DK145921B - METHOD AND APPARATUS FOR MANUFACTURING URICAN FATOIC ACID ADDITION CONSISTING OF SEPARATE SOLID PARTICLES - Google Patents

Description

(19) DENMARK (¾ ® tu) PUBLICATION WRITING (id 145921 b

DIRECTORATE OF

THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 1019/76 (51) Int.CI.3 A 23 K 1/22 (22) Filing Date 10 Mar. 1976 C 07 C 127/00 (24) Race day 10, mar. 1976 (41) Aim. available 12. S ep. 1976 (44) Posted Apr 18 1985 (86) International application no.

(86) International filing day (85) Continuation day (62) Stock application no.

(30) Priority Mar 11 1975 * NO 188, HU

(71) Applicant NOEVENYOLAJIPARI ES MOSOSZERGYåRTO VALLALAT, Budapest XV., HU: BUDAPESTI MUESZAKI EGYETEM, Budapest XI, HU.

(72) Inventor Eva Kurucz, HU: Piroska Lukaes, HU: Lajos Kollar, HU:

Jozsef Barics, HU: Jozsef Gulyas, HU: Laszlo Zolna, HU: et al.

(74) Clerk of the Office of Industrial Excellence v. Svend Sehønning.

(54) Method and apparatus for producing urea-fatty acid adduct = separate solid particles.

The present invention relates to a method and apparatus for producing a urea-fatty acid adduct (molecular compound) consisting of separated solid particles and suitable for adjusting the urea and fat content of feed to ruminants by combining urea, optionally in the form of a heated solution in water, with a melt of one or more heated fatty acids, or a heated fatty acid / fat mixture in a weight ratio of urea to fatty acid of approx. 40:60 to 60:40 (D calculated from the pure urea.

^ It is known that reliable feeding of urea in an appropriate amount for nutritional animal feeding is only possible if the animals at the same time receive an appropriate urea degradation agent-Q material. By delaying the degradation of the urea, this material allows the microorganisms in the rumen to utilize to the maximum the ammonia produced by the hydrolysis of the urea for use in protein synthesis. At the same time, it is a fundamental condition for optimal synthesis of protein and the utilization of the natural proteins and those that are formed, to ensure that the feed at the same time has an appropriate energy content.

This latter condition can easily be achieved by fatty acids which can be utilized quickly and without residues directly as an energy source of both the microorganisms and the fed animal without requiring lipase enzyme activity.

For this reason, the benefit of using urea and fatty acids together has already been recognized, but both in large-scale feeding and in the preparation of so-called feed premixes, the direct and homogeneous mixing of the available fats with the feed has caused serious difficulties in practice. . In order to eliminate these difficulties and to facilitate feeding and regulation, it has already been proposed to use an adduct formed of urea and fatty acids or partially with neutral fats in feed and premixtures. Such adducts, which may contain, for example, 45-60% fatty acid-fat mixture bound as a molecular compound, are suitable on the basis of their composition to adjust the desired concentration of fat necessary in relation to the amount of urea in the feed, and they also have the advantage that the hygroscopic property of the urea does not appear in such adducts. This property also causes difficulties in the case of the homogeneous mixture of free urea in coarse flour feeders, because such a urea-containing mixture is prone to agglomeration and bridging. Thus, the addition of urea-fatty acid adducts to feed ensures the utilization of the urea (due to the retarding effect of the fatty acid) and also the efficient utilization of the energy-rich fats (due to the partial protein-substituting property of the urea), and also eliminates the technological and nutritional properties. difficulties arising from the separate use of urea and fats.

However, the urea fatty acid adducts prepared by known methods are usually of pasty consistency as well as they contain water, so that in this form they are not suitable for mixing with feed in conventional feed mixers or in other simple ways. For this reason, according to Hungarian Patent No. 162,126, a particulate product which can be easily mixed with feed and which contains a urea-fatty acid adduct is prepared in a ratio favorable from a nutritional point of view (40:60 - 60:40 ), by mixing a heated aqueous solution of urea and hot fatty acid (or a mixture of fatty acid and fat) to form an adduct and then adding a particulate carrier which binds the water content and which itself can be utilized for feeding. Appropriate rapeseed pulp is mixed in the mixture and the solid obtained is ground after cooling. In this way, a particulate adduct containing approx. 50% seed route.

