FI65362C - FOER GRANULERING AV FODERBLANDNINGAR AVSETT LIGNOSULFONATBASERAT HJAELPMEDEL FOERFARANDE FOER DESS FRAMSTAELLNING OCH DETTA HJAELPMEDEL INNEHAOLLANDE FODERBLANDNINGAR - Google Patents

Description

65362

Lignosulfonate-based excipient for granulating compound feeds, method thereof. for granulating and containing compound feedingstuffs

The invention relates to a novel lignosulfonate-based excipient for the granulation of compound feedingstuffs, to a process for the preparation of such an excipient and to compound feedingstuffs containing this excipient with improved granulation properties.

In recent years, methods have been extensively researched and devices developed to combine different types of finely divided feed materials, powders and liquids into the most palatable, nutritionally advantageous, mechanically resistant and easy-to-handle granules and other artificially assembled feed preparations.

It is known that the granulability properties of different feed materials vary widely. Despite advances in granulation technology, only a few feed material mixtures can be granulated without granulation aids. Granulating aids either improve the mechanical strength of the granule and / or accelerate the passage of the mixture to be granulated in the granulating machine.

Granulation of animal feeds is now a well-known, large-scale industrial process comprising the following steps: milling, in which the feed materials are divided to the desired degree of milling, mixing in which the various feed components and the selected granulating aid are thoroughly mixed 30 - conditioning, in which the mixture temperature and / or the granule is raised to a predetermined level before granulation, normally using steam - granulation in which the feed mixture is combined by pressing the mixture through holes in the granulation matrix and cutting the compact into granules of the desired length, cooling in which the temperature of the granules is dropped and blowing air drying of the granules takes place, 5 - crushing, in which, if desired, the granules are reduced to granules of the desired size.

The feed material to be granulated is most often a compromise between nutritional, economic and granularity aspects. The granulation aid used and its amount is generally a critical factor in optimizing the quality of the granule with the minimum cost mixture.

Numerous different granulation aids have been proposed, cf. e.g. U.S. Pat. No. 3,035,920 and FI Patents 40,509, 51,035 and 56,925, but these have not proved to be satisfactory in practice and the disadvantages associated with them are well known. Clay and lignosulfonate-based granulating aids and their mixtures currently cover more than 90% of the market due to their low price and large supply. However, their main drawback is that in order to achieve the desired granulating effect, they have to be added to the feed materials in amounts of up to 1.5-4% by weight and even more, based on the dry weight of the composition.

Steam quality and sufficiency and choice of matrix to be used - e.g. however, its thickness, raw material, wear, the shape of the boreholes, and the diameter — often cause such large amounts of excipients to be insufficient to provide a durable grain.

For the preparation of low compound feed mixtures, amounts of granulating agents of 1.5 to 4% are acceptable. With a high feed-30 value in the mixture, amounts of granulating aid of 1.5% to 4% ai are both impractical and expensive, because the feed value loss caused by the granulating aid has to be replaced by more expensive components with a higher feed value.

These, in turn, often impair the granularity of the mixture. Clay supplements of more than 35 1.5% are also nutritionally problematic. 65362 due to the fact that clay tends to bind micronutrients irreversibly Feed materials containing 1.5% and more lignosulfonates tend to cause diarrhea in monogastric animals and also adversely affect the palatability of the feed even so that the animals reject the feed.

By means of the present invention, the above-mentioned drawbacks have been largely eliminated. The granulating aid according to the invention makes it possible to produce cohesive and resilient granules considerably better, as a result of which the amount of excipient used in the feed has been substantially reduced and thus the above-mentioned side effects caused by large amounts of binder can be avoided.

Due to the better cohesiveness of the feed mixture, previously very critical factors during granulation, in particular evaporation conditions and matrix selection, have largely lost their relevance when using the excipient according to the invention, which in turn means easier and cheaper granulating feed material mixtures.

The invention therefore relates to a lignosulfonate-based granulating aid for the granulation of compound feedingstuffs, which contains a dried, substantially water-soluble, oxidatively cross-modified sulphonated lignin-containing substance having a viscosity of up to 25 10,000 cP, measured at 25% by weight in water.

The invention also relates to a new process for the preparation of a granulating aid as defined above, which comprises cross-linking a sulphonated lignin-containing substance with hydrogen peroxide or its derivatives or salts in aqueous solution using a metal ion salt or complex salt capable of occurring conversion of the reaction product to a gel-like or insoluble form, such as by limiting the amount of oxidant used or by decomposing the oxidizing agent and drying the reaction product.

