preferably about 1: 1.

It has proven to be advantageous to include solutions to be sprayed and / or granulated in advance with activated carbon.

According to one embodiment, the solution of the methioninate salt is spray dried in a spray apparatus with a centrifugal sprayer, the temperature differences between the inlet temperature (120 to 200 ° C) and the outlet temperature (60 to 100 ^U C) being as large as possible. The powder thus obtained is then converted into a granulate. This is done by means of a granulating plate, a granulating drum or a mixer. Preferably, the granulate is produced in a high shear mixer (knife head insert) in an Eirich mixer.

generally, the spray-dried powder is granulated together with a preferably saturated solution of methionine salt in a mixer.

% Wt. from 1 to 0.01 to 1: 0.5, preferably from 1: 0.01 to 1: 0.5.

The powder obtained by spray drying generally has a bulk density of 350 to 350

500 kg / nP dust content of at least 1 to 5% / dust test according to Dr. Groscgopoa /.

The granulate has a bulk density of > 700 kg / m < 2 > and a distribution > 650 kg / m < 2 > with a grain size of 63-5000 / m, preferably 100-3000 / m, most preferably 100-1400 / m; $ has a grain size> 100 µm.

The fraction with a grain size of 63 Aim is at most about 2%, preferably 1%, the fraction of dust according to Dr. Groschoooa around Z1 X, preferably Z 1.5

Another variant of the preparation of the granulate according to the invention is the construction granulation in the fluidized bed. In this case, only one spraying step of the sodium methioninate solution and the construction of an animal feed additive granulate are carried out.

In this case, the corresponding fluidized bed reactor may have one or more grinding agitators for controlling the grain size.

Here again, saturated solutions of methioninate are preferably used, although less concentrated solutions may be used.

The weight gain in the fluidized bed is compensated for by the continuous discharge of the granulate despite stationary operation. In a targeted way, plowing is carried out

9 9 9 9 9

998 9 9 99

999997 99 9

9

9900 9 99 99

99

- The grain size required can carry through the drain tube, the granulate can pop through (the P * falls through the cooling zone through the discharge zone). The fine orach removed from the drying chamber together with the drying air separates and returns as solids to the solids. In the case of the production of the melt granules according to the invention, the temperature in the fluidized bed drying section is generally 100 to 200 ° C.

The temperature conduction as well as the possible use of one or more crushing tools in the fluidized bed determine the achievable particle sizes. Preferred granulates having a grain spectrum of between 63 and 5000 µm, preferably between 100 and 3000 µm, most preferably between 100 and 1400 µm, wherein the C% has a grain size of> 100 µm, are formed according to the invention when adding p. * ísad. The dryer must be sized with respect to the amount of air / air velocity so as not to precipitate the granulate, but also to remove fine dust starting from the desired lower grain size.

The granulate so produced preferably has a spherical shape and a bulk material weight of 650 kg / πΡ, preferably 700 kg / m 2, and a dust content of 1%, preferably 0.5 l / dust test according to Dr. Oroschoppa /

Other forming processes, such as extrusion, are also applicable to the production of the granulate of the invention. In this case, the device can be involved in a downstream process.

Thus, for example, it is possible to combine intense amounts

I 9 9 4) 9 9 9

9 9 9

9 9 9

999 999

-8chool with extruder and fluid bed dryer for both continuous and discontinuous processes.

To improve the handling of the granulates to be produced, it is recommended that the methioninate salt solutions be sprayed and granulated in the presence of silicate-based additives.

These include hydrophilic and hydrophobic silicas of a pyrogenic nature or produced by precipitation of 5 to 10 mCO2 / g, preferably spray-dried silica. Fine particle zeolites such as type A or bentonites are also useful.

These additives may either be suspended in the solution to be ruptured, or preferably dispensed into the apparatus in which the solution is to be ruptured and additionally granulated together with the air stream. The amount of other additives is 0.1 to 10% by weight. %, preferably 0.1 to 5% by weight, based on the granulated solid. These additives, in addition to the silicon compounds according to the nature, preferably substances (which are permissible in the field of animal feed), in particular fatty acids and their salts, preferably alkali metal or alkaline earth salts.

Fatty acids include, in particular, stearic acid and palmitic acid or mixtures of alkanecarboxylic acids with up to C C-θ.

-9 • 4 · 4 9 4 4 9 4 4 4444 44 4 4 494 4444 4 »• •• 4 4 · · 4 4

While ungranulated sodium methioninate forms lumps due to its hygroscopic behavior and loses its flowability, this phenomenon does not occur unexpectedly in the granulates of the invention.