Experiments have also been carried out to produce a product which does not contain particulate carrier but only the pure urea fatty acid adduct, in the form of a dry particulate or powdered product which is readily miscible with feed. Such a process is described in U.S. Patent No. 3,748,319, wherein crystalline urea is converted into a slurry with water insufficient to dissolve the urea, then the fatty substance is mixed with the slurry in a high shear stirrer in a weight ratio which is such that a part by weight of the fat component is mixed with 2.5-5.5 parts by weight of urea and finally the aqueous mass thus obtained is dried in an air stream and comminuted, thereby obtaining a dry powdered product in which the fatty acid / urea ratio is at least 1 : 3, but usually it's around 1: 5. According to the description, observing the specified weight ratios and other operating parameters is essential because otherwise dissociation will occur or a product of insufficient quality will be obtained; in case a greater relative amount of fat compound is used, a satisfactory mixture of the aqueous urea slurry and the fat compound cannot be assured. However, the product of the above composition is not at all satisfactory from a nutritional point of view, since its fatty acid content in relation to the amount of urea is too low so that it does not ensure an appropriate energy level. In addition, the mixing must be carried out under high shear conditions and the drying of the large amount of low temperature aqueous material in an air stream makes it difficult to perform the process on a large scale. From a nutritional point of view, the production of an adduct of the desired composition containing urea and fatty acid or a mixture of fatty acid and fats in approximately equal mass-free, filler-free ratios obtained in a dry, non-agglomerated particle or powder form has not been possible at all by the known methods.

The present invention is based on the discovery that it is feasible to produce an adduct which is ideally from a nutritional point of view having a urine-to-fatty acid to weight ratio of 60:40 to 40:60 which is pure. free of fillers, unreacted starting materials and dissociation products, which are in the form of a dry, particulate or powdery, non-agglomerating product, by a technologically simple process if the urea is in the form of a solution with water in a sufficient quantity to to ensure a liquid state and with heating (60-140 ° C) or, in the case of a small amount of water present in the form of a melt, contact a melt of fatty acid (or a mixture of fatty acid and grease) at a temperature of 35-105 ° in such a way that the components are brought into contact with each other immediately before an atomization or just during an atomization, the atomized particles remaining in the air flow in the atomization space for a period of time. is sufficient for crystallization. Thus, the urea solution and the fatty acid melt produced separately and heated first come into contact with each other directly before atomization or even during atomization; the reaction which forms the adduct takes place rapidly and in the case of maintaining the above weight ratio of 60: 40-40: 60 a powdery or particulate loosely-structured adduct is deposited on the bottom of the atomization chamber or the atomization chamber, in which neither the hygroscopic nature of the urea nor the fat compound. adhesive, greasy character takes over.

It is thus the object of the present invention to provide a process for producing a urea-fatty acid adduct having the desired weight ratio and in a form in which neither the hygroscopic nature of the urea nor the sticky nature of the fat take over.

This is achieved by a process of the kind mentioned in the introduction, which is characterized by separately preparing a solution of urea with up to 45% water or a melt of urea with a temperature of 60 to 140 ° C and a melt. of the fatty acid or fatty acids or fatty acid / fat mixture at a temperature of 35 to 105 ° C, they contact each other immediately before a nebulization or just during a nebulization and allow the nebulized particles to move in an air stream until they have crystallized.

It is further the object of the invention to provide an apparatus for carrying out the method according to the invention. This is accomplished by an apparatus with two heatable containers for preparing or receiving the urea solution or urea melt and the fatty acid or fatty acid / fat melt, respectively, a pipeline connecting these containers directly or over an interconnected reaction tube with an atomizer, a compressed air driven two phase atomizer or a a single-phase atomizer and an atomization room with a height several times greater than the width, the atomizer being arranged in the upper part of the atomization room with downward atomization or in the lower part of the atomization room with upward atomization, which is characterized in that it coupled before the atomizer The reaction tube is a reaction chamber surrounded by a reaction chamber with a length / diameter ratio of between 10: 1 and 50: 1 and with baffle plates in its interior.

Thus, the mixing of the heated liquid urea and heated fatty acid (or fatty acid-fat mixture) takes place directly before the atomization in a closed space fronted by the atomizer, which may preferably be a tube reactor of a construction known per se. suitable for causing the adduct formation reaction to proceed at a controlled temperature and with a controlled residence time. However, it is convenient to use a tube reactor having a length-to-diameter ratio of between 10: 1 and 50: 1, which tube interior is provided with baffles spaced apart at a distance of V3 - ½ diameter and positioned at an angle of relative to the other 60-90 °, which plates reduce the free cross-section to Vs ~ Ve of the original dimensions. In such a tube reactor, the linear flow rate of the reaction mixture is increased to the 3- to 6-fold calculated from the free cross section. Such a pipe reactor is shown schematically in FIG. 4 and it is provided with a cooling and heating jacket 1, a reaction room 2 and baffle plates 3. The spraying of the thus obtained and fully or partially reacted liquid mixture can take place in any known direct pressure atomizer such as the so-called single phase nebulizer head, or with a compressed air atomizer, the so-called two-phase nebulizer head. It should also be noted that by appropriately selecting the atomization method and pressure, the particle size of the atomized product and its particle size distribution can be controlled.