65362

The invention further relates to feed compositions for granulation which contain at least 0.05% by weight, preferably 0.2 to 0.6% by weight, of granulation aid as defined above as agents for improving the cohesiveness, strength and resilience of the granules.

The oxidative crosslinking reaction comprises a dehydrogenating polymerization reaction described in e.g. in K. Sarkanen, Lignins, edited by Sarkanen and Ludwig, Wiley-Interscience, and H.H. Nimz et al., Applied Polymer Sympo-10 Sium No. 28, 1225-1230 (1976), John Wiley & Sons Inc.

DE 2222 353, for its part, describes the oxidative crosslinking of sulphite lignite-containing sulphite waste liquors obtained from the manufacture of cellulose to produce a binder for gluing particle board and similar wood products, using hydrogen peroxide III cyanoferrate (II) as the oxidant. with. Oxidative crosslinking of a lignosulfonate-containing substance easily results in the formation of insoluble products, as in this process according to DE-A-2,221,353. However, such insoluble products are unsuitable for the present invention.

Namely, the granulation aid according to the invention with improved properties requires that it can be dried from its aqueous solution into a fine powder which is substantially water-soluble and slightly hygroscopic and that its viscosity is at most 10,000 cP measured at 23 ° C at 25% by weight: aqueous solution with a Brookfield viscometer.

According to the invention, calcium, magnesium, sodium or ammonium-based sulphite waste liquor, or mixtures thereof, which have optionally been increased in lignosulphonate solids content, e.g. by removal of carbohydrates, for example by fermentation or ultrafiltration, are preferably used as starting material for the crosslinking reaction.

65362 5

Although it has been found that lignosulfonate starting materials having a high ratio of lignosulfonates to other solids are best suited for the purposes of the invention to produce a substantially water-soluble crosslinked product, it is to be understood that conventional sulfite waste liquors can also be used to granulate compound feeds.

The concentration of the lignosulfonate-containing starting material is not critical, but for practical reasons it is preferable to use 10 to about 45-55% lignosulfonate solution at the beginning of the reaction and gradually add water as the crosslinking reaction progresses.

The viscosity of the 25% lignosulfonate starting material is generally about 5 to 6 cP.

The crosslinking reaction according to the invention is carried out in aqueous solution, preferably using hydrogen peroxide or other peroxide compounds or its salts as oxidants and salts or complex salts of metal ions which are capable of transitioning from one valence stage to another, at acidic or alkaline pH.

A very useful process for the preparation of the products according to the invention is one in which hydrogen peroxide is used as oxidant in a slightly acidic aqueous solution, pH 3 to 6, together with catalytic amounts of cyanoferrate (II) or cyanoferrate (III) salt, or cobalt-nickel and the like. with complexes.

Although the cyanoferrate (III) salts are toxic, they apparently become non-toxic cyanoferrate (II) salts upon completion of the reaction upon raising the temperature and pH of the reaction medium. Toxicity studies in mice and rats have surprisingly shown that the LD50 values of the untreated lignosulfonate and the granulating aids prepared with cyanoferrate (III) salts do not differ, and also that the excipients according to the invention can be used completely safely in animal feed. > 10 g / kg).

6 65362

Other metal salts, e.g. ferric and ferrous sulphates, can also be used as metal salt activators, provided, however, that the metal ion is one which, under the action of the oxidizing agent, is able to move from one valence stage to another and to form a complex. The metal is added in complex form or is capable of forming a complex with a lignosulfonate, such as iron salts.

Suitable peroxide compounds are, in addition to hydrogen peroxide, e.g. Na 2 O 2, or K 2 S 2 O 8 'and the corresponding acids. When hydrogen peroxide acts as an oxidant, this is suitably used in an amount of about 1-10% by weight (calculated as 100%), based on the dry weight of the crosslinkable lignosulfonate, or an equivalent amount of other peroxide compounds, although these amounts are not critical. A suitable amount of activator-15 is about 0.1 to 1.5% by weight, preferably less than 1.0% by weight based on the dry weight of the crosslinkable lignosulfonate agent.

The oxidative crosslinking reaction is exothermic, so it is preferable to cool the reaction mixture to near room temperature if necessary.

