AU5348199A

AU5348199A - Pourable methionine-containing shaped bodies and process for the production thereof

Info

Publication number: AU5348199A
Application number: AU53481/99A
Authority: AU
Inventors: Klaus Bonig; Hans-Joachim Hasselbach; Gundolf Hornung; Klaus Huthmacher; Martin Korfer
Original assignee: Degussa GmbH; Degussa Huels AG
Current assignee: Evonik Operations GmbH
Priority date: 1998-10-10
Filing date: 1999-10-06
Publication date: 2000-04-13
Also published as: DE19846825A1; KR20000028898A; CN1184897C; EP0992490B2; ES2200450T5; ES2200450T3; EP0992490B1; CA2285820A1; EP0992490A1; CN1250608A; BR9904455A; MXPA99009235A; ATE241598T1; JP4588820B2; JP2000116336A; DE59905726D1

Abstract

Free-running moldings, especially extrudates, containing methionine have a bulk density of 300-850 kg/m<3> and particle size range of 63-5000 mu m and consist mainly, especially 60-98 wt.%, of methionine. An Independent claim is also included for the production of the moldings.

Description

S F Ref: 478075

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

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Name~ an drs Name and Address of Applicant: Actual Inventor(s): Degussa-Huls Aktiengesellschaft Frankfurt am Main D-60287

GERMANY

Martin Korfer, Gundolf Hornung, Klaus Huthmacher, Hans Joachim Hasselbach and Klaus Bonig Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Pourable Methionine-containing Shaped Bodies and Process for the Production Thereof Address for Service: Invention Title: The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845 Pourable Methionine-Containing Shaped Bodies and Process for the Production Thereof The invention relates to pourable methionine-containing shaped bodies and to a process for the production of those products.

The preparation of methionine or of a salt of methionine, the latter especially as an intermediate stage before isolation of the methionine in a corresponding process, using the starting materials methylmercaptopropionaldehyde and hydrogen cyanide, has long been known and is described in a large number of literature references.

The corresponding methionine salt is produced via the intermediate stage of 5-(3mercaptoethyl)-hydantoin and subsequent basic hydrolysis using various alkali metal, alkaline earth metal or ammonium compounds. Methionine is freed from the salt with the aid of acids and is isolated by means of a suitable process. The working-up processes for converting the methionine into a condition suitable for further use generally prove to be very expensive.

The methionine produced according to known processes (US 2 557 913, DE 1906405, JP 42/44056) is distinguished by a more or less strongly pronounced crystalline structure.

It is in the form of a white to creamy-white product; the bulk densities are generally from 600 to 700kg/m 3 the particle spectrum range is very widely spread from <32pm to approximately 1200pm, the pourability can be greatly impaired especially in the case of a plate structure of the methionine.

S: From JP-A-59-199670 there is known a process for producing granulated methionine, in which 20 methionine and other granular organic or inorganic materials are mixed as a powder and granulated with the addition of solvents.

The object of the invention is to make available a process which yields shaped, pourable products having a low dust content.

The invention provides pourable methionine shaped bodies, especially extrudates having a bulk 25 density of from 300 to 850kg/m 3 especially from 600 to 800kg/m 3 and a particle spectrum from 63pm to 5000pm, especially from 500 pm to 1500pm. They contain methionine in a predominant amount, especially from 60 to 98wt%, preferably from 85 to 95wt%. Shaped bodies can be produced according to the process known from the prior art.

In a preferred form, the shaped bodies, for example in the form of extrudates or granulates, also contain foreign substances which act as binders.

Those substances are organic or inorganic in nature and are suitable as additives where the products according to the invention are used as feeds.

In an especially suitable embodiment, those compounds come from the methionine preparation process and are optionally contained in the main product as secondary products without having to be separated off beforehand for purification of the main product.

D,L-methionine or a salt of D,L-methionine is generally prepared starting from the components 3-methylmercapto-propionaldehyde, hydrogen cyanide, ammonia and carbon dioxide, or 5-(2methylmercaptoethyl)-hydantoin.

The synthesis steps can be illustrated by means of the following reaction equations: formation of 5- (2-methylmercapto) -hydantoin: C07243 H3C_ SO HC0 H-N

NH

s H 2HCN 2NH3 2CO2 2H20 (1) formation of the D,L-methionine salt: H3CS

NH.

H-N NH H3Cs O'

M

O M 2 C0 3 3H20 +3CO 2 2NH 3 (2) freeing of D,L-methionine:

NH

2 NH 2 H3C, S OM H3C'S O' H o 2C02 2H 2 0 o 2MHCO 3 (3) M represents an alkali metal, an alkaline earth metal or ammonium, especially potassium.

Processes of that type are described, for example, in DE 1906405.

It is advantageous for the shaping to wash the methionine separated from the preparation process with water or with a mother liquor taken from the preparation. process.

10 It has proved to be especially advantageous if small amounts of dissolved methionine and/or potassium salts, especially potassium carbonate and/or potassium hydrogen carbonate, still adhere to the solid. Those amounts generally range from <0.1 to 10wt%, based on the methionine.