For the preparation of the desired powdery, dry and non-agglomerating product, an important role is played by the atomization space used in downstream flow from the nebulizer, thereby providing a sufficiently long path for the air flow carrying the nebulized particles to suitably way can crystallize in the air flow. This atomization space is usually formed as a cylinder of a suitable length 'of several meters, wherein the atomizer is disposed either at the upper or the lower end so that the atomization can proceed in an upward or downward direction, the precipitated atomized particles being collected in a dry state of the bottom of the cylindrical compartment from which the product obtained can be removed continuously.

Thus, the process of the invention differs primarily from the heretofore used methods of this type for the preparation of solid urea-fatty acid adduct products for use as animal feed supplements by the two components of the adduct, namely the urea and fatty acid (or fatty acid-fat mixture). ) are reacted exclusively with each other in a liquid phase without solid carriers with the avoidance of all foreign materials except the small amount of water used to liquefy the urea using heat, and the two components mentioned are used in a weight ratio of 40:60 and 60:40, since this weight ratio allows, by atomization under the conditions described, to directly obtain a solid, powdery, dry product consisting of separated particles containing both urea and fatty acid in the most favorable weight ratio with consideration for setting the protein value and energy level in the feed and for the use of the urea in ruminants are.

A further advantage of the method according to the invention is that it can be carried out by a continuous operation with simple apparatus, the process parameters being also favorable for the gentle treatment of the materials. The product obtained is a pure adduct which, despite its high fatty acid content, does not contain free fatty acid or fats. It is also because of the favorable conditions of the process that the product obtained does not exhibit oxidation degradation, as shown by the low peroxide number of the product.

Preferred embodiments of the method according to the invention are elucidated in the following by some examples.

Example 1

From 82 kg of urea a solution is prepared by adding 28 kg of water at 102 ° C and mixing 50 kg of so-called "goldron" fatty acid melt at 80 ° C, which is a residue obtained as a by-product of fatty acid production and which also contains 0.1 weight % emulsifier and 0.02 wt. "antioxidant. Then this mixture is atomized from top to bottom in a so-called two-phase atomizer that operates with air with a pressure of 1.7 atmospheres into a cylindrical atomization chamber with a vertical axis of height 6 m and A diameter of 1.3 m. The above quantity of liquid mixture of urea and fatty acid requires 25 Nm of air for atomization. has a peroxide number of 5.3.

The quality of the product was observed by a dynamic microcalorimetric method (DSC). During the heating of the product was obtained with a microcalorimetric, the upper curve of FIG.

1 where the initial straight section of the curve shows that the product did not contain melting point materials below 100 ° C such as free fatty acid or fat, the double peak between 120 and 125 ° C corresponds to the pure adduct and the urea induced by the thermal dissociation of the adduct. The lower curve of the figure is the curve from the experiment repeated with the thermally dissociated product which shows the presence of urea and free fatty acid induced by the irreversible thermal dissociation of the adduct.

Example 2 The procedure described in Example 1 was repeated in the same apparatus and under the same atomization conditions, but with a mixture of a melt at a temperature of 135 ° C won by the addition of 1 kg of water to 65 kg of urea and a "goldron" -melt of 65 kg at 80 ° C.

The resulting product is slightly crumbly and of good quality. The product was tested in the manner described in Example 1.

Example 3

The procedure of Example I was repeated in the same apparatus and under the same atomization conditions, but instead of "goldron", a melt of 80 ° C of 50 kg of tallow acids was used.

The product obtained after cooling was in a slightly crumbling, packable state.

The adduct nature of the product obtained was observed by a differential microcalorimetric method (DSC). The double peak seen between 120 and 135 ° C in FIG. 2 shows the good quality of the product. The peroxide number of the product is 4.8.

Example 4

The procedure of Example 2 was repeated in the same apparatus and under the same atomization conditions, but in the same. for "goldron", an 80 ° C hot melt of 65 kg of tallow acids was used. The quality of the product obtained was the same as the product of Example 2.