Essential to the process of the invention is that the oxidative crosslinking reaction is stopped before the product gels or becomes insoluble.

At the initial stage of gelation, the product is still lubricating to Liu-25 in water, but as the gel ages, it becomes insoluble and unsuitable for the purposes of the invention. The crosslinking reaction can be stopped in a variety of ways, such as by limiting or decomposing the amount of oxidant used when the desired degree of crosslinking is achieved, e.g., by adding a strong reducing agent such as sodium sulfite or diluting the reaction mixture with a starting material such as untreated sulfite waste liquor or water. When hydrogen peroxide acts as an oxidant, this can be decomposed, e.g., simply by heating the reaction mixture suitably to a temperature of up to about 90 ° C.

Oxidative crosslinking causes an increase in viscosity, which in turn provides a simple means of monitoring the coupling reaction and determining the time at which the reaction is stopped, as well as determining the products. In general, granulating aids having a viscosity in the range of 75 to 500 cP, measured in a 25 weight aqueous solution at 23 ° C, are useful for the purposes of the invention, with the amount added to the feed being only about 0.2 to 0.6% by weight. to achieve good cohesiveness. Granulating aids having a viscosity of about 5,000 to 10,000 cP are of limited use when the feed mixture processing temperature and moisture content are exceptionally high. Granulation aids with a low viscosity of about 5-50 cP, on the other hand, require additions of about 0.8 to 1.5% by weight to achieve good cohesiveness with most compound feeds.

The viscosity of the resulting oxidatively crosslinked sulfonated lignin-containing material can be adjusted to the desired value, if desired and necessary, also by adding untreated lignosulfonate-containing material to the final product in suitable amounts so that the viscosity of the granulating aid is less than 10,000 cP at 25% aqueous solution.

The oxidatively crosslinked sulfonated lignin-containing substance can advantageously also be combined with customary inert carriers, such as clay, talc, calcium carbonate or gypsum, without compromising its good granulation properties. The addition of untreated lignosulfonate 30 and / or an inert carrier then takes place preferably before the crosslinked product is dried, but can also take place afterwards.

The pH of the obtained products can be adjusted, if desired, by adding an acid or a base. The pH of the products used for granulating the compound feeds is preferably in the range of 2.5-11.0 δ 65362 as measured in 5% aqueous solution.

The term "oxidatively crosslinked sulfonated lignin-containing material" in this specification and claim means any sulfonated lignin-containing material that has been partially or completely subjected to oxidative crosslinking to produce substantially water-soluble, high viscosity metal catalysts using an oxidant or activator. an ionic salt or complex salt capable of occurring at more than one valence level.

Oxidative crosslinking is thought to lead to the loss of hydroxyl functions and the etheric protection of the groups involved in the formation of hydrogen bridges. - Our finding that the cohesiveness of the feed material mixture can be substantially improved by adding a substantially water-soluble substance containing oxygen-crosslinked sulfonated lignins is therefore also surprising given that the ability to form hydrogen bridges has been considered an essential property of granulating aids.

The following examples illustrate the invention; viscosity values are measured with a Brookfield viscometer in 25% aqueous solution at 23 ° C, and pH values are measured in 5% aqueous solution.

Example 1 800 kg of ferrous sulphate, Fe 2 SO 4 · 7H 2 O, and 17,000 kg of hydrogen peroxide (40%) were added at 25 ° C to 150 tonnes of concentrated (53%) calcium-based spruce sulphite waste liquor obtained by alcoholic fermentation. The batch was divided into three equal parts to prepare three different granulation aids as follows:

Rakeistusapuaine_IA

One third of the above batch was allowed to stand for 36 hours from time to time with cooling to keep the temperature below 35 ° C. After this period, the reaction mixture was at the limit of its gelation point and was diluted with 20 tons of water. During the reaction, the pH had dropped to 2.8 and was readjusted to 4.5 using 50% sodium hydroxide solution and the temperature was raised to 90 ° C for spray drying. After spray-drying, a very fine, slightly hygroscopic powder was obtained which was completely soluble in water and had a viscosity of 8700 cP with a Niro-type spray-dryer.

The granulation ^ ^ IB aEuaine

10 The second third of the batch prepared above was allowed to stand for 36 hours, similar to Example IA, after which 50 tonnes of original untreated waste liquor diluted to a solids content of 40% were added. Further work-up took place as described in Example IA. The viscosity of the spray-dried product was 75 cP.