They remain free-flowing and easy to handle, even in many atmospheric exposures, and have much better properties than a spray-dried powder in terms of a / satiety and ease of handling, b / reduced dust content, c / reduced tendency for clumping due to atmospheric effects d / higher embankment weight.

While the spray-dried product formed after 7 days of storage and ^y% relative villas bone swollen Chu lumps, granules of the invention remains free-flowing and can be easily handled therewith.

The method according to the invention can only be carried out on the basis of: the unexpected circumstance that neither metbioninate nor any of it entering theolts higher than 10 ° C does not decompose into the spray dryer or equivalent devices.

In fact, due to the known alkaline instability of these compounds, a decomposition was expected, which manifested itself, for example, as a yellow color.

These first-produced granulates are also an object of the invention.

Advantageous embodiments of the method of manufacture and itself for 9 9 9 99 99 99. 9 9 999 9999

99 99 99 99 99 999999 9 99 99

9,999 9 9

9999 9 99 <9

The products are the subject of the dependent claims.

Examples of findings

Experimental part

The following tests were performed to determine the granulates of the invention:

1. Hygroscopicity test

To determine the hygroscopicity at room temperature, the following air humidity were adjusted in several dessicators (0.160 mm) by means of saturated solutions (with the substance at the bottom):

% rel. humidity of Ca / NO / _o . 4 H _o 0

2% rel. humidity of KaCl

Now, 5 g of test substance is equally distributed in the binding vessel (50 mm) and the binding vessel is placed open in a desiccator (rhi) of the desired air humidity / at room temperature. After 1, 2, 3, 5 and 7 days, the binding flasks are removed from the desiccator, evaluated optically and weight gain is recorded. In several cases, if necessary, the water content can be additionally determined by Karl-Fischer titration.

2. Clumping test

Screen printing punches, which are always filled with 20 g of the test substance and provided with a pickled from • · φ • · ··· φ φ ··

-11 • ···· 9 · · · · · · · · · ·

in the desiccator at room temperature and relative air humidity of 55% at 76% (adjusted with saturated saline solutions, see point 1). After 3 days, the moldings thus obtained are placed carefully in a horizontally rotating cylindrical screen (55 rpm). After engagement of the rotating sieve, the abrasion time in s is determined, after which a defined amount of abrasion (10 g (weight under the sieve)) emerges from the cylindrical sieve. The shorter the wear times, the less pronounced the tendency to clumping.

Dust measurement according to Dr. O ^ oschoapa

100 g of the test substance was added p ^x es addition funnel 1 to the second frequency třasadlového doaravníku třasadlového doaravníku 2 is adjusted via the controller so that the powder Telia slowly and uniformly into the funnel. 3 * p ^y powder falls es funnel 3 and a filling pipe 4 into the inner cylinder 5 of the test apparatus which is placed underneath, while the dust is collected outside this vessel onto the base plate 6 vnějš'ho cylinder 7 / cf. Fig. 1 /.

Upon completion of the powder passage, the remaining powders remaining in the conveyor belt 2 and in the funnel 3 are transferred to the test apparatus by brush. After a waiting time of 5 minutes, the dust deposited on the polished bottom plate is weighed. The dust content is given as a percentage of the weight.

EXAMPLE ^P-D s, breast is natriummehioninát / topics /, dried

9

9 ► 4

I 4

9 4

By spraying, the molar ratio of Met: Na = 1: 1 / or granulation, the methioninate solution being redissolved with activated carbon.

NaMet analysis data

bulk density / kg / raV 500 density of the compressed powder / kg / m ^ / 600 size distribution, grain /%> / Z. 200 / µm 90% o% dust /% / = 4 / dust test according to Dr. Groschoppa FIG n * (dust test machine)

The spray-dried product was granulated under the following conditions in an Eirich mixer (Table 1).

Table 1: Granulaee conditions in prill oroduct granulate A amount of NaMet (spray-dried) / kg / 2.5 amount of granulation fluid / ml / 530

Liquimeth / 60% Met / Granulator 3

1.66 / + 83 g 'stearic acid as an additive /

390 mixer speed / rev / mi.n /

3000

3000 • ·

-13 • 4 • 4

The granulate was checked for its handling properties (teb.2)

Table 2: Properties related to maneuverability with the granulate

product granulate A granulate Synthetic density / kg / m ^ / 740 800 density of the compressed powder / kg / nr / 840 900 grain size distribution /IN 100 µm 7 9 100 to 500 µm 51 53 500 to 100 µm 23 23 1000 to 1400 µm 6 5 14CO to 3150 9 8 3150 to 5000 µm 4 2 dust content /% / 0.2 0.1

In particular, however, the data of hygroscopic behavior and the tendency to clumping of sodium methioninate in the form of spray-dried granules are particularly relevant. tab. 3 /.