U5921 9

Example 5

The procedure of Example 1 was repeated in the same apparatus and under the same conditions and using the same amounts, but instead of the two-phase air-working atomizer, a so-called single-phase pressure nozzle operating without air was used. The amounts of Example 1 were atomized in 15 minutes.

The product collected on the bottom of the nebulizer compartment had a temperature of 50 ° C and after cooling a light crumbling, easily packable product of a quality similar to that of Example 1 was obtained.

Example 6

A process was performed as described in Example 5, but as a cooling medium, 2000 Nm of air is blown into the atomization chamber for 15 minutes. The product collected on the bottom of the atomization chamber had a temperature of 30 ° C. The quality of the product was similar to that of Example 1.

Example 7

The procedure described in Example 6 was repeated in the same apparatus and under the same atomization conditions, but with the mixture described in Example 2. The product was a dry, powdery adduct of a quality consistent with the quality of the product obtained in Example 2.

Example 8

The procedure described in Example 6 was repeated in the same apparatus and under the same atomization conditions, but with the mixture described in Example 3. The product was a smooth liquid, powdery adduct of good quality.

145921 ίο

Example 9 In a container, a solution of 105 ° C was prepared from 82 kg of urea and 20 kg of water. In another container, at 50 ° C, 83 kg of "goldron" type fatty acid, which also contained 0.1% by weight emulsifier and 0.02% antioxidant, was melted. A two-head Bran Lubbe Normados NC 32 type pump had one suction tube blinded with the container of urea and the other suction tube connected to the container of fatty acid melt. The two-stage pump pressure rise tube was connected to a tube of 10 m in length and an internal diameter of 12.5 mm and the latter tube was connected to a tube reactor which served to mix the urea solution with the fatty acid and to conduct adduct. -dannelses reaction. The construction of this tube reactor is shown in FIG. 4 showing the reaction chamber with baffle plates 3 arranged within a cooling and heating jacket 1. The length of the reaction chamber is 0.55 m and its internal diameter 38 mm, the baffles have a surface area constituting 2 / e of the inner cross-section of the tube reactor and they are arranged with an angular difference of 60 ° and with a gap of 15 mm. The outlet opening of the tube reactor was connected to a "duplex" atomizer that operated with 1.7 atmospheric air to atomize the mixture arriving from the tube reactor from top to bottom into a vertical axis, cylindrical form atomizer chamber with a height of 6 m and an internal diameter of 1.3 m.

The feed pump was set such that the residence time of the mixture of the liquids fed at the same rate into the tube reactor of FIG. 4 was 10 seconds. The complete feeding and atomization of the above amount of material took a 3 hour and 25 Nm of air was required to atomize the liquid reaction mixture.

The falling dry product was collected at the bottom of the atomization chamber. 160 kg of solid product were obtained, which upon cooling proved to be a slightly crumbling urea-fatty acid adduct prepared for packaging and with a peroxide number of 4.6. The quality of the product was observed by a dynamic microcalorimetric method, the curve shape is shown in FIG. 3 and the double peak obtained between 120 and 135 ° C shows that the product was a pure adduct which did not contain free fatty acid or fats.

Example 10

The procedure of Example 9 was repeated with unchanged amounts of material, but instead of a tube of 10 m in length, the urea solution and the fatty acid melt passed through a tube of 2.2 m in length directly to the tube reactor placed before the atomizer head in the flow direction with the residence time of the reaction mixture of urea and fatty acid in the tube reactor were 6 seconds. Qualities! of the precipitated dry product was consistent with the quality of the product described in Example 9.

Example 11

The procedure described in Example 9 was repeated in the same apparatus and with the same arrangement but with a single-phase nebulizer head instead of a two-phase nebulizer head. The amount of material specified in Example 9 was atomized in 15 seconds. The residence time of the reaction mixture in the tube reactor was 2½ seconds.

The precipitated dry product had a temperature of 45 ° C and its quality corresponded to the quality of the product described in Example 9.

Example 12

The procedure described in Example 11 was carried out in the same apparatus and under the same atomization conditions, but as cooling medium 2000 Nm 2 of air at 20 ° C was introduced into the atomization chamber. The temperature of the precipitated dry product was 30 ° C and its quality was the same as the quality of the product described in Example 9.

Example 13

A procedure as described in Example 9 was repeated, but instead of "goldron", sebum fat was used.

In other respects, the conditions were identical to those stated above and an adduct of similar good quality was obtained.