A residual moisture content in the range of from 8 to 40wt%, especially from 12 to *:based on the total weight, has proved to be advantageous for the shaping.

15 In a preferred form, the shaped articles, for example in the form of an extrudate, also contain a binder in an amount of from >0 to 20wt%, based on methionine. Inorganic compounds such as potassium carbonate and/or potassium hydrogen carbonate are especially suitable as binders.

In order to improve the shaping process, organic binders are also additionally used, individually or together.

20 Those organic binders include dissolved methionine and other substances, such as methylcellulose, ethylcellulose, carboxymethylcellulose, carboxyethylcellulose, carboxypropylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, cellulose acetate dibutylaminoacetate and other cellulose derivatives, starch, hydroxypropyl starch, sugar, dextrin, gelatin, other natural high-molecular weight substances, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylacetal dibutylaminoacetate, it being possible to use one of those substances on its own or several of those substances together and thus improve the shaping. The binders are preferably used in the form of aqueous solutions.

In order to improve handling of the shaped bodies to be produced, it is recommended to shape the methionine in the presence of silicate-based additives.

Those additives include hydrophilic and hydrophobic silicas of pyrogenic nature, or silicas of from 5 to 300m 2 /g prepared by precipitation, preferably spray-dried silicas. Finely divided zeolites, for example of type A, or bentonites may also be used.

C07243 3 The amount of those and other additives is from 0.1 to 10wt%, preferably from 0.1 to based on the methionine. Of course, in addition to the silicate-like compounds, those additives preferably include substances that are permitted in the feeds sector, especially fatty acids and their salts, preferably alkali metal or alkaline earth metal salts.

The fatty acids include especially stearic acid and palmitic acid or mixtures of fatty acids containing from 16 to 18 carbon atoms or their above-mentioned salts. Binders, additives and also feed-effective compounds are added to the suspension of the methionine either in solid form or, optionally, in the form of an aqueous solution, or are added to the separated methionine prior to shaping (eg. extrusion).

The feed-effective compounds include other amino acids, such as lysine, threonine or alanine or their salts, N-acylamino acids, N-hydroxymethylmethionine calcium salts, 2-hydroxy-4methylmercaptobutyric acid and other amino acid hydroxy analogues, fish meal, casein, other proteins, vitamin A, vitamin A acetate, vitamin A palmitate, vitamin D3, vitamin E, nicotinic acid, nicotinic acid amide, pantothenic acid calcium, 3-carotene.

Those compounds are used in a total amount of from 0 to 30 40wt%, especially from 1 to based on methionine.

*The shaped bodies produced according to the invention are then suitable as a complex feed for S.feeding animals.

The invention also provides a process for the production of methionine-containing shaped 20 bodies, characterised in that the water is removed from an aqueous methionine suspension down to from 8 to 40wt%, based on the total amount, and the solid so obtained is shaped, but especially extruded. In particular, a residual moisture content of from 12 to 25wt% has proved to be advantageous for the shaping.

That is the case especially when the methionine is processed following the preparation process 25 and the suspension contains potassium carbonate/hydrogen carbonate and organic secondary products.

The use of a twin screw extruder has proved to be especially suitable for the shaping. The solid is then generally forced through an extrusion die at extrusion pressures of up to 60bar at temperatures of from 20 to 1200C.

In that manner, extrudates having extrudate diameters of from 500tm to 5000J.m, preferably from 800 to 1000Jm, are produced.

The length of the extrudate can either be adjusted by mechanical cutting, or the extrudate breaks off as it emerges from the die owing to a suitable selection of the process parameters.

Other suitable apparatuses or processes for the production of shaped bodies which may be mentioned are single screw extruders, ring die presses or pan-grinding apparatuses.

If shaping is carried out at an elevated product temperature, then additional evaporation, of water takes place, which markedly facilitates the subsequent drying step.

In some cases it is advantageous to treat the resulting shaped bodies in a so-called "spheroniser" prior to final drying, in order to achieve a rounding of the particles.

C07243 The subsequent step, which optionally takes place in vacuo, of drying off from the shaped bodies the residual moisture that is still present must be carried out mechanically in a very gentle manner at least at the beginning in order to prevent the shaped bodies from being damaged or destroyed.

A combination of a drying belt for partially drying the shaped bodies, especially extrudates, and subsequent final drying in a disk dryer has proved successful. The product temperatures are in the range of from 50 to 140°C, preferably from 90 to 110°C.

Especially after that drying process, the shaped bodies have the desired high mechanical strength. That allows the product to be handled simply. The bulk density is then generally from 600 to 800kg/m3.

The dust content is generally measured by the method of Dr. Groschopp.

Examples Example 1 Methionine having a residual moisture content of 25wt%, a 5 K2C0 3 content of 1.7% and a KHCO3 content of 2.8% is used.

It is fed to a twin screw extruder at a rate of 10kg/h. 120g/h of tylose are added to the intake via a second metering device. The extruder is heated to 110°C and the methionine/tylose mixture is extruded at a pressure of 15bar through a die having 150 0.8mm holes. Granulation is carried out by means of a blade rotating directly at the die. The granulate has a moisture content on exit of 23wt% 20 and is pre-dried on a drying belt and subjected to final drying on a disk dryer. The particle spectrum is from 400 to 1000gpm. The methionine content of the end product is 88wt%. The dust content is and the particles have high strength.