In substantially the same way, it is possible to adjust the viscosity of the final product to a value that is untreated in the waste liquor and oxidatively. between the viscosity values of the crosslinked substance by simply mixing 20 suitable amounts of waste liquor and reaction product. Granulation £ uaine_IC

To one third of the above charge was added 10 tons of water and the charge was allowed to stand for 20 hours while cooling from time to time. Adjusting to pH 4.5, raising the temperature to 25 ° C to 90 ° C and spray drying gave a product with a viscosity of 580 cP.

Example II

Sufficient 50% sulfuric acid and solid sodium sulfate were added to the sulfite waste liquor of Example I prepared by alcoholic fermentation to adjust the pH to 3.5 and to precipitate substantially all of the calcium as calcium sulfate.

To 48 tons of the filtered solution with a solids content of 44% by weight due to the diluting effect of the filter cake washings was added 25 kg of potassium ferricyanide, K 2 Fe (CN) g, and 2000 kg of hydrogen peroxide solution (40%). The mixture was allowed to stand for 10 hours at 25 ° C with periodic cooling. 8 tons of water were added, after which the mixture was divided into two similar portions, which were treated as follows to prepare two qualitatively different granulation aids.

Granulating aid_ IIA_

Half of the above batch was allowed to stand for another 10 hours, after which the temperature was raised to 75 ° C and the pH was adjusted to 8.8 using 50% sodium hydroxide solution. The temperature was then raised to 90 ° C. Spray drying gave a sodium-based product with a pH of 8.5 and a viscosity of 40 cP.

15 Rake i s t u sapua ine_ I IB_

An additional 1500 kg of hydrogen peroxide solution (40%) was added to the second half of the above batch and after three hours 10 tons of water were poured into it. The product appeared gel-like after 8 hours but dissolved easily when the temperature was raised to 75 ° C and sufficient sodium hydroxide solution was added to pH 8.8. The spray-dried product had a pH of 8.5 and a viscosity of 9500 cP.

Example III

To 25 tons of calcium-based spruce sulfite waste liquor obtained through ethanol and protein fermentation (PEKILO) with a solids content of 46% was added enough 50% sulfuric acid to adjust the pH to 3.2. The precipitated calcium sulfate was filtered off, after which 10 kg of potassium ferricyanide and 1000 kg of hydrogen peroxide-30 solution (40%) were added to the filtrate, whereby the mixture became thick within 2 hours. The reaction mixture, which had a solids content of 41% at this stage, was further diluted with 7 tons of water. Raising the temperature to 75 ° C and adding sufficient sodium hydroxide solution to pH 10.5 gave a spray-dried product having a pH of 10.4 and a viscosity of 240 cP.

, V

65362

Example IV

To 35 tons of magnesium-based sulfite waste broth with a pH of 3.3 and a solids content of 53% were added 150 kg of potassium ferrocyanide, K 2 Fe (CN) g · 3H 2 O, and 4000 kg of hydrogen peroxide solution (40%). The solution was continuously cooled to keep the temperature below 35 ° C and began to thicken after 14 hours. It was diluted with 12 tons of water and its temperature and pH were adjusted to 75 ° C and 9.0, respectively. The pH of the spray-dried product was 8.2 and the viscosity was 10 cP.

Example V

This example illustrates the use of a water-insoluble inert material as a carrier for an oxidatively crosslinked, water-soluble, sulfonated lignin-containing granulation aid.

To 50 tons of concentrated (53%) calcium-based spruce sulfite liquor obtained by alcoholic fermentation was added at 25 ° C sufficient 50% sodium hydroxide solution to raise the pH to 7.5. While continuously cooling, 80 kg of potassium ferrocyanide were added, followed by 2000 kg of hydrogen peroxide solution (40%) and 30 tons of water. After a reaction time of 4 hours, the viscosity of the solution was 35 cP. The temperature of the solution was then raised to 85 ° C and 20 tonnes of fine talc were added while continuously heating and stirring vigorously. Spray drying gave a fine, free-flowing powder with an ash content of about 55%.