When comparing the various product forms, the granulate shows a markedly lower weight gain (= water absorption). Especially significant are the differences between the spray dried product and the granulate p ^γ, and the relative air humidity of 55%.

P ^r, and relative humidity are numerical differences smaller, ootický impression shows the considerable benefits • ^ • · · · · · «• • 9 9 9 9 9

-14oro shape granulate.

Weight gains and? up to about 18% show greater or less buildup of deposits on the product surface.

While a short impact of the glass container was sufficient for the granulate to recover the free-flowing product, the spray dried powder was crushed after exposure to atmospheric influences to produce a bulk material.

This impression is confirmed by the results of the determination of the tendency to clump / tub. 3 /. With less clumping ⁱⁿ the lon and oninátu ummetl Paint the granulate manifests itself clearly to the shorter periods of abrasion.

Table 3 'hygrosconicity and clumping tendency of sodium methioninate in spray-dried form and as granulate product

MaMet / dried granulate A granulate 8 years of drying /

8? rel. humidity □ ^ 'weight gain ///

after 1 day 8.4 5.8 4.0 after 2 days 11.8 5.7 4.6 oo 3 days 12.1 7.1 5.3 after 4 days 11.4 7.7 5.4 after 5 days 13.4 7.8 5.6 prone to clumping 60 20 May 13 abrasion time / s /

• ·

-15ookr. TABLE 3 Product NaMet / dried granulate A granulate 3 years of sputtering tm /% rel, humidity * weight gain / $ /

no 1 days 12.4 10.1 8.9 oo 2 days 17.7 13.6 11.4 no 3 days 23.6 15.0 14.5 after 4 days 25.7 26.3 24.7 no 5 days 31.0 33.6 31.2 he clings to clumpy 235 145 147

abrasion time / s /

Claims (15)

P A T 2 C O N T R O L A process for the manufacture of a bulk animal feed additive based on methioninate, characterized in that the methioninate salt solution is converted into a granulate. 2. A process according to claim 1, wherein the solution of the methioninate salt is spray dried and the powder thus obtained is then granulated. Method according to claim 1, characterized in that the solution of the methioninate salt in the fluidized bed is simultaneously spray-dried and granulated. Process according to one or more of Claims 1 to 3, characterized in that the solution of the methioninate salt is converted by extrusion into a granulate. ?. Process according to one or more of Claims 1 to 4, characterized in that the solution of the methioninate salt is spray-dried and / or dissolved before spray-drying _. The granulation is treated with activated carbon. Method according to one or more of Claims 1 to 5, characterized in that the solution of the methioninate salt is sprayed and / or granulated in the presence of silicate-based additives. Method according to claim 6, characterized in that the additive used is 4 · · · · · · · · 17 a hydrophilic or hydrophobic silicic acid, made of precipitated or pyrogenic nature, in an amount of 0.1 to 10% by weight, based on the solid. Process according to Claim 6, characterized in that the additive used is a finely divided zeolite or bentonite in an amount of 0.1 to 10% by weight, based on the solid. The process according to claim 6, characterized in that fatty acids and / or their alkali metal or alkaline earth salts are used in an amount of 0.1 to 10% by weight, based on the solid. Method according to one or more of the preceding claims, characterized in that a 10 to 70% solution based on methicinate is used. A method according to claim 10, characterized in that .mu.Ci se t 'm, that 25 to 50% is used roztek. 12. Way according to one of the previous claims, v y z n o no learning that a solution of Na-methioninate and / or K-methioninate is used. Method according to claim 12, characterized in that a solution is used for: 4 4 · 4 • 444 44 44 -18trium methioninate. Method according to one or more of the preceding claims, characterized in that after spray-drying, a powder is obtained with spray-drying. a specific gravity in the range of J50 to 500 kg / m &lt; 2 &gt; and this is granulated. Method according to one or more of the preceding claims, characterized in that the spray-dried powder is granulated together with a saturated solution of the methioninate salt in a high shear mixer. 16. The method of claim 15, wherein the weight ratio of powder to saturated aothioninate solution, based on solids, is in the range of 1: C, C1 to 1: C, 5. Method according to one or more of the preceding claims, characterized in that the construction granulation is carried out in a case-by-case manner using grinding tools, Method according to one or more of the claims, characterized in that an extrusion forming process is used for the production of the granulate, optionally in combination with an intensive mixer or fluidized bed dryer. 19. A high flowability methioninate granulate having a a bulk density of > 650 kg / mP, a b) a grain size distribution of 6 to 5000 µm, a c) a dust content of 11%.