Example 2 Example 1 is repeated, with the difference that extrusion is carried out using a die having 1.2mm holes at a pressure of 13bar. The throughput is 12kg/h. The granulate has a moisture content on exit of 23 The particle spectrum is from 600 to 1500.m.

Example 3 Methionine having a residual moisture content of 32wt%, a K 2 C0 3 content of 2.0wt% and a

KHCO

3 content of 3.2wt% is dried in a contact dryer to a residual moisture content of 16wt%. The product is then extruded, without further additives, in a twin screw extruder at a temperature of 30 0

C

and a throughput of 15kg/h through a die having 0.8mm holes. After granulation by means of a blade, the particles are subsequently rounded in a spheroniser. Final drying is carried out in a disk dryer.

This procedure yields spherical particles having a particle spectrum from 300 to 1000gm. The dust content is Example 4 Example 3 is repeated, with the difference that a ring die press is used for the shaping instead of an extruder. The particle spectrum is from 400 to 1200pm. The dust content is C07243

Claims

1. Pourable methionine containing shaped bodies, having a bulk density of from 300 to 850kg/m 3 and a particle spectrum from 63 tm to 5000tm and having a predominant methionine content.

2. Methionine-containing shaped bodies according to claim 1, which are extrudates.

3. Methionine-containing shaped bodies according to claim 1 or claim 2, having a methionine content from 60 to 98%, based on the total weight.

4. Methionine-containing shaped bodies according to any one of claims 1 to 3, having a methionine content of from 85 to

5. Shaped bodies according to any one of claims 1 to 4, containing an organic and/or inorganic binder.

6. Shaped bodies according to claim 5, containing as binder potassium carbonate or potassium hydrogen carbonate, individually or together.

7. Shaped bodies according to claim 6, in which the binder comes from the mother liquor of the methionine preparation.

8. Shaped bodies according to any one of claims 1 to 7, additionally containing organic binders, which include dissolved methionine, methylcellulose, ethylcellulose, carboxymethylcellulose, carboxyethylcellulose, carboxypropylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, 0. cellulose acetate dibutylaminoacetate and other cellulose derivatives, starch, hydroxypropyl starch, 20 sugar, dextrin, gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylacetal dibutylaminoacetate, individually or in admixture with one another.

9. Shaped bodies according to any one of claims 1 to 8, containing hydrophilic and/or hydrophobic silicas and/or silicate-based additives.

Shaped bodies according to any one of claims 1 to 9, containing other feed-effective *.oo 25 compounds.

11. Shaped bodies according to claim 10, wherein the feed-effective compounds are lysine, threonine or alanine or their salts, N-acyl-amino acids, N-hydroxymethylmethionine calcium salts, 2- hydroxy-4-methylmercaptobutyric acid and other amino acid hydroxy analogues, fish meal, casein, other proteins, vitamin A, vitamin A acetate, vitamin A palmitate, vitamin D3, vitamin E, nicotinic acid, nicotinic acid amide, pantothenic acid calcium, 3-carotene, individually or together.

12. Pourable methionine containing shaped bodies, substantially as hereinbefore described with reference to any one of the examples.

13. Process for the production of pourable methionine containing shaped bodies, characterised in that the water is removed from an aqueous methionine suspension down to from 8 to 40wt%, based on the total weight, and the solid so obtained is subjected to a shaping process, and is subsequently dried.

14. Process according to claim 13, characterised in that the shaping process is extrusion. Process according to claim 13 or claim 14, characterised in that, prior to shaping, the methionine separated from the preparation process is washed with water.

C07243 6

16. Process according to claim 13 or claim 14, characterised in that, prior to shaping, the methionine separated from the preparation process is washed with a mother liquor taken from the preparation process.

17. Process according to any one of claims 13 to 16, characterised in that, prior to shaping, organic and/or inorganic binders are added to the methionine separated from the preparation process.

18. Process according to any one of claims 13 to 17, characterised in that a silicate-like filler, especially a hydrophilic or hydrophobic silica, is added to the methionine prior to shaping.

19. Process according to any one of claims 13 to 18, characterised in that one or more other feed-effective compounds are added to the methionine prior to shaping.

20. Process according to any one of claims 13 to 19, characterised in that the water- containing methionine is extruded at a temperature of from 20 to 120°C, is optionally spheronised and is subsequently dried.

21. Process according to claim 20, characterised in that the water-containing methionine is extruded in a twin screw extruder.

22. Process according to any one of claims 13 to 21, characterised in that the extrudates are optionally dried on a drying belt and optionally additionally on a disk dryer at temperatures of from to 140°C, optionally in vacuo.

23. Process for the production of pourable methionine containing shaped bodies, said process being substantially as hereinbefore described with reference to any one of the examples. 20 Dated 29 September 1999 DEGUSSA-HOLS AKTIENGESELLSCHAFT Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON •ooo°* o C07243