To demonstrate the improved cohesiveness of the compound feeds of the invention, three different types of feed compositions were prepared using the granulation aids prepared above in amounts of 0.1-1% by weight and for comparison also 3% by weight of a commercial calcium lignosulfonate feed binder. The compound feeds were granulated under identical conditions. The granules were compared for hardness and elasticity 12 65362 using a Rahi hardness tester and rotating the granules for 3 minutes in a drum mixer and measuring the fines released from the granules. Measurements were made three times and samples were taken from the condenser, the first immediately at the beginning of 5, the second at about the middle, and the third at the end. Prior to measurement, each sample was allowed to stand for 30 minutes.

To simplify the experiments, the granulating aids were added to the feed mixtures in the form obtained in the previous examples. It will be appreciated that they may also be added with a vitamin-10 trace element premix or other feed components or as mixtures with clays, matrix lubricants, etc.

Example A Granulated livestock feed 15 In a mixer, 900 kg of ground barley, 600 kg of ground oats, 240 kg of dried grain flour, 500 kg of soybean powder, 490 kg of ground wheat, 75 kg of skimmed milk powder, 75 kg of dicalcium phosphate, 25 kg of salt, 35 kg of salt were thoroughly mixed. ground limestone, 10 kg of magnesium-20 oxide and 10 kg of vitamin-trace element premix together with rake seating aid. 9% by weight of molasses was then added to the mixture and fed to a Buhler Miag Dpab-type granulating machine, where the temperature was raised to 67 ° C and the total humidity to 16.9% using steam.

The mixture was pressed at a rate of 15 tn / h through a matrix with holes with a diameter of 8.5 mm. The fine fraction was then screened off and the granules were cooled and dried.

The following two compound feeds were prepared in essentially the same manner.

30 Example B

Granulated chicken feed 13 65362

Granulated chicken feed was prepared by mixing granulating aids in a mixture of 44% by weight of ground barley, 25% by weight of ground wheat, 16% by weight of soybean powder, 4.5% by weight of herring flour, 3.2% by weight of 5 fats, 3.0% by weight -% ground oats, 2.0% by weight of feed yeast, 1.7% by weight of dicalcium phosphate, 0.5% by weight of calcium carbonate, 0.25% by weight of sodium bicarbonate and 0.7% by weight of vitamin trace element premix.

The mixture was fed into a humidification chamber and evaporated to 72 ° C, increasing the moisture content to 15.4%. The moist feed was then pressed through a matrix with holes 3.2 mm in diameter at a rate of 3 tn / h, after which the granules were screened and cooled.

Example C

15 Granulated fur animal feed

Granulated fur animal feeds were prepared by mixing granulating aids in a mixture of 30% by weight of pre-cooked wheat flour, 10% by weight of finely ground soybean meal, 8% by weight of rapeseed oil, 48% by weight of herring powder and 20% by weight of a vitamin-trace element premix. An additional 6% by weight of molasses was added to the blends and evaporated to 70 ° C, raising the total moisture content to 16.2%. The mixtures were then fed to a Buhler DFPC type granulation machine and pressed through a matrix with a hole diameter of 4.5 mm. The feeds were then screened and cooled in a manner similar to that described above.

For the granulated feed mixtures A-C prepared with the granulating aids of the above-mentioned Examples I to V, the hardnesses and fines content mentioned in the following table were measured in the above-mentioned test system.

It can be seen from the table that, compared to the conventional calcium-based lignosulfonate feed binder, the granulation auxiliaries according to the invention give good results at considerably lower application rates.

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Claims (8)

1. For granulating feed mixtures of lignosulphonate-based granulating aids, characterized in that it contains dried, substantially water-soluble, by oxidative cross-linking, modified sulfonated lignins containing material, and that its viscosity is not more than 25 cps in weight. %: aqueous solution at 23 ° C. 2. Granulation aid according to claim 1, characterized in that its viscosity is 75-500 cP. Granulation aid according to claim 1 or 2, characterized in that its pH is 2.5-11 measured in a 5% by weight aqueous solution. A process for the preparation of a granulating aid according to any of the preceding claims, wherein the sulfonated lignin-containing material is subjected to a cross-linking reaction with hydrogen peroxide or derivatives or salts thereof, in an aqueous solution in the presence of an activator in the form of a site or a complex salt of a metal ion, which can occur at several different valence levels, characterized in that the crosslinking reaction is stopped before the reaction product passes in a gel or insoluble form, e.g. by limiting the amount of oxidant used or decomposing the oxidant, and the reaction product is dried. 5. A method according to claim 4, characterized in